Carbohydrate Polymers 261 (2021) 117848

Contents lists available at ScienceDirect

Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Review

Cellulose nanocrystals suspensions: Liquid crystal anisotropy, rheology and

films iridescence
Ulises Casado, Verónica L. Mucci, Mirta I. Aranguren *
Instituto de Investigaciones en Ciencia y Tecnología de Materiales (INTEMA), Universidad Nacional de Mar del Plata (UNMdP) - Consejo Nacional de Investigaciones en
Ciencia y tecnología (CONICET), Facultad de Ingeniería, Av. Juan B Justo 4302, (7600), Mar del Plata, Argentina

A R T I C L E I N F O A B S T R A C T

Keywords: The properties of aqueous suspensions of cellulose nanocrystals (CNC) and their casted films are revised. The bio-
Nanocellulose nanoparticles are briefly introduced, including modifications of the crystals and the suspending media. The
Cellulose nanocrystals formation of CNC-derived liquid crystals (LC) and their resulting rheological behavior are presented. The effects
Liquid crystals
of different variables are addressed: CNC aspect ratio, surface chemistry, concentration, time required for the
Rheology
appearance of an anisotropic phase and addition of other components to the suspension media. The changes on
Iridescent films
the structure induced by alignment, and by conditions of the drying process are also reported. The optical
properties of the films are considered, and the effect of the above variables on the final transparency, iridescence
and overall optical response of these bio-inspired photonic materials. Control of the reviewed variables is needed
to achieve reliable materials in applications such as sensors, smart inks and papers, transparent flexible supports
for electronics, decorative coatings and films.

1. Introduction Once the cellulose is obtained, different processes that involve me­
chanical, chemical and /or enzymatic methods, and frequently combi­
Cellulose, the most abundant biopolymer in nature, is formed by the nations of some of them, are used to obtain microfibrillated cellulose,
β(1-4) -linkage of anhydro D-glucose units (AGU). Given its abundance MFC, (or nanofibrillated cellulose, NFC), while oxidation (via 2,2,6,6-1
and wide geographical availability, it is not surprising that during the tetramethylpiperidine-1-2 oxyl (TEMPO)) or acidolysis and further
last few decades, it has received a great deal of attention from re­ sonication is required to obtain cellulose nanocrystals, CNC.
searchers worldwide, who systematically focused their efforts on the The NFC consists of long fibrils (generally, with lengths in the order
study of the particular properties of micro and nanocellulose fibers. of microns) with a thickness ranging from 5 nm to 50 nm. In any of those
Although nanocellulose can be extracted from some animals (ex.: tuni­ cases, each nanofibril contains crystalline and amorphous segments, and
cates) (Hong et al., 2020) and can be secreted by microorganisms thus, they are flexible and form highly entangled networks. On the other
(bacterial nanocellulose) (Gama et al., 2016) the greatest volume is hand, cellulose nanocrystals (CNC) are rod like acicular rigid nano­
obtained from vegetable sources (Kumar, Pathak, & Bhardwaj, 2020). particles, with a non-cylindrical cross-section with thickness of the order
Because of its origin, this type of cellulose must be first separated from of 3–10 nm (although reports of 15–20 nm can also be found) (Bercea &
the other components of the plants (mostly lignin and hemicelluloses). Navard, 2000; Boluk, Lahiji, Zhao, & McDermott, 2011; Liu, Chen, Yue,

Abbreviations: AFM, Atomic Force Microscope; AGU, anhydro D-glucose units; ATRP, atom-transfer radical polymerization; CNC, cellulose nanocrystals; CNC-
MDS, chloro(dodecyl)dimethylsilane; CNC-MPM, 3-(trimethoxysilyl)propyl methacrylate; CNC-T, CNC oxidized via TEMPO; CNC-TMS, trimethylchlorosilane; DSs,
degree of surface substitution; FESEM, Field Emission Scanning Electron Microscope; G’, shear storage modulus; G", shear loss modulus; IR, infrared; LC, liquid
crystal; LEDs, light-emitting diodes; MPM, 3-(trimethoxysilyl)propyl methacrylate; MFC, microfibrillated cellulose; n, refractive index; N1, first normal stress dif­
ference; NFC, nanofibrillated cellulose; NMR, nuclear magnetic resonance; p, pitch length; PAAS, sodium polyacrylate; PDMAEMA, poly 2-(dimethylamino ethyl
methacrylate); pe, aspect ratio, L/d, as calculated from rheological experiments; PEG, polyethylene glycol; POM, polarized optical microscopy; RAFT polymerization,
reversible addition-fragmentation chain transfer polymerization; SANS, small angle neutron scattering; T, period of oscillation of the viscosity in start-up tests; TEM,
Transmission Electron Microscopy; TEMPO, 2,2,6,6-1 tetramethylpiperidine-1-2 oxyl; Tg, glass transition temperature; TMS, trim ethylchlorosilane; UV, ultraviolet;
UV–vis, ultraviolet–visible; WBPU, waterborne polyurethane; γ̇, shear rate; η, viscosity; λ, wavelength; θ, angle between of incident light to the surface.
* Corresponding author.
E-mail address: [email protected] (M.I. Aranguren).

https://doi.org/10.1016/j.carbpol.2021.117848
Received 17 December 2020; Received in revised form 5 February 2021; Accepted 19 February 2021
Available online 26 February 2021
0144-8617/© 2021 Elsevier Ltd. All rights reserved.
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

Chen, & Wu, 2011; Ureña-Benavides, Ao, Davis, & Kitchens, 2011) and represent a promising, green chemistry alternative to conventional
length in the order of ~100− 200 nm. reinforcement of polymers (Eichhorn et al., 2010; Habibi, Lucia, &
CNC have been obtained in aqueous suspension, frequently by acy­ Rojas, 2010). Their beneficial effect in nanocomposites has been espe­
dolysis with 64 wt.% sulfuric acid at 45− 60 ◦ C and different times of cially important when good interfacial compatibility was achieved.
reaction (Dong, Revol, & Gray, 1998; Dumanli, Kamita et al., 2014; Pan, Particularly, the network of nanofibrils in fibrillated celluloses largely
Hamad, & Straus, 2010; Revol et al., 1994; Dumanli, van der Kooij et al., contributes to the cohesion, modulus and strength of a material (Hor­
2014; Mu & Gray, 2015; Buffa, Grela, Aranguren, & Mucci, 2016; Wilts, maiztegui et al., 2016). On the other hand, CNC can be incorporated to
Dumanli, Middleton, Vukusic, & Vignolini, 2017). In general, the length polymer latex, suspensions and solutions, and then be casted or pro­
and aspect ratio of CNCs decrease with increasing time or temperature of cessed in the same way as the neat polymer latex/solution (Buffa et al.,
the hydrolysis (Korolovych et al., 2018), with large aggregates or un­ 2018; Hormaiztegui, Mucci, & Aranguren, 2019; Kose, Tran, Lewis,
modified cellulose frequently eliminated from the media by centrifu­ Hamad, & MacLachlan, 2019; Mondragon et al., 2018).
gation or filtration through fine cloth. The final step is usually the The other very interesting characteristic that has received attention
sonication of the suspension under cooling ice bath to avoid overheating in the last years is the optical behavior of CNC suspensions. In fact,
and de-esterification of the sulfate groups (Shafiei-Sabet, Hamad, & although in the middle of the XXth century, some reports appeared on
Hatzikiriakos, 2012). The CNCs can then be stored as an aqueous sus­ CNC (Marchessault, Morehead, & Koch, 1961; Rånby, 1951), it was not
pension (usually referred as never dried CNC), to avoid "hornification", and until the last part of that century that a more systematic study of the
the irreversible or partially irreversible formation of H-bonds between nanocrystals and their suspensions was undertaken (Dong et al., 1998;
the cellulose fibrils. This process results in the impossibility to regain the Revol et al., 1994).
same degree of re-dispersion in water as with never dried-CNC (Sha­ Self-organizing molecules are not unknown in nature, they produce
fiei-Sabet et al., 2012; Shafiei-Sabet, Hamad, & Hatzikiriakos, 2014). mesostructures with special properties. Polysaccharides are known to
Because of the presence of sulfate groups in the CNC that generate display this characteristic that allows them to meet structural re­
repulsive forces between the crystals, the CNC suspensions are very quirements in plants (e.g. cellulose) and animals (e.g. chitin). For
stable. However, a result of this modification is the reduced thermal example, the self-organization of chitin in the presence of proteins and
resistance of the CNC with degradation beginning at lower temperature salts is responsible for the exoskeleton of the arthropods, some of them
with respect to that of pure cellulose (Aguayo et al., 2018; Roman & presenting iridescence and structural coloration. This phenomenon is
Winter, 2004; Vanderfleet et al., 2019). created by the microstructures of the material that interfere with the
The morphology of CNC has profound effect on their behavior and light. Thus, these materials show structural color (a particular wave­
thus, different microscopies, Atomic Force Microscopy (AFM), Field length is reflected) that changes gradually with the angle of the incident
Emission Scanning Electron Microscopy (FESEM), Transmission electron light and the angle to the observer. Similarly, CNC, form very stable
microscopy (TEM) have been applied to its study. Examples of the aqueous suspensions that can spontaneously phase separate into
different microscopic results are shown in Fig. 1. (Bercea & Navard, isotropic and anisotropic phases in a particular range of concentration,
2000; Boluk et al., 2011; Liu et al., 2011; Ureña-Benavides et al., 2011) that is, they form lyotropic liquid crystals. The anisotropic phase dis­
In order to improve the dispersion in organic solvents, the compat­ plays a chiral nematic liquid crystalline order also called cholesteric
ibility with different polymeric matrices, and to change rheological ordering (De France, Yager, Hoare, & Cranston, 2016).The characteris­
behaviors or to reduce the energy required for the cellulose fibrillation, tics of the anisotropic phase, as well as the range of concentrations in
several researchers have dedicated their efforts to study the chemical which it appears, depend on the dimensions of the nanocrystals, their
modifications of CNCs taking advantage of well known reactions for aspect ratio, chirality, their surface chemistry (all of which depend on
carbohydrates (Aranguren, Mucci, & Peresin, 2017; Belgacem & Gan­ the cellulose source and the purification and processing conditions) and
dini, 2005; Buffa, Casado, Mucci, & Aranguren, 2019; Ljungberg et al., also on the ionic strength of the suspension (Korolovych et al., 2018).
2005; Mosiewicki, Marcovich, & Aranguren, 2011; Nigmatullin et al., The chiral nematic ordering of the liquid suspensions can be retained
2018; Reboredo, Marcovich, & Aranguren, 2008; Sammartino, Rebor­ with some alterations, during drying, leading to glossy, iridescent films
edo, & Aranguren, 2016; Shafiei-Sabet, Hamad, & Hatzikiriakos, 2013). (Beck, Bouchard, Chauve, & Berry, 2013; Giese & Spengler, 2019;
These reactions also change the surface charge of the CNC (and thus, the Majoinen et al., 2016; Revol, Godbout, & Gray, 1997). However,
ionic strength of the suspension), as well as the apparent volume occu­ attaining long range order is still a challenging goal.
pied by each rod because of the modified apparent aspect ratio (Buffa This work will focus on the cellulose nanocrystals obtained from
et al., 2019). Although the chemical modification of CNC is not the focus vegetable sources and particularly on the rheology of the liquid sus­
of this work, a brief summary of the subject is provided as supporting pensions formed and the optical characteristics of the films produced
information (SI), for the sake of completion. from them.
Due to their excellent mechanical properties, relatively low cost,
biocompatibility and rich surface chemistry MFC, NFC and CNCs

Fig. 1. Micrographs of CNC obtained by sulfuric acidolysis in aqueous media: A) TEM image (own result), B) AFM image (Adapted from Moberg et al. (2017)
Cellulose, doi:10.1007/s10570-017-1283-0under the Creative Commons CC BY license.) and C) SEM image (Adapted from Zhang et al. (2013) Journal of Materials,
doi:10.1155/2013/614507under the Creative Commons CC BY license).

2
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

2. CNC suspensions and development of a LC phase tube, while the anisotropic LC phase appears as a bright region, which
allows an easy estimation of the volume fraction occupied by the
As mentioned before, rod-like CNCs in aqueous suspensions can self- anisotropic phase (Fig. 3 C). When the anisotropic phase is observed by
organize in chiral-nematic order above a critical concentration, which polarized optical microscopy (POM), it is possible to observe the char­
results in interparticle distances below ~ 50 nm (Honorato-Rios et al., acteristic fingerprint texture of the chiral nematic phase of CNC aqueous
2016; Lagerwall et al., 2014; Marchessault, Morehead, & Walter, 1959; suspensions (Fig. 3 D) (Honorato-Rios et al., 2016). The periodic change
Revol & Marchessault, 1993; Revol, Bradford, Giasson, Marchessault, & in coloration corresponds to the periodic change of the director with
Gray, 1992; Wang, Hamad, & MacLachlan, 2016). This phase has been respect to the polarized light. Thus, the pitch is equal to twice the
consistently shown to be left handed (Dong & Gray, 1997; Gray, 2016; spacing between identical color bands.
Honorato-Rios et al., 2016). The CNC self-align, forming pseudolayers, The variation of the ionic strength of the medium modifies the
each of which presents a common average orientation described by the electrical double layer around the particles, which in turn changes the
"director" (Lettinga, Dogic, Wang, & Vermant, 2005; Onsager, 1949; concentration range for phase coexistence, the pitch of the helical
Pleiner & Brand, 1996, 2016). The director rotates around a helicoidal mesostructure and the rheology of the suspensions. A high concentration
axis from one pseudolayer to the next. The distance along the helix axis of salt can also reduce so much the thickness of the electrostatic double
to complete a whole turn is called the pitch, as shown in Fig. 2. layer around the crystals that agglomeration results and viscosity in­
Additionally, the crystals present a twisted structure and thus the creases. Similarly, to the effect observed with high CNC concentrations,
surface charges on the nanoparticle appear as if helically distributed on the increased viscosity may inhibit the formation of an ordered phase.
a rod (this is reinforced by the presence of the sulfate groups or other The physical modification of the suspending medium can be ach­
chemical groups attached on the surface, for example, carboxylic groups ieved by simple addition of a dispersing agent. Buffa et al. (2019) ob­
in oxidized CNC-T). This twist has also been reported as responsible of tained CNC aqueous suspensions adding gum arabic, while Kose et al.
the periodic change of orientation of the director (Honorato-Rios et al., (2019) and Mu and Gray (2014) used glucose, to increase the flexibility
2016). and to vary the pitch of prepared CNC films, respectively. The most usual
The LC arrangement described occurs in a limited range of concen­ way to vary the ionic strength of the medium is by adding salts. For
trations and the time required to achieve a high degree of order can go example, Shafiei-Sabet et al. (2014) dispersed CNC in deionized water or
from hours to (most usually) days. At low concentration, the suspensions NaCl solution to vary the pitch of the systems.
are isotropic. The interaction between the rods is low and their behavior Honorato-Rios et al. (2016) presented an interesting study in which
is not affected by the presence of other crystals in the suspension. At high the charges on the CNC surface and the ionic strength of the suspending
concentrations, the viscosity of the suspension becomes so high that the aqueous media were varied. The study confirmed the most common
mobility of the CNCs is highly compromised and they cannot rearrange observed behavior in which addition of salt to the media results in the
to achieve order; the ordering process is kinetically arrested and the reduction of the effective diameter of the CNC rods and consequently on
system reaches a gel-like state. This process can complicate the identi­ the increase of the aspect ratio and decrease of their effective volume
fication of the concentration at which all the sample is in the LC phase. (thus, of the effective volume concentration of the rods in the suspen­
The intermediate range of concentrations at which the coexistence of sion). Consequently, the critical concentration for the anisotropic phase
isotropic and anisotropic phases is found varies from one system to was shifted to higher values due to the salt addition. It was also showed
another. It depends on the size, aspect ratio and polydispersity of the that the concentration of the isotropic and anisotropic phases becomes
CNCs (thus, from their source and the process selected to obtain them), less differentiated. As the salt concentration is increased, the limit be­
the ionic strength of the media, as well as the surface charges of the tween phases is more diffuse (the concentrations in the two phases are
crystals (De France et al., 2016; Li et al., 2015; Shafiei-Sabet et al., 2013, more similar) and thus, the isotropic phase also shows some birefrin­
2014; Wu et al., 2014; Zhang, Cheng, Chang, & Zhang, 2018). gence between cross polarizers, making more difficult the determination
To experimentally measure the volume of the two phases, usually of the volume fraction of the phases. The authors related this observa­
glass test tubes containing the samples are allowed to rest in order to tion to a change from a first order transition, which should appear as a
achieve equilibrium (Fig. 3 A and B) and then they are observed between discontinuous transition (a clean phase separation) to a second order
cross-polarizers. The isotropic phase appears as a dark region in the transition for which critical fluctuations are important and the transition

Fig. 2. Chiral nematic ordering in the CNC dispersions. The "pitch" length corresponds to a whole turn of the director. Adapted from Kose et al. (2019) Nature
Communications 10, doi: 10.1038/s41467-019-08351-6 under the Creative Commons CC BY license.

3
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

Fig. 3. Phase separated suspensions at different CNC concentrations. When observed between cross-polarizers, the bottom phase corresponding to the anisotropic
cholesteric phase appears bright: A) CNC with relative low surface charge, L-CNC, B) suspensions prepared with CNC of relatively high surface charge, H-CNC; C)
volume fraction of the anisotropic phase, obtained from the samples shown in (A) and (B); D) fingerprint texture of sample L-CNC shown in Figure A, prepared at 10
wt.% in deionized water. Adapted from Honorato-Rios et al. (2016) Frontiers in Materials 3. doi:10.3389/fmats.2016.00021 under the Creative Commons CC
BY license.

appears to be more gradual. Additionally, even in the absence of added growth rate (Ureña-Benavides et al., 2011) of the curve or as a small
salt, increasing the concentration of CNC (obtained from sulfuric acid­ jump (Bercea & Navard, 2000), which depends on the particular system,
olysis) also increases the ionic strength of the suspensions because the aspect ratio and surface charge of the CNC, ionic strength of the media,
CNC are surface-charged and thus, at high concentration of CNC it may etc. Fig. 4 A illustrates this type of behavior that, as it is shown, appears
become difficult to assess the phase separation. at different shear rates. Similar observation has also been reported for
chitin suspensions (João et al., 2017).
3. Rheology of CNC suspensions b- Unusual dependence of the viscosity on the shear rate (Fig. 4 B).
There is a range of concentrations at which the plot of viscosity vs. shear
The first investigations in this field were carried out by Marchessault rate shows three regions: a shear thinning (region I), a "plateau" (region
et al. (1961), who showed that cellulose nanocrystals obtained by hy­ II) and another shear thinning region (region III) (Onogi & Asada, 1980).
drolysis in concentrated sulfuric acid behave hydrodynamically in The two shear thinning regions, at low and high shear rates, are related
aqueous suspension as rigid particles of high aspect ratio, and this to the orientation of domains and of individual particles, respectively
behavior was directly related to the size and length distribution of the (Burghardt & Fuller, 1991; Larson, 1993; Lettinga et al., 2005; Menzel,
crystals. 2015; Mewis, Mortier, Vermant, & Moldenaers, 1997; Rahman, 2013;
The systematic study of the flow properties of nanometric cellulose Walker, Wagner, Larson, Mirau, & Moldenaers, 1995; Zakharov, Vaku­
systems was undertaken much later. For example, Orts, Godbout, Mar­ lenko, & Thoen, 2003). The intermediate region may appear as a
chessault, and Revol (1998) investigated aqueous suspensions of CNC plateau, or as a short region of lower slope than those of the shear
obtained from spruce and cotton using rotational viscometry and they thinning regions and extending through different ranges of shear rates,
related their results to those obtained by small angle neutron scattering generally short ones, while some authors have resorted to describe it as a
(SANS). They focused on characterizing the chiral nematic behavior of hesitation in the viscosity curve (Echeverria, Almeida, Aguilar Gutier­
the suspensions and the order that could be induced by magnetic and rez, Rey, & Godinho, 2017; Li et al., 1996). c-Long oscillatory response
shear alignment of the crystals. They found a non-monotonous variation for the shear viscosity in start-up tests (Fig. 4C). This response arises
of the viscosity as a function of the shear rate, something already from the rods undergoing periodic motions, when the suspension is
observed in LC polymeric solutions (Onogi & Asada, 1980). subjected to relatively low flow rates (at high flow rates, flow alignment
Later works were undertaken to relate the suspensions rheology to is more probable to occur) (Matveichuk, 2013). In a start-up test, flow is
variables such as surface chemistry, suspending media, concentration induced by the sudden application of a constant shear rate. The usual
and aspect ratio of the nanoparticles (Hubbe et al., 2017). The goal of response is a short transient (sometimes with the appearance of one or
the studies, besides the obvious characterization of the CNC suspensions, very few maxima of decreasing amplitude) that leads to the steady shear
was to gain understanding to tailor the film manufacturing process, for viscosity. In the case of the LC considered here, the response is an
example aligning domains or the nanorods by flow. The persistence of a oscillatory viscosity (non sinusoidal) with a constant period that persists
LC phase or the complete alignment of CNC in the final films affects their on time and is a function of the shear rate and of the aspect ratio of the
morphology and thus, iridescence and mechanical properties. particle (Moldenaers & Mewis, 1990; Picken, Aerts, Doppert, Reuvers, &
However, in order to comprehend the results of the various studies Northolt, 1991; Vermant, Moldenaers, Picken, & Mewis, 1994).
performed on CNC suspensions, a brief overview of the rheological d- Appearance of a negative first normal stress difference (N1). The
behavior of LC formed by rigid chains or, as in the present case, rigid measurements performed on this type of LC show that N1 goes through a
nanoparticles, is introduced here. LC systems of elongated particles minimum that may reach negative values. (Kiss & Porter, 1996), what is
(including rods) have a particular rheological behavior that character­ associated to the movements of the elongated particles or rods when
izes them when careful tests are performed. Although not all the features they are aligned with the flow (Larson, 1990; Narimissa, Rahman,
may be present in a given system, most of them appear and are related to Gupta, Kao, & Bhattacharya, 2014; Xu, 2014). This response has also
the morphology of the particles, the interparticle interactions and the been reported for a derived cellulose polymer aqueous solution
capacity for rearrangement and orientation during flow (Buffa et al., (hydroxypropylcellulose, HPC) (Echeverria et al., 2017; Huang, Magda,
2019; Xu, 2014). & Larson, 1999).
a- Dependence of the shear viscosity with the CNC concentration. e- Non-applicability of the Cox-Merz rule (Fig. 4 D). When the
The viscosity of the suspensions does not grow monotonically with the response of a material complies to the Cox-Merz rule, the shear viscosity
concentration and may show a local maximum (Kiss & Porter, 1998; vs. shear rate (s− 1) and the complex viscosity vs. angular frequency (rad.
Wissbrun, 1981). This maximum has been seen by some authors (Li, s− 1) coincide. It is not always applicable, and in particular not in the case
Revol, & Marchessault, 1996), but it may also appear as a change in the of the CNC suspensions (Buffa et al., 2019; Ureña-Benavides et al.,

4
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

Fig. 4. Example of the rheological behavior for CNC aqueous suspensions containing 0.1 wt.% arabic gum (GA) (own results). A) steady shear viscosity as a function
of concentration for several shear rates. B) steady shear viscosity for 5.1 wt.% CNC suspension showing three regions behavior. C) periodic oscillations of the shear
viscosity as response to a shear start-up test for a 2.4 wt.% CN suspension at 10 s− 1; D) curves of shear and complex viscosity vs. shear rate and angular frequency,
respectively, for 5.1 wt.% CNC + 0.1 wt.% GA suspension, showing the failure of the applicability of the Cox –Merz rule (own results).

2011). This and all the above features were also reported for micro­ storage and loss moduli, does not produce clean curves for these prop­
crystalline cellulose in a solution of ionic liquid media of 1-allyl-3-me­ erties (Lee & Brant, 2002; Ureña-Benavides et al., 2011).
thylimidazolium chloride (AMIMCl) (Song, Zhang, Niu, & Wang, 2010).
f- Impossibility to produce concentration-master curves from small
amplitude sinusoidal oscillation tests (Fig. 5). The technique of pro­ 3.1. Effect of the aspect ratio of the cellulose nanocrystals
ducing a master curve by frequency shifting the curves of the dynamic
properties (log-log plots) obtained at a fixed concentration, such as An important variable affecting the arrangement in LC is the aspect
ratio of the suspended nanoparticles. Since the morphology of CNC

Fig. 5. Example of the failure in the application of the obtention of a master curve (B) from the results of (A) G’ and G" vs angular frequency for CNC aqueous
suspensions with 0.1 wt.% GA (own results).

5
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

influence its diffusion in suspension, it plays an important role on the vegetable origin. These authors showed that below 0.4 wt.% of cellulose
rheological behavior of their suspensions. Wu et al. (2014) focused on whiskers the viscosity vs. shear rate showed a low shear rate Newtonian
this aspect of the subject by using CNCs from switchgrass and from plateau followed by a shear thinning region and a second plateau at high
cotton obtained by acid hydrolysis, with aspect ratios, L/d, of 39 and 13, shear rates. The behavior is typical of isotropic suspensions with the
respectively. They first observed that the critical concentrations corre­ initial plateau being strongly dependent on the concentration. At an
sponding to the appearance of the anisotropic phase and of the gel-like intermediate concentration range (1 wt.% − 3.5 wt.%), the viscosity as a
behavior were lower for switchgrass-CNC than for cotton-CNC. At a function of the shear rate showed two shear thinning regions at low and
fixed concentration, the viscosity of the switchgrass-CNC was higher high shear rates, separated by a region of very weak thinning (region II),
than that of cotton-CNC. Both observations were attributed to the higher which is typical in LC suspensions and LC polymer solutions. As already
aspect ratio of the first ones. Overall, the qualitative behavior of the mentioned, this particular behavior is the result of the rod orientation
samples was the same, but the range of concentrations at which the coupled to a polydomain structure. At low shear rates, the individual
transitions occurred was different. Similar results were obtained by Li domains (that may have different orientations of the CNC) are aligned
et al. (2015), who worked with CNC of different aspect ratios obtained by the flow. The polydomain texture can "anchor" the orientation of the
by varying the time of the sulfuric acidolysis of NFC and by Zhang et al. whiskers, but is sensitive to shear (Walker & Wagner, 1994; Walker,
(2018) who worked with CNC from different sources and different Kernick, & Wagner, 1997). As the shear rate increases, the small do­
aspect ratios: cotton pulp (L/d = 15), algae (L/d = 18), and tunicate (L/d mains tend to disappear in favor of the larger ones that coalesce leading
= 75), and found that CNC with higher aspect ratio reached both critical to more aligned rods. In the final thinning region, at high shear rates the
transitions (isotropic to biphasic phase and biphasic to anisotropic individual rod-like crystals become mostly aligned with the flow (Buffa
phase) at lower concentrations. et al., 2019; Burghardt & Fuller, 1991; Larson, 1993; Menzel, 2015;
Buffa et al. (2019) showed an interesting application of the rheo­ Mewis et al., 1997; Rahman, 2013; Walker et al., 1995; Zakharov et al.,
logical results in this kind of systems: the possibility to estimate an 2003).
effective aspect ratio of the CNC rods from steady shear start up mea­ The increase of viscosity with the concentration observed at low CNC
surements. As already mentioned, these systems show long-time tran­ concentrations is a result of the volume required for "tumbling" of the
sients in start-up of steady-shear, with a periodic oscillation of the rod-like crystals around their length, which requires a large excluded
viscosity that does not diminishes with time (Lettinga et al., 2005). This volume and occurs due to the flow induced orientation. At higher con­
leads to the persistent oscillation of the viscosity (as illustrated in Fig. 4 centration, ordered domains are present in the suspensions and they slip
C). For long rods, the oscillation period can be written as a function of one with respect to the other. This type of flow requires less excluded
the shear rate and the aspect ratio (Mewis & Wagner, 2012). volume, so the rate of increase in viscosity is reduced. The change in the
flow may result in a maximum in the curve followed by a minimum or in
logT = log(2π∙pe) − logγ̇ (1)
a simple inflexion in the curve, depending on the size and size distri­
Thus, by measuring the period of oscillation, T, and using the value bution of the rods as well as, on the interactions between the crystals
of shear rate applied, γ̇, the authors estimated a pe = L/d = 22.2, for (Bercea & Navard, 2000; Ureña-Benavides et al., 2011). At even higher
sulfated CNC from microcrystalline cellulose, which was in very good concentrations, the viscosity increases again due to the increase in
agreement with estimations made from TEM images. concentration and at still higher concentrations the crystals agglomer­
ation (due to gel formation) may induce a second arrest in the rate of
3.2. Effect of ultrasonication viscosity increase. This observation is qualitatively in agreement with
similar ones reported by other authors, although the values of the crit­
Shafiei-Sabet et al. (2012) studied the effects of sonication on the ical concentrations vary from one system to the other depending on the
microstructure and rheological response of aqueous suspensions of CNC particular characteristics of the CNCs (Buffa et al., 2019; Ure­
from black spruce kraft pulp with L/d~14. Ultrasound energy in the ña-Benavides et al., 2011).
range of 0–5000 J/g of cellulose whiskers was applied to various sus­ Hubbe et al. (2017) have summarized the effect of the repulsive
pensions and its shear viscosity was measured at steady state. Before forces between CNC surfaces by saying that at low concentrations the
sonication, the samples analyzed (5 and 7 wt.%, at 25 ◦ C) behaved like a repulsive forces maintain the nanoparticles separated and thus, they
gel, with a shear thinning behavior that covered the whole range of have a lubricating effect. However, at high CNC concentration, the
shear rates studied. After applying ultrasonication, its viscosity dropped repulsive forces make the particles appear more crowded, which results
significantly and showed the 3-regions of rheological behavior, typical in higher viscosity of the suspension.
of a lyotropic LC. The observation was explained as the breaking of the The concentration of CNC also affects the applicability of the Cox -
gel structure of the samples due to sonication. As a result, the formation Merz rule. While completely isotropic (low concentration) samples obey
of the LC phase was no longer inhibited by gelation, which was the rule (or show little deviation), samples containing an anisotropic
corroborated by microscopic optical observations, where fingerprint contribution do not follow it (Buffa et al., 2019; Ureña-Benavides et al.,
textures characteristic of chiral nematic structure were detected. Similar 2011). Ureña-Benavides et al. (2011) also showed that there is a drastic
observations were reported on ultrasonication used to improve disper­ change of the dynamic mechanical properties (at small amplitude si­
sion (Beuguel, Tavares, Carreau, & Heuzey, 2018; Gicquel et al., 2019). nusoidal oscillations) that occurs in a very narrow range of concentra­
Gicquel et al. (2019) also reported that ultrasonication resulted in the tions that corresponds to the limit of the biphasic coexistence and the
increase of the critical concentrations (isotropic to anisotropic and appearance of the gel-like behavior. For their particular system (CNC
anisotropic to gel transitions), and also of the width of the biphasic from cotton powder), samples up to 10.4 vol.% of CNC behave like
range, affecting the viscosity of the suspensions at each concentration. viscous fluids (tan δ > 1), while samples with concentration greater than
12 vol.% showed elastic behavior (tan δ < 1). The elastic module was
3.3. Effect of the CNC concentration independent of frequency at concentrations > 14.5 vol.% CNC, indi­
cating the formation of rigid gel. In this range of concentrations, the
The already mentioned three regions, present in the viscosity vs. shear viscosity showed a power-law behavior in all the range of shear
shear rate plots, appear in the region of coexistence of the isotropic and rates measured, while the fingerprint texture, typical of the chiral
anisotropic phases. The work of Bercea and Navard (2000) is an example nematic order, disappeared. The authors also attempted to produce
of this, although because it used CNC from tunicates with very large concentration-based master curves, but when viscosity and /or loss
aspect ratios (whiskers of L/d ~ 140), the limits of coexistence shifted to modulus were taken as the basis for the calculation of the frequency
much lower concentrations than those reported from CNCs from shifts, the curves produced for the storage modulus were not smooth.

6
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

The explanation was that elastic relaxations exist, which vary with the Other authors studied the effect of adding salts with cations of
concentration because of the corresponding variation of the morphology different valence (Bertsch et al., 2019; Phan-Xuan et al., 2016). Bertsch
and of the interfacial area between LC and isotropic regions. Apparently, et al. (2019) worked with chloride salts from different cations (Na+, K+,
these microstructural changes did not affect the viscous relaxations. Mg2+, Ca2+) over a wide range of concentrations to determine the effect
It is particularly important to determine the range of high concen­ on the gelation of CNC (L/d = 20) aqueous dispersions. They used dy­
tration behavior, since in that condition the morphology is frozen and namic frequency sweeps on samples of 1.3 and 5 wt.% CNC, which
thus, the formation of potentially iridescent domains in the derived films showed a viscoelastic liquid character in absence of salt. They indicated
is compromised. from these results that the gel formation is due to a decrease in elec­
trostatic repulsion. They found that divalent chloride salts induced gel
3.4. Effect of suspending media modifications and CNC surface formation at lower concentrations due to a more efficient charge
modifications screening, in agreement with Phan-Xuan et al. (2016), who stated that
multivalent cations were more efficient in inducing aggregation and
The ionic strength of the media may be varied by addition of elec­ decreasing the concentration for the appearance of gelation. Addition­
trolytes or by changing the surface charge of the CNC themselves. ally, Bertsch et al. (2019) found that the maximum gel strength was
Actually, the mere variation of the concentration of CNC also results in independent of the cation valence and radius, which differs from the
the change of the ionic strength in the suspension and the addition of results of other authors (Chau et al., 2015; Lenfant, Heuzey, van de Ven,
salts to the media may lead to similar changes in the rheological & Carreau, 2017), that indicated that potentially stronger gels are
response, although at CNC different concentrations (Bertsch et al., 2019; formed with divalent cations due to intermolecular bridges.
Phan-Xuan et al., 2016). Bertsch et al. (2019) also reported a salt-induced transition from
The variation of the degree of sulfation was the strategy used by semidilute cholesteric dispersions to colloidal glasses for charged
Shafiei-Sabet et al. (2013), who worked with CNC from black spruce anisotropic CNC suspensions. They demonstrated that the Cox – Merz
(Lav. = 100 nm, dav. = 7 nm) subjected to two different post-hydrolysis rule failed, and that complex viscosity and shear viscosity matched for
processes. While the sulfation degree did not have significant influence isotropic fluids, but diverged for structured fluids.
on the shear viscosity at the isotropic regime, the transition from It has also been reported that chemical modifications of the CNC
isotropic liquid to anisotropic chiral nematic LC occurred at smaller CNC result in suspensions that may form LC, but at different ranges of weight
concentrations as the degree of sulfation increased. Additionally, a concentrations that the unreacted crystals. The modification leads to
lower degree of sulfation causes a decrease in the electrostatic repulsion variations in the wavelength reflected and also to great differences in the
of whiskers, which leads to a higher probability of aggregation. Conse­ rheological properties. Nigmatullin et al. (2018) reacted octylamine
quently, these samples reached a the gel-like behavior at lower CNC moieties on sulfated CNCs. In contrast to the original CNCs, frequency
concentrations than a sample with a higher sulfation degree (10 and 12 sweeps showed G’ > G" at all concentrations studied, while the shear
wt.%, respectively). viscosity was also higher for the suspensions of the modified CNCs.
The addition of NaCl is the most frequently used strategy to vary the Although the three regions of viscosity vs. shear rate were observed for
ionic strength of the suspension media. For example, Shafiei-Sabet et al. the suspensions of the modified CNCs, they did not show birefringence
(2014) varied the concentration of salt working at fixed CNC concen­ and long range ordering was not observed. Instead, hydrophobic in­
trations. For an isotropic sample (3 wt.% for the CNC considered in the teractions drove their association into a network and the formation of a
study) in the presence of NaCl (0–10 mM), the viscosity (vs. shear rate) gel of higher strength.
decreases as the ionic strength increases. This was explained because the Buffa et al. (2019) analyzed the rheological behavior of sulfated
presence of NaCl compresses the thickness of electrical double layer of CNCs, TEMPO oxydated and reacted with chloro(dodecyl)dimethylsi­
the CNC. The compressed double layers and the low concentration of lane and with trimethoxysilyl propylmethacrylate, (CNC, CNC-T,
CNC result in lower viscosity at higher ionic strength. This effect was CNC-MDS and CNC-MPM), as well as the effect of adding a dispersing
also reported for suspensions at the semi-dilute concentration regime by agent (gum arabic, GA) to the suspension. Several aspects of these sus­
Boluk et al. (2011). In the biphasic regime (7 and 10 wt.% CNC), Sha­ pensions were considered, in particular, the persistent oscillation
fiei-Sabet et al. (2014) found that the addition of NaCl up to 5 mM, observed in the shear viscosity during a start-up test was utilized to
reduced the viscosity at high shear rates, similarly to the observed estimate the effective aspect ratio of the crystals subjected to the test. An
behavior in isotropic suspensions. However, at low shear rates (region I) interesting result was the effect of the modifications of the CNC surface
an increase of the viscosity was registered and attributed to structural and media on the effective L/d value, which lead to different periods of
changes in the chiral nematic domains. Polarized optical microscopy oscillation in the viscosity. The addition of gum arabic to the media did
(POM), used in combination with rotational rheometry to capture the not have much effect on the measured aspect ratio (26.2 instead of 22.2
microstructure of different samples, supported these observations. By as measured in the CNC suspension). On the other hand, a large effect
adding NaCl, the size of the chiral nematic domains decreased signifi­ was detected on CNC-T and silanized CNCs suspensions, as a result of the
cantly and finally vanished for NaCl above 10 mM. The increase in chiral increase of the effective crystal thickness due to the double layer
interactions, due to the reduced double layer thickness, reduced the thickness in CNC-T and the grafted silanes onto the CNC surface (L/d ~
pitch size and led to domains with smaller size (Dong, Kimura, Revol, & 11.4–12.6). Among other differences, CNC-MPM formed suspensions of
Gray, 1996; Hirai, Odani, & Nakajima, 1991) and to suspensions of low viscosity, because the grafted molecule consists of a short chain and
higher viscosity at low shear rates. The study of the frequency sweeps of only reduced the electrostatic interactions between the crystals, but
CNC suspensions with concentrations between 7 and 10 wt.% showed without developing strong interactions between the grafted polymer
that when NaCl was added up to 5 mM, they have a fluid-like behavior chains.
(G">G’), as they did without salt addition, although presenting higher Mu and Gray (2014) presented results from the incorporation of
G’ value due to the smaller domains with more packed structures. For glucose into CNC suspensions and reported that this addition reduced
the same concentrations of CNC but higher NaCl concentrations (10 and the pitch of the chiral nematic liquid crystal suspension, also reducing
15 mM), the shear viscosity was higher and showed just shear thinning the concentration needed to reach the kinetic arrest (the gel-like state
behavior. Additionally, the use of frequency sweep tests on these same was reached at lower CNC concentrations).
samples showed that by addition of 15 mM NaCl, the sample showed a Boluk, Zhao, and Incani (2012) studied the effect of dilu­
gel-like behavior and high storage modulus. Both results were explained te–semidilute carboxymethyl cellulose, CMC, (Mw =700 kDa) in a 0.67
by the occurrence of extensive aggregation in the system, which caused vol.% of CNC suspension. A gel was formed by addition of CMC (0.5 wt.
gelation to occur at a relatively low concentration of CNC. %) into the CNC suspension. Further addition of 1.0 wt.%, 2.0 wt.% and

7
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

3.0 wt.% CMC to the suspension, resulted in stronger gels and the last 4.1. Development of structure during drying of casted films
two systems formed two phases, since increased thickening of CMC
prevented the dispersion of the CNCs through the whole sample. The initial step in the formation of an anisotropic phase corresponds
Polarized optical microscopy (POM) showed that although the 0.67 vol. to the nucleation of droplets that appear in the bulk of the isotropic
% CNC suspension is an isotropic system, the addition of 0.5 wt.% CMC phase and slowly separate because of small density differences derived
produced dark and bright areas reflecting the mixture of iso­ from the arrangement of the CNC in the droplets. The more efficient
tropic–anisotropic phases. order of the CNCs leads to a difference in packing (and thus, different
Tailoring the viscosity of modified CNC has also been the target concentration) that results in a difference in density. These droplets,
although for different applications, such as 3D printing in which shear called tactoids, nucleate in the isotropic phase with spherical, ellipsoidal
thinning and thixotropy are needed to ensure good flow conditions and of flattened ellipsoidal shapes and they already contain inside CNC ar­
rapid conversion to solid like behavior (Rees et al., 2015). ranged in chiral nematic order (Fig. 6 A). Parallel birefringent bands
(Wang et al., 2016) are separated by several times the lengths of the
4. Drying and film morphology CNCs, which is consistent with a chiral nematic order in which the pe­
riodic spacing would correspond to that of the length of the mesogens
Since the first works confirming that the structure development in (Gray, 2013).
the dispersions were preserved in the dried films, the interest in Wang et al. (2016) proposed an interesting method to freeze the
obtaining optically active nanocellulose films has witnessed an accel­ tactoids as they are formed, further grew and coalesced. The method
erating growth (Giese & Spengler, 2019; Lagerwall et al., 2014; Majoi­ consisted on mixing the CNC suspension with an acrylamide monomer,
nen, Kontturi, Ikkala, & Gray, 2012; Revol et al., 1997). The chiral which was crosslinked by photopolymerization at different times during
nematic order retained in the dried films results in interesting optical drying after casting of the liquid mixture in Petri dishes. While the
properties. For example, the film can selectively reflect light with presence of the monomer may change quantitatively the characteristics
wavelengths that depend on the pitch length. The value of the wave­ of the phase separated, it does not appear to change the nature of the LC
length reflected, λr, depends on the pitch, p, and the average refractive formation that begins with the nucleation of the tactoids, which further
index of the film, nav, which is approximately 1.56 for the CNC condense in larger structures forming layered structures at the bottom of
(Dumanli, Kamita et al., 2014, Dumanli, van der Kooij et al., 2014; the anisotropic ordered phase.
Lizundia, Puglia, Nguyen, & Armentano, 2020; Wilts et al., 2017) ac­ Regarding the more efficient space filling inside the tactoids and the
cording to: related difference in density between the phases, Wang et al. (2016) also
reported that a 4.08 wt.% suspension allowed to stand and reach equi­
λr = nav ⋅psinθ (2)
librium separated into an isotropic phase with a concentration of 3.75
where θ is the angle between the incident light and the cholesteric wt.% and a chiral nematic phase with 4.46 wt.%, which represented
layers. Thus, if the pitch is in the visible range, the films obtained, may densities of 1.0150 and 1.0165 g/cm3, respectively. The lower and more
show structural colors (de Vries, 1951; Fernandes et al., 2017). ordered phase is formed by larger tactoids (more mature) than the ones
Dumanli, Kamita et al. (2014), Dumanli, van der Kooij et al. (2014) still present in the isotropic phase. As the drying continues, the tactoids
showed that strong colors were observed only in reflected left hand in the ordered phase coalesce (introducing defects when the layers of
circularly polarized light and almost colorless images were obtained different tactoids are not oriented in the same direction), forming long
using right hand circularly polarized light, confirming the left handiness range lamellar structures from the fused tactoids. The periodic spacing
of the helicoidal arrangement of CNC (Lagerwall et al., 2014; Park et al., of these structures appears highly decreased with respect to that
2014). observed in the tactoids in suspension. This layered structure formed by
Certainly, the most challenging goal is to develop processes that are coalescence and sedimentation of the tactoids has also chiral nematic
repeatable, simple and commercially viable for delivering materials ordering and is responsible for the iridescence of the resulting films.
with controlled and tunable structures. Intended applications include Depending on the pitch, the resulting multilayer may result in Bragg
sensors, decorative coatings and security papers (Beck et al., 2013; reflection in the visible spectrum (Korolovych et al., 2018). Fig. 6 B
Zhang, 2012; Zhang, Chodavarapu, Kirk, & Andrews, 2013). shows an example of the layered structure than can be found in CNC
Drying of CNC suspensions that show LC behavior can lead to films films (Guidetti, Atifi, Vignolini, & Hamad, 2016).
with special optical properties. However, not only the characteristics Gray and Mu (2015) presented a description of the process of phases
achieved after phase separation in the liquid suspension and method of formation and the evolution towards the final pitch in the films. As
extending the liquid (casting, coating/shearing) are important in Wang et al. (2016), they also found that the pitch is reduced during the
determining the features of the final film, but the drying process also drying step because of the increasing concentration of the nanocrystals.
affects the final structure. As the drying takes place, the concentration of However, when the critical concentration for kinetic arrest is reached
the suspension increases, which leads to the reduction of the interpar­ the pitch is frozen in the structure.
ticle separation and the decrease of the pitch. At some point, a con­ If the initial concentration of the suspension is below the critical
centration is reached where kinetic arrest takes place due to the value for the appearance of the anisotropic phase, during drying the
increased viscosity of the media and the highly restricted mobility of the concentration of CNC increases and reaches such critical concentration.
CNC (Honorato-Rios et al., 2016), which may potentially lead to the gel However, it may occur that the time for drying is too fast for allowing
state as explained in the rheology section. Because the exposed top the phases to reach the chiral nematic order and the sample may reach
surface is likely to dry sooner than the interior of the sample (Lagerwall the concentration at which kinetic arrest occurs before that ordering
et al., 2014), the drying process produces concentration gradients and takes place. Thus, the final film will not be iridescent and the structure
diffusion effects that may complicate the process to arrive to a final film will probably show an isotropic character (Gray & Mu, 2015). Thereby,
morphology. Dumanli, Kamita et al. (2014), Dumanli, van der Kooij it seems preferable that the samples are in the biphasic coexistence
et al. (2014) on the other hand, controlled the drying process by using range of concentrations, to allow for the structures to consolidate the
fixed humidity environments during the drying step. They found a anisotropic ordering before reaching the gel-like state during drying.
discontinuity in the reduction of the pitch that took place during the The drying process also affects the topology. Gray and Mu (2015)
final step of drying, which was related to the above mentioned kinetic observed differences when using free drying surfaces (coffee stain effect
arrest. was reported), covered surfaces (drying of the suspensions occurred
from the edges of a covered drop), or vacuum drying.

8
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

Fig. 6. A) tactoids are seen in this image of optical microscopy of a CNC suspension (own results). Red circles help to find some of the tactoids, but smaller one can
also be found in the image. B) SEM image of the layered structures in a CNC film. Scale bar is 200 nm. Adapted from Guidetti et al. (2016). Advanced Materials. doi:
10.1002/adma.201603386 under the Creative Commons CC BY license.

4.2. Forced Alignment of the cellulose nanocrystals 5. CNC films properties

Magnetic and electric fields have been utilized to improve the Because of the layered structures occurring in the self assembled CNC
alignment of the CNC in LC systems (Zhu et al., 2020). However, films and the periodic modulation of the refractive index due to the
application of electric fields requires the redispersion of CNC in chiral ordering in these materials, the films behave as photonic crystals.
non-polar organic solvents to avoid complications due to the conduc­ That means that they present a 1D photonic band gap or stop-band, a
tivity of water (De France et al., 2016; Frka-Petesic, Jean, & Heux, spectral range of high reflectivity, which has been proposed to be used in
2014). reflective coatings for increasing the efficiency of light-emitting diodes,
Sugiyama, Chanzy, and Maret (1992) found that cellulose presented LEDs (Giese & Spengler, 2019). When the periodicity of the arrangement
anisotropic diamagnetic susceptibility. Thus, when CNC was subjected (pitch) is in the submicron range it affects the propagation of visible
to a strong magnetic field, the crystallites were oriented with their long light and different colors across the visible spectrum can be observed
axes perpendicular to the field. Thus, cellulose is a negative diamagnetic (Gray, 2013; Honorato-Rios et al., 2016; Mu & Gray, 2014). Addition­
anisotropic material (Frka-Petesic, Sugiyama, Kimura, Chanzy, & Maret, ally, because of the left helical arrangement of the structure, the light
2015; Revol et al., 1994). becomes circularly polarized (left circularly polarized light is reflected,
Revol et al. (1994) showed that if a large magnetic field is applied to while right circularly polarized light is transmitted through the film)
aqueous suspensions of low concentration of CNC (isotropic regime), the (Dumanli, Kamita et al., 2014, Dumanli, van der Kooij et al., 2014;
CNCs could be oriented perpendicularly to the applied field to achieve a Honorato-Rios et al., 2016; Lagerwall et al., 2014).
nematic order. However, if the concentration is high enough for an Preparation of iridescent films from liquid crystalline phases of CNC
anisotropic phase to be present, rather than untwisting the chiral has also been investigated because iridescence provides a bright and/or
nematic structure, the tactoids become oriented so that the axis of the metallic appearance to the films (Fig. 7 A) that may be of high interest
cholesteric helix is parallel to that of the field, meaning that the orien­ for decorative applications (coatings, paints), but also in photonics
tation of the rotating directors of the CNC planes are perpendicular to (optical sensors and filters) (De France et al., 2016; Vlad-Cristea, Landry,
the magnetic field. Because the tactoids become coaligned, fewer dis­ Blanchet, & Ouellet-Plamondon, 2013; Wilts et al., 2017).
locations are present and a more uniform orientation is achieved. Wilts et al. (2017) considered CNC films for color selective polari­
De France et al. (2016) showed that cooperative ordering favors the zation filters. They found that the films were efficient preferential chiral
orientation in the field. Magnetic fields of 0.56–1.2 T were not suffi­ reflectors of left circularly polarized light. They confirmed that the
ciently strong to orient samples with concentrations of 1.65 and 4.13 wt. wavelength of the reflectance peak shifts to longer lengths as the pitch of
% CNC, a goal that had been previously reached by working with CNC the layered structures increases, thus, being potentially applicable as
from tunicates (Frka-Petesic et al., 2015; Sugiyama et al., 1992). They tunable photonic materials. The authors found that the films presented
concluded that higher field, higher CNC aspect ratio and /or higher selective reflectance (higher reflectance of the left polarized light with
concentration may be required to achieve orientation. By using long respect to right polarized light) when the incident angles of light were
CNCs, it was also demonstrated that the orientation is accompanied by lower than 50◦ . According to these results, the films could be used as
the untwisting of the helix and consequently of the increase of the pitch color-selective polarization filters for light at small angles of incidence.
(red-shift) (Frka-Petesic et al., 2015). Korolovych et al. (2018) investigated the structures generated from
Kvien and Oksman (2007) used CNC from microcrystalline cellulose sulfated CNC prepared from different sources: microcrystalline cellu­
to prepare a composite aqueous suspension with poly(vinylalcohol) lose, as well as softwood and hardwood pulps. They noticed that the
(PVA). In that case, the authors reported to have obtained CNC align­ CNC from the pulps showed less size polydispersity and were about 20 %
ment by applying a strong magnetic field of 7 T. Under those conditions, longer than those obtained from microcrystalline cellulose and also
they obtained transparent, birefringent films of ~90 microns in thick­ formed longer locally twisted aggregates. According to these authors,
ness, with a final concentration of 2 wt.% of CNC in PVA. The authors this aggregation led to increased chiral pitch with improved optical
measured the storage modulus (G’) in the parallel direction to the appearance and overall structural uniformity. They observed the char­
applied magnetic field (4.21 ± 0.06 GPa) and found that it was acteristic layered structure on the dried films with all the CNC films
considerably lower than G’ measured in the transverse direction (6.19 ± showing selective reflectance maxima of the reflected light with left
0.2 GPa). This observation supported the conclusion that the CNCs were circular polarization at 343− 435 nm.
aligned perpendicularly to the applied field, as reported above. While modifying the surface charge on the CNC or ionic strength of
the suspending media has proved to be a means of changing the helix
pitch in the aqueous suspensions (a change that will further affect the
layer separation in the films), annealing of the tactoids formed in

9
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

Fig. 7. A) Iridescent film prepared from a CNC

suspension (left) and film prepared after further
sonication (right); B) CNC-elastomer nano­
composite stretched at increased elongations
and observed between cross-polarizers (scale
bar is 1 cm); C) comparison of the optical
response of the neat elastomer (upper sample)
and the CNC nanocomposite (lower sample), in
the unstretched condition (left-C1) and the
stretched condition (right-C2). Figure A adapt­
ed from Vlad-Cristea et al. (2013) ISRN Nano­
materials, doi: 10.1155/2013/930236 under
the Creative Commons CC BY license. Figures B
and C adapted from Kose et al. (2019) Nature
Communications doi: 10.1038/s41467-019-0835
1-6. under the Creative Commons CC BY license
(supplementary information).

suspension also produces a change in pitch (red shift has been observed) concentration utilized 1 wt.% of NFC, with the Young’s modulus
(Korolovych et al., 2018; Tran, Hamad, & MacLachlan, 2018; Wang increasing from 3.4 to 4.4 GPa; tensile strength from 14.25 to 25.88 MPa
et al., 2016). and elongation at break from 0.466 to 1.24 %. Remarkably, the material
The ordering of the CNCs has also other consequences besides those not only gained in modulus but it also became tougher, which is of
related to optical behavior, for example, the barrier properties of a paramount importance if the final application requires subjecting the
random structured CNC film are different from those of an ordered one. film to bending stress while supporting flexible electronics. Actually, the
In addition, the mechanical properties are different, with the ordered nanopapers obtained were writable and a conductive path was printed
film presenting higher Young modulus, but lower strain at break (a more on such nanopaper to allow a LED to light. The conductive nanopaper
brittle material). Thus, the films obtained from neat CNC chiral nematic could be bended without altering the efficiency of the conductive path,
suspensions are very brittle and so, they are of limited use in applica­ confirming the potential to create bendable, writable electronics that are
tions. Because of the inherent fragility of all-CNC made films, different also iridescent and fully biodegradable.
authors have looked for means to increase the flexibility of the films Bardet, Belgacem, and Bras (2015) presented a study in which the
without losing the optical response. CNCs films were flexibilized by the addition of up to 10 wt.% of an
Thus, Xiong et al. (2014) prepared films of CNC containing low anionic polymer, sodium polyacrylate (PAAS), and a neutral one, a
percentages of nanofibrilar cellulose. Notably, the resulting all-cellulose polyethylene glycol (PEG) of low molecular weight (200 g/mol). None
hybrid nanopapers resulted in more transparent films than the one of these polymers caused flocculation. The anionic one, because of its
prepared from only CNC. The explanation being that the more flexible large capacity for water absorption, was capable of changing the pitch of
NFCs contributes to fill the potential voids left by the CNC ordered the obtained films that as a result reflected different visible colors. On
structure, which was supported by AFM and SEM observations. In their the other hand, the neutral polymer acted mostly as a steric stabilizer
work, films of ~ 50 nm in thickness were prepared from the CNC and led to improved flexibility, but it reduces somehow the iridescence
(prepared by sulfuric acidolysis of cotton fibers), with the addition of of the films.
NFC (from never dried bamboo bleached fibers) in the range of 0− 10 wt. On the other hand, induced structural color resulting from the
% (dry basis). The usual colorful patterns found in POM were still incorporation of CNC into polymeric matrices has also been subject of
relatively strong at low NFC concentrations, although they dimmed as study. In the following paragraphs, these materials are considered
the percentage of NFC increased and disappeared completely at 10 wt. (Bardet et al., 2015; Kelly et al., 2013).
%. The authors found a remarkable improvement of the mechanical Kelly et al. (2013) prepared suspensions of CNC (from sulfuric acid
properties with respect to the neat CNC nanopaper, at even the lowest hydrolysis) and added different acrylic monomers, a crosslinker and a

10
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

photoinitiator. By selecting the monomer it was possible to tailor the intense band gap. This was not the case in latexes with smaller nano­
response of the films to swelling with different solvents, thus producing particles that interfered with a lower number of CNC layers.
different changes in the iridescent colors (showing red-shift in the Drying at 75 ◦ C rapidly led to the kinetic arrest, so ordering was
swollen samples) of even shift to the near IR region. Additionally, the inhibited. However, drying at 25 ◦ C and annealing at 75 ◦ C led to better
iridescence was modulated by the concentration of the components ordered structures with band gaps ~400 nm, since the capacity of the
utilized, CNC concentrations of ~10 wt.% and 66 wt.% were considered. latex to be deformed at the high temperature allowed the rearrangement
Larger chiral shifts were obtained by increasing the polymer/CNC ratio. of the CNC. Besides, low Tg latexes (rubbery at the temperature of
The films that were obtained by casting and drying followed by UV preparation) were less disrupting of the liquid crystalline order because
curing, could also be imprinted by selecting the areas exposed to UV the particles could be deformed during the arrangement. It was
curing. With this method, the imprinted figure could be seen only when concluded that the best combination would be obtained using small
the films were swollen. particle latexes, negatively charged and with low Tg in order to control
Giese, Khan, Hamad, and MacLachlan (2013) presented a rather and tune the photonic behavior of the nanocomposite films.
simple yet effective means of changing the pitch and so the color of The same group (Thérien-Aubin, Lukach, Pitch, & Kumacheva, 2015)
thermosetting melamine-urea-formaldehyde-cellulose composites. As in also used dyed-labeled poly(ethyl methacrylate) latex (nanoparticles
the previous case, the color of the films was controlled through the ratio with ~154 nm in diameter and a Tg of 68 ◦ C) and produced films con­
polymer/ CNC (increasing the ratio produced red shift, even reaching taining the polymeric nanoparticles and CNC (~13 nm in diameter and
the near IR region) and of the ionic strength of the CNC aqueous sus­ ~180 nm in length). The chiral self assembling of CNC could be
pension (salt addition), but the novelty was the control through the observed up to a latex volume fraction of 0.31. Below that fraction, the
application of pressure to the formed film. This method resulted in the films obtained showed the typical layered structure of the CNC films, but
compression of the helical pitch, which produced a blue-shift of the films with the latex nanoparticles included. They also showed homogeneous
color. Tilting of the layers was mentioned as a possible additional reason fluorescence due to the well distributed latex and also birrefringence
for the observed changes. By applying pressure using a stamp a pattern and circular dichroism.
could be imprinted. Further curing of the films (at room temperature for On this same line of work, Wan et al. (2018) considered the effect of
120 h or at 120 ◦ C for 2 h) fixed the structure and no more changes could producing blends of CNC suspensions and commercially available
be induced by pressure. anionic waterborne polyurethane dispersions (WBPU). As in the case of
Kose et al. (2019) also pursued this idea by including CNC in an Thérien-Aubin et al. (2015b), they used dispersions of small particles
elastomeric matrix. To prepare such a nanocomposite film, they first diluted down to 5 wt.%, added a small concentration of a isocyanate
prepared a film from a suspension of CNC (2 wt.%) and added glucose (1 crosslinker and further blended with a suspension of CNC (3.5 wt.%)
wt.%), which allowed to obtain non-cracked CNC films with LC order. prepared with the usual sulfuric acid method. Samples were prepared
The film was further swollen with dimethylsulfoxide and then with with different concentrations of WBPU (0− 100 wt.%). The thickness of
acrylate monomers. The polymerization reaction was carried out at 60 the films was kept between 20–40 microns. Samples containing up to 60
◦
C with added initiator. The nanocomposite films contained approxi­ wt.% of the polyurethane (PU) showed chiral nematic order, while
mately 9 wt.% of CNC and had about 600 microns in thickness. The film further addition of PU lead to the coexistence of CNC-rich ordered re­
was stretchable and could revert to the original length when the stress gions and PU-rich regions of low or no order. The color of the films was
was removed. If the sample was placed in between cross-polarizers a tuned by addition of the WBPU. Since the refractive index of the CNC
brilliant interference was observed with changing colors in response to and that of the PU were relatively close (~1.50, for the PU), the UV–vis
the extension applied. The change of colors was related to the untwisting spectrum showed that the maximum of the band gap was also tuned by
of the helical chiral nematic structure (increased pitch) during extension the changed structure (~332 nm for the neat CNC to ~625 nm for the
and twisting back, when contraction took place. The Fig. 7 B shows this 40/60 CNC/WBPU). The authors also studied the effect of solvent on the
colored response of the sample subjected to different extensions. Fig. 7 C films. As the solvent swells the film, the pitch changes and a red shift of
(C1 and C2) is included to support the fact that intense birefringence is the color is observed. The original color could be recovered after drying,
the result of the presence of the CNC arrangement, and not due to the which makes these materials potentially useful as sensors.
much less intense optical response resulting from the orientation of the New optical responses have been obtained by sensible modifications
polymer chains due to the sample stretching. of CNC solid iridescent films. Fernandes et al. (2017) mimicked the
Different authors (Nguyen, Hamad, & MacLachlan, 2017; Thérie­ structure found in the cuticle of the beetle Plusiotis Resplendens, that
n-Aubin, Lukach, Pitch, & Kumacheva, 2015) have found out that in reflects both left and right circularly polarized light. To do so they
several cases the addition of other nanoparticles (inorganic or organic prepared a sandwich structure of two layered CNC films with a microgap
polymeric ones) does not destroy the chiral nematic arrangement of the that was further infiltrated with 4-cyano-4′ -pentylbiphenyl nematic LC.
CNC suspensions. The anisotropic medium LC acted as half-wave phase retarder, with the
In the case of organic nanoparticles, latexes have been considered. overall result of the composite films reflecting left and right polarized
Depending on the characteristics of the latexes the photonic crystal light.
structures of the CNC can be preserved or destroyed. A rather complete
study focused on identifying the optimum characteristics of the latex to 6. Summary and outlook
utilize was presented by Thérien-Aubin et al. (2015a). These authors
prepared latexes exhibiting positive or negative surface charges, The overview presented illustrates the rich and varied behavior of
different Tg (from − 48 ◦ C to 68 ◦ C) and particle diameters of ~50 nm the CNC systems. The large interest on these materials arises and keeps
and ~150 nm with narrow polydispersity. It was found that positively growing because of their environmentally friendly nature, their large
charged latexes destroyed more easily the liquid crystal ordering than availability, and because of their exceptional properties. The promises
the negatively charged latexes, because they contributed more effi­ on CNC derived materials and applications are many, but there are many
ciently to the kinetic arrest by increasing viscosity (gel-like state). On the variables that should be adjusted to tailor the final properties of the CNC
other hand, negatively charged latexes with small nanoparticles showed liquid suspensions and films. The richness and variety of adjustments
slight red shift (~380 nm to ~410 nm) and lower intensity of the band offer at the same time promises and challenges. The variables that can be
gap at 25 wt.% of the latex. A much lower intensity was observed at 50 adjusted to fit a given requirement are many: the characteristics of the
wt.% of the latex and all order disappeared at higher concentrations. It crystals (mainly their aspect ratio, but also their surface chemistry),
was also demonstrated that large particles lead to the formation of their concentration in liquid suspensions, any chemical added to the
CNC-rich and latex-rich regions, resulting in reduced order and less suspensions (salts, monomers, dispersants, latexes, etc.), the time

11
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

allotted for phase equilibration, the rate of the drying process, the use of Bercea, M., & Navard, P. (2000). Shear dynamics of aqueous suspensions of cellulose
whiskers. Macromolecules, 33(16), 6011–6016. https://doi.org/10.1021/ma000417p
electrical, magnetic or shear induced alignment. The optimization and
Bertsch, P., Sánchez-Ferrer, A., Bagnani, M., Isabettini, S., Kohlbrecher, J., Mezzenga, R.,
control of these variables will allow developing the aimed applications et al. (2019). Ion-induced formation of nanocrystalline cellulose colloidal glasses
and although there has been an undeniable progress, there is still a containing nematic domains. Langmuir, 35(11), 4117–4124. https://doi.org/
strong need of better adjusting the balance between ordering and drying 10.1021/acs.langmuir.9b00281
Beuguel, Q., Tavares, J. R., Carreau, P. J., & Heuzey, M.-C. (2018). Ultrasonication of
rates. spray- and freeze-dried cellulose nanocrystals in water. Journal of Colloid and
In particular, there is need to use simple and rapid alignment for CNC Interface Science, 516, 23–33. https://doi.org/10.1016/j.jcis.2018.01.035
that persists during drying. The correct balance between low viscosity Boluk, Y., Lahiji, R., Zhao, L., & McDermott, M. T. (2011). Suspension viscosities and
shape parameter of cellulose nanocrystals (CNC). Colloids and Surfaces A:
during shearing to allow for orientation and rapid arrest/gellification Physicochemical and Engineering Aspects, 377(1–3), 297–303. https://doi.org/
due to drying needs the advancement of experimentation and modelling 10.1016/j.colsurfa.2011.01.003
to achieve the level needed for commercial repeatability on the product Boluk, Y., Zhao, L., & Incani, V. (2012). Dispersions of nanocrystalline cellulose in
aqueous polymer solutions: Structure formation of colloidal rods. Langmuir, 28(14),
manufacture. However, the academic and industrial interests in the 6114–6123. https://doi.org/10.1021/la2035449
cellulose nanomaterials that has lead to the upscaling of MFC/NFC and Buffa, J. M., Casado, U., Mucci, V., & Aranguren, M. I. (2019). Cellulose nanocrystals in
CNC productions from laboratory to pilot or full productions in the last aqueous suspensions: Rheology of lyotropic chiral liquid crystals. Cellulose. https://
doi.org/10.1007/s10570-019-02278-3
decades, support the expectancy for continuous progress in the pro­ Buffa, J. M., Grela, M. A., Aranguren, M. I., & Mucci, V. (2016). EPR spectroscopy applied
cessing of these new materials. Stretching may also be a useful technique to the study of the TEMPO mediated oxidation of nanocellulose. Carbohydrate
to obtain the desired orientation, when the films are produced with a Polymers, 136, 744–749. https://doi.org/10.1016/j.carbpol.2015.09.094
Buffa, J. M., Mondragon, G., Corcuera, M. A., Eceiza, A., Mucci, V., & Aranguren, M. I.
polymeric ligand with the macromolecular chains assisting in the crystal
(2018). Physical and mechanical properties of a vegetable oil based nanocomposite.
orientation. Application of magnetic fields and combination of applied European Polymer Journal, 98, 116–124. https://doi.org/10.1016/j.
field and shear flows are other promising techniques to obtain the level eurpolymj.2017.10.035
of orientation required at large scale. Burghardt, W. R., & Fuller, G. G. (1991). Role of director tumbling in the rheology of
polymer liquid crystal solutions. Macromolecules, 24(9), 2546–2555. https://doi.org/
On the other hand, the fragility of all-CNC films makes other alter­ 10.1021/ma00009a063
natives such as hybrid MFC-CNC films and polymer composites with Chau, M., Sriskandha, S. E., Pichugin, D., Thérien-Aubin, H., Nykypanchuk, D.,
high CNC content more attractive for further commercial manufacture. Chauve, G., et al. (2015). Ion-mediated gelation of aqueous suspensions of cellulose
nanocrystals. Biomacromolecules, 16(8), 2455–2462. https://doi.org/10.1021/acs.
Polymers such as UV-curing acrylates and WBPUs appear as most biomac.5b00701
interesting prospects, although other polymers are being proposed, in all De France, K. J., Yager, K. G., Hoare, T., & Cranston, E. D. (2016). Cooperative ordering
cases with the aim of improving flexibility without compromising and kinetics of cellulose nanocrystal alignment in a magnetic field. Langmuir, 32(30),
7564–7571. https://doi.org/10.1021/acs.langmuir.6b01827
transparency. This may prove to be the most promising technique and de Vries, H. (1951). Rotatory power and other optical properties of certain liquid
the one with most rapid development in the short time for producing crystals. Acta Crystallographica, 4(3), 219–226. https://doi.org/10.1107/
iridescent and optically active CNC films. S0365110X51000751
Dong, X. M., & Gray, D. G. (1997). Induced circular dichroism of isotropic and
magnetically-oriented chiral nematic suspensions of cellulose crystallites. Langmuir,
Declaration of Competing Interest 13(11), 3029–3034. https://doi.org/10.1021/la9610462
Dong, X. M., Kimura, T., Revol, J.-F., & Gray, D. G. (1996). Effects of ionic strength on the
isotropic− Chiral nematic phase transition of suspensions of cellulose crystallites.
The authors report no declarations of interest. Langmuir, 12(8), 2076–2082. https://doi.org/10.1021/la950133b
Dong, X. M., Revol, J., & Gray, D. G. (1998). Effect of microcrystallite preparation
Acknowledgements conditions on the formation of colloid crystals of cellulose. Cellulose, 5(1), 19–32.
Dumanli, A. G., Kamita, G., Landman, J., van der Kooij, H., Glover, B. J., Baumberg, J. J.,
et al. (2014). Controlled, bio-inspired self-assembly of cellulose-based chiral
The authors acknowledge the funding from Agencia Nacional de reflectors. Advanced Optical Materials, 2(7), 646–650. https://doi.org/10.1002/
Promoción Científica y Tecnológica (ANPCyT) (PICT-2017- 1318), adom.201400112
Dumanli, A. G., van der Kooij, H. M., Kamita, G., Reisner, E., Baumberg, J. J., Steiner, U.,
Consejo Nacional de Investigaciones Científicas y Técnicas(CONICET)
et al. (2014). Digital color in cellulose nanocrystal films. ACS Applied Materials &
(PIP 2017 0100677) and Universidad Nacional de Mar del Plata Interfaces, 6(15), 12302–12306. https://doi.org/10.1021/am501995e
(UNMdP) (15/G557, ING561/19). Thanks are also due to Lic. Juan Echeverria, C., Almeida, P. L., Aguilar Gutierrez, O. F., Rey, A. D., & Godinho, M. H.
Manuel Buffa for the preparation of the CNC + GA suspensions and for (2017). Two negative minima of the first normal stress difference in a cellulose-
based cholesteric liquid crystal: Helix uncoiling. Journal of Polymer Science Part B:
the image used in Fig. 6 A and to Professor Jorge Froilán González for his Polymer Physics, 55(10), 821–830. https://doi.org/10.1002/polb.24332
critical reading of the manuscript. Eichhorn, S. J., Dufresne, A., Aranguren, M., Marcovich, N. E., Capadona, J. R.,
Rowan, S. J., et al. (2010). Review: Current international research into cellulose
nanofibres and nanocomposites. Journal of Materials Science, 45(1), 1–33. https://
Appendix A. Supplementary data doi.org/10.1007/s10853-009-3874-0
Fernandes, S. N., Almeida, P. L., Monge, N., Aguirre, L. E., Reis, D., de Oliveira, C. L. P.,
Supplementary material related to this article can be found, in the et al. (2017). Mind the Microgap in iridescent cellulose nanocrystal films. Advanced
Materials, 29(2), 1603560. https://doi.org/10.1002/adma.201603560
online version, at doi:https://doi.org/10.1016/j.carbpol.2021.117848. Frka-Petesic, B., Jean, B., & Heux, L. (2014). First experimental evidence of a giant
permanent electric-dipole moment in cellulose nanocrystals. EPL (Europhysics
References Letters), 107(2), 28006. https://doi.org/10.1209/0295-5075/107/28006
Frka-Petesic, B., Sugiyama, J., Kimura, S., Chanzy, H., & Maret, G. (2015). Negative
diamagnetic anisotropy and birefringence of cellulose nanocrystals. Macromolecules,
Aguayo, M., Fernández Pérez, A., Reyes, G., Oviedo, C., Gacitúa, W., Gonzalez, R., et al.
48(24), 8844–8857. https://doi.org/10.1021/acs.macromol.5b02201
(2018). Isolation and characterization of cellulose nanocrystals from rejected fibers
Gama, M., Dourado, F., & Bielecki, S. (Eds.). (2016). Bacterial nanocellulose: From
originated in the kraft pulping process. Polymers, 10(10), 1145. https://doi.org/
biotechnology to bio-economy. Elsevier.
10.3390/polym10101145
Gicquel, E., Bras, J., Rey, C., Putaux, J.-L., Pignon, F., Jean, B., et al. (2019). Impact of
Aranguren, M. I., Mucci, V., & Peresin, M. S. (2017). Spectroscopy studies of cellulose
sonication on the rheological and colloidal properties of highly concentrated
nanofiber- and cellulose nanocrystal-based nanocomposites. Handbook of
cellulose nanocrystal suspensions. Cellulose, 26(13–14), 7619–7634. https://doi.org/
nanocellulose and cellulose nanocomposites (pp. 581–608). John Wiley & Sons, Ltd.
10.1007/s10570-019-02622-7
https://doi.org/10.1002/9783527689972.ch17
Giese, M., & Spengler, M. (2019). Cellulose nanocrystals in nanoarchitectonics – Towards
Bardet, R., Belgacem, N., & Bras, J. (2015). Flexibility and color monitoring of cellulose
photonic functional materials. Molecular Systems Design & Engineering, 4(1), 29–48.
nanocrystal iridescent solid films using anionic or neutral polymers. ACS Applied
https://doi.org/10.1039/C8ME00065D
Materials & Interfaces, 7(7), 4010–4018. https://doi.org/10.1021/am506786t
Giese, M., Khan, M. K., Hamad, W. Y., & MacLachlan, M. J. (2013). Imprinting of
Beck, S., Bouchard, J., Chauve, G., & Berry, R. (2013). Controlled production of patterns
photonic patterns with thermosetting amino-formaldehyde-cellulose composites.
in iridescent solid films of cellulose nanocrystals. Cellulose, 20(3), 1401–1411.
ACS Macro Letters, 2(9), 818–821. https://doi.org/10.1021/mz4003722
https://doi.org/10.1007/s10570-013-9888-4
Gray, D. (2013). Iridescent films from cellulose nanocrystals: Chiral nematic or smectic
Belgacem, M. N., & Gandini, A. (2005). The surface modification of cellulose fibres for
multi-lamellar structure? J-FOR, 3, 6–8.
use as reinforcing elements in composite materials. Composite Interfaces, 12(1–2),
41–75. https://doi.org/10.1163/1568554053542188

12
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

Gray, D. (2016). Recent advances in chiral nematic structure and iridescent color of Liu, D., Chen, X., Yue, Y., Chen, M., & Wu, Q. (2011). Structure and rheology of
cellulose nanocrystal films. Nanomaterials, 6(11), 213. https://doi.org/10.3390/ nanocrystalline cellulose. Carbohydrate Polymers, 84(1), 316–322. https://doi.org/
nano6110213 10.1016/j.carbpol.2010.11.039
Gray, D., & Mu, X. (2015). Chiral nematic structure of cellulose nanocrystal suspensions Lizundia, E., Puglia, D., Nguyen, T.-D., & Armentano, I. (2020). Cellulose nanocrystal
and films; polarized light and atomic force microscopy. Materials, 8(11), 7873–7888. based multifunctional nanohybrids. Progress in Materials Science, 112, Article
https://doi.org/10.3390/ma8115427 100668. https://doi.org/10.1016/j.pmatsci.2020.100668
Guidetti, G., Atifi, S., Vignolini, S., & Hamad, W. Y. (2016). Flexible photonic cellulose Ljungberg, N., Bonini, C., Bortolussi, F., Boisson, C., Heux, L., & Cavaillé. (2005). New
nanocrystal films. Advanced Materials, 28(45), 10042–10047. https://doi.org/ nanocomposite materials reinforced with cellulose whiskers in Atactic
10.1002/adma.201603386 polypropylene: Effect of surface and dispersion characteristics. Biomacromolecules, 6
Habibi, Y., Lucia, L. A., & Rojas, O. J. (2010). Cellulose nanocrystals: Chemistry, self- (5), 2732–2739. https://doi.org/10.1021/bm050222v
assembly, and applications. Chemical Reviews, 110(6), 3479–3500. https://doi.org/ Majoinen, J., Hassinen, J., Haataja, J. S., Rekola, H. T., Kontturi, E., Kostiainen, M. A.,
10.1021/cr900339w et al. (2016). Chiral plasmonics using twisting along cellulose nanocrystals as a
Hirai, A., Odani, H., & Nakajima, A. (1991). Determination of degree of deacetylation of template for gold nanoparticles. Advanced Materials, 28(26), 5262–5267. https://doi.
chitosan by 1H NMR spectroscopy. Polymer Bulletin, 26(1), 87–94. org/10.1002/adma.201600940
Hong, H.-J., Yu, H., Hong, S., Hwang, J. Y., Kim, S. M., Park, M. S., et al. (2020). Majoinen, J., Kontturi, E., Ikkala, O., & Gray, D. G. (2012). SEM imaging of chiral
Modified tunicate nanocellulose liquid crystalline fiber as closed loop for recycling nematic films cast from cellulose nanocrystal suspensions. Cellulose, 19(5),
platinum-group metals. Carbohydrate Polymers, 228, Article 115424. https://doi.org/ 1599–1605. https://doi.org/10.1007/s10570-012-9733-1
10.1016/j.carbpol.2019.115424 Marchessault, R. H., Morehead, F. F., & Koch, M. J. (1961). Some hydrodynamic
Honorato-Rios, C., Kuhnhold, A., Bruckner, J. R., Dannert, R., Schilling, T., & properties of neutral suspensions of cellulose crystallites as related to size and shape.
Lagerwall, J. P. F. (2016). Equilibrium liquid crystal phase diagrams and detection of Journal of Colloid Science, 16(4), 327–344. https://doi.org/10.1016/0095-8522(61)
kinetic arrest in cellulose nanocrystal suspensions. Frontiers in Materials, 3. https:// 90033-2
doi.org/10.3389/fmats.2016.00021 Marchessault, R. H., Morehead, F. F., & Walter, N. M. (1959). Liquid crystal systems from
Hormaiztegui, M. E. V., Mucci, V. L., Santamaria-Echart, A., Corcuera, M.Á., Eceiza, A., & fibrillar polysaccharides. Nature, 184(4686), 632–633. https://doi.org/10.1038/
Aranguren, M. I. (2016). Waterborne polyurethane nanocomposites based on 184632a0
vegetable oil and microfibrillated cellulose. Journal of Applied Polymer Science, 133 Matveichuk, O. O. (2013). Constitutive modeling of concentrated solutions of main-chain
(47). https://doi.org/10.1002/app.44207 liquid crystalline polymers. https://doi.org/10.6100/IR750672
Hormaiztegui, M. E. V., Mucci, V. L., & Aranguren, M. I. (2019). Composite films Menzel, A. M. (2015). Tuned, driven, and active soft matter. Physics Reports, 554, 1–45.
obtained from a waterborne biopolyurethane. Incorporation of tartaric acid and https://doi.org/10.1016/j.physrep.2014.10.001
nanocellulose. Industrial Crops and Products, 142, Article 111879. https://doi.org/ Mewis, J., & Wagner, N. J. (2012). Colloidal suspension rheology. Cambridge University
10.1016/j.indcrop.2019.111879 Press.
Huang, C.-M., Magda, J. J., & Larson, R. G. (1999). The effect of temperature and Mewis, J., Mortier, M., Vermant, J., & Moldenaers, P. (1997). Experimental evidence for
concentration on N1 and tumbling in a liquid crystal polymer. Journal of Rheology, the existence of a wagging regime in polymeric liquid crystals. Macromolecules, 30
43(1), 31–50. https://doi.org/10.1122/1.551037 (5), 1323–1328. https://doi.org/10.1021/ma961146e
Hubbe, M. A., Tayeb, P., Joyce, M., Tyagi, P., Kehoe, M., Dimic-Misic, K., et al. (2017). Moberg, T., Sahlin, K., Yao, K., Geng, S., Westman, G., Zhou, Q., et al. (2017).
Rheology of nanocellulose-rich aqueous suspensions: A review. BioResources, 12(4), Rheological properties of nanocellulose suspensions: Effects of fibril/particle
9556–9661. dimensions and surface characteristics. Cellulose, 24, 2499–2510. https://doi.org/
João, C. F. C., Echeverria, C., Velhinho, A., Silva, J. C., Godinho, M. H., & Borges, J. P. 10.1007/s10570-017-1283-0
(2017). Bio-inspired production of chitosan/chitin films from liquid crystalline Moldenaers, P., & Mewis, J. (1990). Relaxational phenomena and anisotrophy in
suspensions. Carbohydrate Polymers, 155, 372–381. https://doi.org/10.1016/j. lyotropic polymeric liquid crystals. Journal of Non-Newtonian Fluid Mechanics, 34(3),
carbpol.2016.08.039 359–374. https://doi.org/10.1016/0377-0257(90)80029-Y
Kelly, J. A., Shukaliak, A. M., Cheung, C. C. Y., Shopsowitz, K. E., Hamad, W. Y., & Mondragon, G., Santamaria-Echart, A., Hormaiztegui, M. E. V., Arbelaiz, A., Peña-
MacLachlan, M. J. (2013). Responsive photonic hydrogels based on nanocrystalline Rodriguez, C., Mucci, V., et al. (2018). Nanocomposites of waterborne polyurethane
cellulose. Angewandte Chemie International Edition, 52(34), 8912–8916. https://doi. reinforced with cellulose nanocrystals from sisal fibres. Journal of Polymers and the
org/10.1002/anie.201302687 Environment, 26(5), 1869–1880. https://doi.org/10.1007/s10924-017-1089-z
Kiss, G., & Porter, R. S. (1996). Rheology of concentrated solutions of poly(γ-benzyl- Mosiewicki, M. A., Marcovich, N. E., & Aranguren, M. I. (2011). Characterization of fiber
glutamate). Journal of Polymer Science Part B: Polymer Physics, 34(14), 2271–2289. surface treatments in natural fiber composites by infrared and Raman spectroscopy.
https://doi.org/10.1002/polb.1996.938 Interface engineering of natural fibre composites for maximum performance (pp.
Kiss, G., & Porter, R. S. (1998). Flow induced phenomena of lyotropic polymer liquid 117–145). Elsevier. https://doi.org/10.1533/9780857092281.1.117
crystals: The negative normal force effect and bands perpendicular to shear. In Mu, X., & Gray, D. G. (2014). Formation of chiral nematic films from cellulose
W. Brostow (Ed.), Mechanical and thermophysical properties of polymer liquid crystals nanocrystal suspensions is a two-stage process. Langmuir, 30(31), 9256–9260.
(pp. 342–406). Springer US. https://doi.org/10.1007/978-1-4615-5799-9_11. https://doi.org/10.1021/la501741r
Korolovych, V. F., Cherpak, V., Nepal, D., Ng, A., Shaikh, N. R., Grant, A., et al. (2018). Mu, X., & Gray, D. G. (2015). Droplets of cellulose nanocrystal suspensions on drying
Cellulose nanocrystals with different morphologies and chiral properties. Polymer, give iridescent 3-D “coffee-stain” rings. Cellulose, 22(2), 1103–1107. https://doi.org/
145, 334–347. https://doi.org/10.1016/j.polymer.2018.04.064 10.1007/s10570-015-0569-3
Kose, O., Tran, A., Lewis, L., Hamad, W. Y., & MacLachlan, M. J. (2019). Unwinding a Narimissa, E., Rahman, A., Gupta, R. K., Kao, N., & Bhattacharya, S. N. (2014).
spiral of cellulose nanocrystals for stimuli-responsive stretchable optics. Nature Anomalous first normal stress difference behavior of polymer nanocomposites and
Communications, 10(1), 510. https://doi.org/10.1038/s41467-019-08351-6 liquid crystalline polymer composites. Polymer Engineering and Science, 54(6),
Kumar, V., Pathak, P., & Bhardwaj, N. K. (2020). Waste paper: An underutilized but 1300–1312. https://doi.org/10.1002/pen.23675
promising source for nanocellulose mining. Waste Management, 102, 281–303. Nguyen, T.-D., Hamad, W. Y., & MacLachlan, M. J. (2017). Near-IR-sensitive
https://doi.org/10.1016/j.wasman.2019.10.041 upconverting nanostructured photonic cellulose films. Advanced Optical Materials, 5
Kvien, I., & Oksman, K. (2007). Orientation of cellulose nanowhiskers in polyvinyl (1), 1600514. https://doi.org/10.1002/adom.201600514
alcohol. Applied Physics A, 87(4), 641–643. https://doi.org/10.1007/s00339-007- Nigmatullin, R., Harniman, R., Gabrielli, V., Muñoz-García, J. C., Khimyak, Y. Z.,
3882-3 Angulo, J., et al. (2018). Mechanically robust gels formed from hydrophobized
Lagerwall, J. P. F., Schütz, C., Salajkova, M., Noh, J., Hyun Park, J., Scalia, G., et al. cellulose nanocrystals. ACS Applied Materials & Interfaces, 10(23), 19318–19322.
(2014). Cellulose nanocrystal-based materials: From liquid crystal self-assembly and https://doi.org/10.1021/acsami.8b05067
glass formation to multifunctional thin films. NPG Asia Materials, 6(1), e80. https:// Onogi, S., & Asada, T. (1980). rheology and rheo-optics of polymer liquid crystals. In
doi.org/10.1038/am.2013.69 G. Astarita, G. Marrucci, & L. Nicolais (Eds.), Rheology: Volume 1: Principles (pp.
Larson, R. G. (1990). Arrested tumbling in shearing flows of liquid-crystal polymers. 127–147). Springer US. https://doi.org/10.1007/978-1-4684-3740-9_9.
Macromolecules, 23(17), 3983–3992. https://doi.org/10.1021/ma00219a020 Onsager, L. (1949). The effects of shape on the interaction of colloidal particles. Annals of
Larson, R. G. (1993). Roll-cell instabilities in shearing flows of nematic polymers. Journal the New York Academy of Sciences, 51(4), 627–659. https://doi.org/10.1111/j.1749-
of Rheology, 37(2), 175–197. https://doi.org/10.1122/1.550440 6632.1949.tb27296.x
Lee, H.-C., & Brant, D. A. (2002). Rheology of concentrated isotropic and anisotropic Orts, W. J., Godbout, L., Marchessault, R. H., & Revol, J.-F. (1998). Enhanced ordering of
xanthan solutions. 1. A Rodlike low molecular weight sample. Macromolecules, 35(6), liquid crystalline suspensions of cellulose microfibrils: A small angle neutron
2212–2222. https://doi.org/10.1021/ma011526m scattering study. Macromolecules, 31(17), 5717–5725. https://doi.org/10.1021/
Lenfant, G., Heuzey, M.-C., van de Ven, T. G. M., & Carreau, P. J. (2017). A comparative ma9711452
study of ECNC and CNC suspensions: Effect of salt on rheological properties. Pan, J., Hamad, W., & Straus, S. K. (2010). Parameters affecting the chiral nematic phase
Rheologica Acta, 56(1), 51–62. https://doi.org/10.1007/s00397-016-0979-7 of nanocrystalline cellulose films. Macromolecules, 43(8), 3851–3858. https://doi.
Lettinga, M. P., Dogic, Z., Wang, H., & Vermant, J. (2005). Flow behavior of colloidal org/10.1021/ma902383k
rodlike viruses in the nematic phase. Langmuir, 21(17), 8048–8057. https://doi.org/ Park, J. H., Noh, J., Schütz, C., Salazar-Alvarez, G., Scalia, G., Bergström, L., et al.
10.1021/la050116e (2014). Macroscopic control of helix orientation in films dried from cholesteric
Li, J., Revol, J.-F., & Marchessault, R. H. (1996). Rheological properties of aqueous liquid-crystalline cellulose nanocrystal suspensions. ChemPhysChem, 15(7),
suspensions of chitin crystallites. Journal of Colloid and Interface Science, 183(2), 1477–1484. https://doi.org/10.1002/cphc.201400062
365–373. https://doi.org/10.1006/jcis.1996.0558 Phan-Xuan, T., Thuresson, A., Skepö, M., Labrador, A., Bordes, R., & Matic, A. (2016).
Li, M.-C., Wu, Q., Song, K., Lee, S., Qing, Y., & Wu, Y. (2015). Cellulose nanoparticles: Aggregation behavior of aqueous cellulose nanocrystals: The effect of inorganic salts.
Structure–Morphology–Rheology relationships. ACS Sustainable Chemistry & Cellulose, 23(6), 3653–3663. https://doi.org/10.1007/s10570-016-1080-1
Engineering, 3(5), 821–832. https://doi.org/10.1021/acssuschemeng.5b00144

13
U. Casado et al. Carbohydrate Polymers 261 (2021) 117848

Picken, S. J., Aerts, J., Doppert, H. L., Reuvers, A. J., & Northolt, M. G. (1991). Structure Tran, A., Hamad, W. Y., & MacLachlan, M. J. (2018). Tactoid annealing improves order
and rheology of aramid solutions: Transient rheological and rheooptical in self-assembled cellulose nanocrystal films with chiral nematic structures.
measurements. Macromolecules, 24(6), 1366–1375. https://doi.org/10.1021/ Langmuir, 34(2), 646–652. https://doi.org/10.1021/acs.langmuir.7b03920
ma00006a023 Ureña-Benavides, E. E., Ao, G., Davis, V. A., & Kitchens, C. L. (2011). Rheology and phase
Pleiner, H., & Brand, H. R. (1996). Hydrodynamics and electrohydrodynamics of liquid behavior of lyotropic cellulose nanocrystal suspensions. Macromolecules, 44(22),
crystals. In A. Buka, & L. Kramer (Eds.), Pattern formation in liquid crystals (pp. 8990–8998. https://doi.org/10.1021/ma201649f
15–67). New York: Springer. https://doi.org/10.1007/978-1-4612-3994-9_2. Vanderfleet, O. M., Reid, M. S., Bras, J., Heux, L., Godoy-Vargas, J., Panga, M. K. R., et al.
Pleiner, H., & Brand, H. R. (2016). Tetrahedral order in liquid crystals. Brazilian Journal (2019). Insight into thermal stability of cellulose nanocrystals from new hydrolysis
of Physics, 46(5), 565–595. https://doi.org/10.1007/s13538-016-0438-z methods with acid blends. Cellulose, 26(1), 507–528. https://doi.org/10.1007/
Rahman, A. (2013). Rheology of thermotropic liquid crystal polymers for injection moulding. s10570-018-2175-7
PhD Thesis. RMIT University. Vermant, J., Moldenaers, P., Picken, S. J., & Mewis, J. (1994). A comparison between
Rånby, B. G. (1951). Fibrous macromolecular systems. Cellulose and muscle. The texture and rheological behaviour of lyotropic liquid crystalline polymers during
colloidal properties of cellulose micelles. Discussions of the Faraday Society, 11(0), flow. Journal of Non-Newtonian Fluid Mechanics, 53, 1–23. https://doi.org/10.1016/
158–164. https://doi.org/10.1039/DF9511100158 0377-0257(94)85039-9
Reboredo, M. M., Marcovich, N. E., & Aranguren, M. I. (2008). Selected topics on Vlad-Cristea, M. S., Landry, V., Blanchet, P., & Ouellet-Plamondon, C. (2013).
polypropylene/wood flour composites: Thermal, mechanical and time dependent Nanocrystalline cellulose as effect pigment in clear coatings for wood. ISRN
response. In D. Nwabunma, & T. Kyu (Eds.), Polyolefin composites (pp. 150–177). Nanomaterials, 2013, 1–12. https://doi.org/10.1155/2013/930236
Wiley-Interscience. Walker, L., & Wagner, N. (1994). Rheology of region I flow in a lyotropic liquid-crystal
Rees, A., Powell, L. C., Chinga-Carrasco, G., Gethin, D. T., Syverud, K., Hill, K. E., et al. polymer: The effects of defect texture. Journal of Rheology, 38(5), 1525–1547.
(2015). 3D bioprinting of carboxymethylated-periodate oxidized nanocellulose https://doi.org/10.1122/1.550557
constructs for wound dressing applications. BioMed Research International, 2015, 1–7. Walker, L. M., Kernick, W. A., & Wagner, N. J. (1997). In situ analysis of the defect
https://doi.org/10.1155/2015/925757 texture in liquid crystal polymer solutions under shear. Macromolecules, 30(3),
Revol, J.-F., & Marchessault, R. H. (1993). In vitro chiral nematic ordering of chitin 508–514. https://doi.org/10.1021/ma960590e
crystallites. International Journal of Biological Macromolecules, 15(6), 329–335. Walker, L. M., Wagner, N. J., Larson, R. G., Mirau, P. A., & Moldenaers, P. (1995). The
https://doi.org/10.1016/0141-8130(93)90049-R rheology of highly concentrated PBLG solutions. Journal of Rheology, 39(5),
Revol, J.-F., Godbout, D. L., & Gray, D. G. (1997). Solidified liquid crystals of cellulose 925–952. https://doi.org/10.1122/1.550624
with optically variable properties (Patent No. 5,629,055). Wan, H., Li, X., Zhang, L., Li, X., Liu, P., Jiang, Z., et al. (2018). Rapidly responsive and
Revol, J.-F., Godbout, L., Dong, X.-M., Gray, D. G., Chanzy, H., & Maret, G. (1994). Chiral flexible chiral nematic cellulose nanocrystal composites as multifunctional
nematic suspensions of cellulose crystallites; phase separation and magnetic field rewritable photonic papers with eco-friendly inks. ACS Applied Materials & Interfaces,
orientation. Liquid Crystals, 16(1), 127–134. https://doi.org/10.1080/ 10(6), 5918–5925. https://doi.org/10.1021/acsami.7b19375
02678299408036525 Wang, P.-X., Hamad, W. Y., & MacLachlan, M. J. (2016). Structure and transformation of
Revol, J.-F., Bradford, H., Giasson, J., Marchessault, R. H., & Gray, D. G. (1992). tactoids in cellulose nanocrystal suspensions. Nature Communications, 7(1), 11515.
Helicoidal self-ordering of cellulose microfibrils in aqueous suspension. International https://doi.org/10.1038/ncomms11515
Journal of Biological Macromolecules, 14(3), 170–172. https://doi.org/10.1016/ Wilts, B. D., Dumanli, A. G., Middleton, R., Vukusic, P., & Vignolini, S. (2017). Invited
S0141-8130(05)80008-X Article: Chiral optics of helicoidal cellulose nanocrystal films. APL Photonics, 2(4),
Roman, M., & Winter, W. T. (2004). Effect of sulfate groups from sulfuric acid hydrolysis Article 040801. https://doi.org/10.1063/1.4978387
on the thermal degradation behavior of bacterial cellulose. Biomacromolecules, 5(5), Wissbrun, K. F. (1981). Rheology of rod-like polymers in the liquid crystalline state.
1671–1677. https://doi.org/10.1021/bm034519+ Journal of Rheology, 25(6), 619–662. https://doi.org/10.1122/1.549634
Sammartino, E. K., Reboredo, M. M., & Aranguren, M. I. (2016). Natural fiber- Wu, Q., Meng, Y., Wang, S., Li, Y., Fu, S., Ma, L., et al. (2014). Rheological behavior of
polypropylene composites made from caranday palm. Journal of Renewable Materials, cellulose nanocrystal suspension: Influence of concentration and aspect ratio. Journal
4(2), 101–112. https://doi.org/10.7569/JRM.2014.634144 of Applied Polymer Science, 131(15). https://doi.org/10.1002/app.40525. n/a-n/a.
Shafiei-Sabet, S., Hamad, W. Y., & Hatzikiriakos, S. G. (2014). Ionic strength effects on Xiong, R., Han, Y., Wang, Y., Zhang, W., Zhang, X., & Lu, C. (2014). Flexible, highly
the microstructure and shear rheology of cellulose nanocrystal suspensions. transparent and iridescent all-cellulose hybrid nanopaper with enhanced mechanical
Cellulose, 21(5), 3347–3359. https://doi.org/10.1007/s10570-014-0407-z strength and writable surface. Carbohydrate Polymers, 113, 264–271. https://doi.
Shafiei-Sabet, S., Hamad, W. Y., & Hatzikiriakos, S. G. (2012). Rheology of org/10.1016/j.carbpol.2014.06.069
nanocrystalline cellulose aqueous suspensions. Langmuir, 28(49), 17124–17133. Xu, T. (2014). Inorganic nanocylinder lyotropic liquid crystals: Rheology, phase behavior and
https://doi.org/10.1021/la303380v film self-assembly. PhD Thesis. Auburn University.
Shafiei-Sabet, S., Hamad, W. Y., & Hatzikiriakos, S. G. (2013). Influence of degree of Zakharov, A. V., Vakulenko, A. A., & Thoen, J. (2003). Tumbling instability in a shearing
sulfation on the rheology of cellulose nanocrystal suspensions. Rheologica Acta, 52 nematic liquid crystal: Analysis of broadband dielectric results and theoretical
(8–9), 741–751. https://doi.org/10.1007/s00397-013-0722-6 treatment. The Journal of Chemical Physics, 118(9), 4253–4260. https://doi.org/
Song, H., Zhang, J., Niu, Y., & Wang, Z. (2010). Phase transition and rheological 10.1063/1.1542597
behaviors of concentrated Cellulose/Ionic liquid solutions. The Journal of Physical Zhang, Y. P. (2012). Nanocrystalline cellulose for covert optical encryption. Journal of
Chemistry B, 114(18), 6006–6013. https://doi.org/10.1021/jp1013863 Nanophotonics, 6(1), Article 063516. https://doi.org/10.1117/1.JNP.6.063516
Sugiyama, J., Chanzy, H., & Maret, G. (1992). Orientation of cellulose microcrystals by Zhang, Y., Cheng, Q., Chang, C., & Zhang, L. (2018). Phase transition identification of
strong magnetic fields. Macromolecules, 25(16), 4232–4234. https://doi.org/ cellulose nanocrystal suspensions derived from various raw materials. Journal of
10.1021/ma00042a032 Applied Polymer Science, 135(24), 45702. https://doi.org/10.1002/app.45702
Thérien-Aubin, H., Lukach, A., Pitch, N., & Kumacheva, E. (2015a). Structure and Zhang, Y. P., Chodavarapu, V. P., Kirk, A. G., & Andrews, M. P. (2013). Structured color
properties of composite films formed by cellulose nanocrystals and charged latex humidity indicator from reversible pitch tuning in self-assembled nanocrystalline
nanoparticles. Nanoscale, 7(15), 6612–6618. https://doi.org/10.1039/C5NR00660K cellulose films. Sensors and Actuators B: Chemical, 176, 692–697. https://doi.org/
Thérien-Aubin, H., Lukach, A., Pitch, N., & Kumacheva, E. (2015b). Coassembly of 10.1016/j.snb.2012.09.100
nanorods and nanospheres in suspensions and in stratified films. Angewandte Chemie Zhu, Q., Yao, Q., Sun, J., Chen, H., Weihua, X., Liu, J., et al. (2020). Stimuli induced
International Edition, 54(19), 5618–5622. https://doi.org/10.1002/anie.201500277 cellulose nanomaterials alignment and its emerging applications: A review.
Carbohydrate Polymers, 230, Article 115609. https://doi.org/10.1016/j.
carbpol.2019.115609

14