International Journal of Biological Macromolecules 148 (2020) 811–816

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International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Rheology of regenerated cellulose suspension and influence of

a r t i c l e i n f o a b s t r a c t

Article history: Cellulosic colloidal suspensions present unique opportunities for rheological modification of complex fluids. In
Received 3 December 2019 this work, the rheological behavior of regenerated cellulose (RC) suspensions, including their oscillating shear
Received in revised form 16 January 2020 and time-dependent behavior, as well as yield stress, were studied. The rheological effects of sodium alginate's
Accepted 17 January 2020
addition to aqueous RC solutions subject to shear flow were investigated. The results reveal that the RC suspen-
Available online 18 January 2020
sion exhibited “gel-like” behavior and had a shear-thinning property. At increasing RC concentrations, the sus-
Keywords:
pensions' yield stress and the extent of viscosity recovery after plastic deformation had both increased. The
Regenerated cellulose viscoelastic suspensions underwent a transition from “solid-like” to “liquid-like” behavior upon sodium alginate's
Rheology inclusion. Sodium alginate was found to enhance RC suspensions' viscosity recoverability. Furthermore, with in-
Sodium alginate creasing concentrations of sodium alginate, the yield stress of RC suspension began to decrease and then
Yield stress vanished, occurring below the 1:1 RC: sodium alginate weight ratio with total solid content fixed at 1 wt%, due
Viscosity recovery to RC's inability to form an extended network RC. This study yields insights into the rheology of RC suspensions
and the influence of sodium alginate and supports both their usage as rheological modifies in applications such as
coatings, drug delivery systems, and additive manufacturing techniques such as 3D printing.
© 2020 Published by Elsevier B.V.

1. Introduction gaining further insight into the rheology of cellulosic colloids is es-
sential for their advancement.
Cellulosic colloids utilizing nanomaterials such as cellulose nano- Cellulosic colloids have been studied for some time now, and much
fibers and cellulose nanocrystals often feature favorable properties is known about their physical and chemical properties [11–15]. Cellu-
such as high available surface area per unit mass, low density, supe- losic colloids are natively hydrophilic due to cellulose's four secondary
rior mechanical strength and can be easily functionalized at the alcohol and two primary alcohol moieties per monomer, and thus
cellulose's primary alcohol sites [1–5]. Cellulose's unique suite of their often fibrillary morphology tends to swell in the presence of
physical and chemical properties combined with their readily avail- water. Cellulose's fibrillary morphology and swelling property lead to
able, easily renewable and environmentally benign and non-toxic, an entangled three-dimensional cellulose network [12]. Colloidal cellu-
biocompatible nature has led to its adoption in many successful ap- lose tends to exhibit higher viscosities with increasing degrees of fibril-
plications in both the industrial and daily use fields, such as drug de- lation and/or increasing colloidal concentration [16,17]. Fibrillation
livery excipients and reinforcing agents in polymer composites and increases the available cellulosic surface area which in turn increases
coatings, as well as personal care products [6–10]. For many of cellulosic network strength via an increased extent of van der Waals
these applications, especially coatings and personal care products, forces and intermolecular hydrogen bonding, increasing such colloids'
resistance to flow. The viscosity of such colloids typically exhibits
shear-thinning behavior due to disruption of the entangled three-
dimensional cellulosic networks and their intermolecular interactions
at higher shear frequencies [18,19]. This shear-thinning behavior is
⁎ Corresponding author at: Key Lab of Science and Technology of Eco-textile, Ministry of
Education, College of Chemistry, Chemical Engineering and Biotechnology, Donghua
often beneficial for product manufacturing, and is often crucial for vari-
University, Shanghai 201620, People's Republic of China. ous industrial operations such as storage, filtering, pulping, mixing, and
E-mail address: [email protected] (X. Sui). fine-tuning aesthetics [12,20]. Additionally, colloidal yield stress also

https://doi.org/10.1016/j.ijbiomac.2020.01.172
0141-8130/© 2020 Published by Elsevier B.V.
812 Y. Jiang et al. / International Journal of Biological Macromolecules 148 (2020) 811–816

strongly affects manufacturability and must be taken into account dur- 2.2. Preparation of regenerated cellulose
ing process manufacturing calculations [21]. Fluids that do not flow un-
less they are subjected to yield stress are widely used in both cosmetic The regenerated cellulose suspension was prepared by a modified
and industrial applications; well-known examples include mayonnaise literature procedure [32]. 2 g of wood pulp was wetted with 6 mL of de-
(an emulsion), shaving foam, both wet and dry sand and toothpaste ionized water and was then mixed with 200 mL of 85% aqueous phos-
[22]. Furthermore, in nearly all processing steps the viscosity recovery phoric acid, and the mixture was stirred at 350 rpm for 24 h at 0 °C.
properties of cellulose colloids are of upmost importance, as these sus- Afterward, the cellulose solution was added to 500 mL of deionized
pensions are often subject to a broad range of shear rates depending water to obtain a milky dispersion, which was then centrifuged at
on the processing step. For example, the viscosity of coating formulation 11,000g (Thermo, Multifuge X1R, USA) until a constant pH of 7 was
after mechanical action (such as brushing) can affect the resulting coat- obtained. The precipitated RC was collected and then treated with a
ing surface smoothness [23]. Too high of viscosity can cause stalactites high-pressure homogenizer (Spxflow, APV2000, Germany) at 100 bar.
to form on the coating blade, which can cause surface imperfections The RC solid content of the final suspension was 2% (w/w).
such as scratches and streaks [24], while too low of viscosity can lead
to sagging, such as drips, in the final dried film [25]. During additive 2.3. Scanning electron microscopy
manufacturing, a near-instant viscosity recovery is often desired, as,
for example, an ideal 3D printing ink formulation, which behaves as a A scanning electron microscope (SEM) (Hitachi, S-4800, Japan) was
fluid during its passage through the printing nozzle yet recovers its used to analyze the morphology of the original wood pulp. The solution
high viscosity soon after printing [26,27]. Despite this, to our knowl- was drop cast and allows the dry at ambient conditions, and then the
edge, few works exist which study the yield stress and viscosity recov- samples were sputtered coated with a 5 nm thick layer of osmium
ery of colloidal cellulose suspensions. (Neo Osmium Coater, Meiwafosis) at 5 mA for 5 s. The electron images
Native cellulose can be fibrillated by either acid hydrolysis and/or were obtained at an acceleration voltage of 5 kV.
mechanical treatments to produce various forms of cellulosic colloidal
suspensions, such as cellulose nanocrystals (CNC) and microfibrillated 2.4. Transmission electron microscopy
cellulose (MFC). However, CNC yield is generally low and was reported
to be approximately 30% due to complete hydrolysis of amorphous cel- The morphology of RC was characterized using transmission elec-
lulose domains by acid. Mechanical treatments require relatively high tron microscopy (TEM, JEM-2100, JEOL, Japan). Samples were prepared
energy inputs, reaching 25,000 kWh per ton needed to prepare MFC. by drop casting 30 μL of an aqueous RC dispersion (RC content
In contrast with other nanocellulose materials, regenerated cellulose 0.1 mg/mL) onto a carbon coated copper grid. The samples were subse-
(RC) can be prepared in high yield (N80%) by simple solvent dissolution quently dried in an oven held at 50 °C for 2 h. After drying, the samples
and successive anti-solvent regeneration, increasing their economic were observed at 200 kV.
viability and decreasing their environmental impact. In contrast with
other nanocellulose materials, regenerated cellulose (RC) can be pre- 2.5. Rheological measurements
pared in high yield (N80%) by simple solvent dissolution and successive
anti-solvent regeneration [28–30]. In our previous work, RC was used as Rheological analyses were performed on a Thermo Haake-Mars 60
a viscoelastic additive to improve waterborne polyacrylate latex resin rheometer with a parallel plate (35 mm in diameter). Amplitude
sag resistance, as its inclusion promotes high zero-shear viscosity and sweeps were conducted by altering shear strain from 0.1% to 100% at a
shear-thinning properties at elevated shear rates [31]. Additionally, fixed frequency of 1 Hz. The samples were also subjected to frequency
creep measurements showed that RC inclusion reduced latex creep sweeps ranging from 0.1 to 10 Hz at a fixed strain of 1% to study their
microstress (1 Pa) and imparted high elastic deformation recoverability viscoelastic behavior. Thirdly, time-dependent fluid analyses under
due to RC network formation and the resulting increase in particle- shear rates alternating from 0.1 s‐1 at 2 Pa to 10 s‐1 at 20 Pa and finally
particle interactions. back to 0.1 s‐1 at 2 Pa were carried out to study the viscosity recovery
In this work, we obtained further insight into the rheology of cel- behavior of the samples. Finally, the samples' stress/strain curves were
lulose colloids, with an emphasis on elucidating rheological proper- obtained by subjecting the samples to shear-stresses which were pro-
ties essential to manufacturing such as yield stress and RC viscosity gressively increased from 1 Pa to 50 Pa, and the samples' yield stress
recovery after subjection to high shear rates (plastic deformation). was calculated from these results. A log-log plot of the stress/strain
Furthermore, in this study, the effect of the water-soluble polymer curve produced two linear segments. The intersection of the linear seg-
sodium alginate on the rheology of regenerated cellulose suspen- ments indicated the crossover from elastic behavior to flow and gave
sions during shear flow was also investigated. The “solid-like” to “liq- the yield stress. All rheological measurements were carried out at 25 °C.
uid-like” behavior transition of the viscoelastic RC/sodium alginate
colloid at varying component concentrations were found. Further- 3. Results and discussion
more, the addition of sodium alginate to RC colloids was found to
promote rapid viscosity recovery in response to plastic deformation. The morphology of wood pulp as-received and subsequently regen-
This study deepens our understanding of RC rheology and extends erated cellulose was observed by SEM and TEM, respectively. The mor-
their potential scope as rheological modifies in other chemical fami- phological analysis revealed the presence of individual large fibers
lies yet to be realized. (diameter ~30 μm) in the raw wood pulp which were not observed in
regenerated cellulose. As shown in the TEM (Fig. 1b), regenerated cellu-
lose had a diameter of 20–40 nm in the nanometer range and several
2. Materials and methods micrometers in the length, consistent with that of our previous report
[19,32]. Well-dispersed, stable regenerated cellulose suspensions were
2.1. Materials obtained by advanced fibrillation from as-received wood pulp. As
shown in the insert of Fig. 1b, the stability of such RC suspensions did
Bleached soft wood pulp was obtained from Xinxiang Natural Chem- not change with extended storage of up to 7 days. The stability of
ical Co., Ltd. Phosphoric acid (reagent grade 85 wt%) and sodium algi- these RC suspensions is not due to electrostatic repulsions, as they fea-
nate were supplied by Sinopharm Chemical Reagent Co. Ltd., China. All ture a low zeta potential value (approximately −10 mV) as reported
chemicals were used as received. Aqueous solutions were prepared in our previous work [33] and are thus insensitive to changes in electro-
using deionized water. lytes and pH [34]. RC fibers tend to form locked flocs due to their large
 Y. Jiang et al. / International Journal of Biological Macromolecules 148 (2020) 811–816 813

Fig. 1. (a) SEM image of raw wood pulp, (b) TEM image of regenerated cellulose (RC). In the insert, photograph of 1 wt% RC suspension after 7d storage.

aspect ratio, which promotes the formation of three-dimensional (3D) entanglements. The RC suspension viscosity as a function of frequency,
entanglements, which are further enhanced by intermolecular interac- with varied RC concentrations, is shown in Fig. 3b. With an increase in
tions such as van der Waals' forces and hydrogen bonding. The flocs the RC concentration, the viscosity of the suspension increased, again
remain stable under sufficiently gentle shearing (shear rate 1 s−1) and due to increased extent of van der Waals forces and hydrogen bonding
remain well-dispersed in aqueous solutions, despite being denser than per unit volume. The viscosity of all suspensions regardless of RC con-
water. RC suspensions appear white due to the entangled RC fibers act- centration exhibited shear-thinning behavior due to disruption of the
ing as Mie scattering centers. entangled three-dimensional RC network, breaking up RC intermolecu-
To characterize their mechanical response to oscillatory forces, the lar forces and disrupting adoption of the gel phase in favor of a more
RC suspensions were subjected to an oscillating shear deformation liquid-like phase.
with a successively increased strain amplitude from 0.1% to 100% at Viscosity and viscosity recovery time measurements at lower and
1 Hz, and then the shear storage (G′) and loss (G″) moduli were evalu- higher shear rates (0.1 s‐1 and 10 s‐1) were also conducted, revealing
ated as a function of the shear strain amplitude. In the linear viscoelastic the thixotropic and structure-recovery properties of the RC suspension.
region, i.e. where the moduli are independent of the applied shear As shown in Fig. 4, an increase in the RC concentration led to an increase
strain, G′ is higher than G″, indicating a solid- or gel-like behavior [35]. in the apparent viscosity of the RC suspension, over a shear rate range of
As shown in Fig. 2, above a certain “critical” strain amplitude (strain am- 0.1‐10 s‐1. All of the RC suspensions displayed a shear-sensitive behavior
plitude = 8%), which was nearly identical for all the suspensions, both whereby the viscosity at the lower shear rate (0.1 s‐1) was greater than
the moduli and viscosity of all suspensions started to decrease, corre- one thousand times that at a higher shear rate (10 s‐1) as shown in
sponding to a breakdown or disruption of the elastic network formed Table 1. When the shear rate was set back to the original value
by the RC fibers. (0.1 s‐1), the viscosity of the RC suspension recovered after 180 s. The
In addition to the amplitude sweeps described above, frequency viscosity of all RC suspensions after subjection to the 10 s‐1 shear rate
sweeps of viscoelastic parameter measurements ranging from 0.1 to was relatively low compared to the original value under lower shear
10 Hz at a fixed strain of 1% were made on the RC samples, to further rate, only 26.1% of original viscosity at 1 wt% RC and 14.1% at 0.5 wt%
study the effect of RC concentration on their resulting structural proper- RC, indicating that the disrupted 3D entangled network between RC fi-
ties. As shown in Fig. 3a, an increase in the RC concentration resulted in bers during higher shearing rates cannot readily self-assemble [36]. The
a progressive increase in the gels' strength, as indicated by an increase in observed lack of full viscosity recovery for all samples may be due to
G′, G″ and viscosity. The RC suspensions displayed “solid-like” behavior irreversible degradation of the RC flocs, promoting smaller entangled
due to molecular interactions within and between neighboring RC RC flocs and perhaps even individual RC strands in the colloid [37].

Fig. 2. (a) The storage and loss modulus as a function of amplitude modulated sweeps show increasing colloidal stiffness as RC concentration increases. The critical strain, represented by
the black vertical line, mark breakdown or disruption of the RC network. (b) Viscosity as a function of applied shear strain shows RC colloids of various concentrations.
814 Y. Jiang et al. / International Journal of Biological Macromolecules 148 (2020) 811–816

Fig. 3. Characterization of colloidal RC viscoelastic behavior as a function of applied frequency at fixed shear amplitude 1%. (a) Shear stress storage and loss moduli as a function of applied
frequency both increase with increasing RC concentrations. (b) Viscosity of RC solutions increases with increasing RC concentrations due to the development of more entangled cellulosic
networks. Furthermore, their viscosity exhibits shear-thinning behavior due to increasing disruptions to the RC network, breaking up RC intermolecular forces and disrupting adoption of
the gel phase in favor of a more liquid-like phase.

Fig. 4. Time-dependent behavior of RC suspensions mixed at 0.1 s‐1 and 10 s‐1. (a) Viscosity is reduced by about three orders of magnitude upon subjection to high shear rate, due to
disruption of the RC's inter- and intramolecular forces. As previously seen, viscosity of samples with higher RC loading is higher than samples with lower RC loading. (b) The viscosity
recoverability of RC suspensions at three concentrations. Greater RC loading promotes increased viscosity recoverability due to the increased interactions between RC fibers and
agglomerates per unit volume.

Colloidal yield stress is proportional to the coherence of the RC net- entangled colloidal systems, the yield stress represents the point
work structure. Fluids that do not flow unless they are subjected to yield where the applied force is capable of breaking down or disrupts the
stress are particularly important for tuning the final appearance of prod- elastic network.
ucts, drip reduction of coatings, preventing unwanted flow, and imped- Polyelectrolytes and their resulting influence on the fluid's ionic
ing settling of suspended fine particles [38]. As shown in Fig. 5, an strength must be taken into account when developing a total descrip-
increase in the RC concentration resulted in an increase of the suspen- tion of a colloid's behavior. Towards this end, we studied the influence
sions' yield stress, as indicated by a right shift of yield stress from
3.2 Pa to 10.1 Pa, due to enhancement of the extended RC network.
For applied stresses less than the yield stress, the material deforms elas-
tically and will return to its original shape when the applied stress is
removed. As shown in Fig. 5, when the shear stress is above the yield
stress, the system will plastically deform and further deformation
occurs rapidly, even with small applied shear stress increase. In such

Table 1
Effect of RC content on viscosity at lower and higher shear rates (0.1 s‐1 and 10 s‐1).

RC content (wt%) 0.1 s‐1 (mPa·s)a 10 s‐1 (mPa·s) 0.1 s‐1 (mPa·s)b

6807 4 960
0.5

34,765 25 7961
0.8

84,991 84 22,182
1
Fig. 5. Yield stress of RC suspensions at varying concentrations. An increase in the RC
a
The viscosity at the lower shear rate (0.1 s−1). concentration resulted in an increase in the yield stress, as indicated by increase of the
b
The viscosity at original value (0.1 s−1) after a higher shear rate (10 s−1). yield stress from 3.2 Pa at 0.5% RC to 10.1 Pa at 1% RC, due to the enhanced RC network.
 Y. Jiang et al. / International Journal of Biological Macromolecules 148 (2020) 811–816 815

Fig. 6. Frequency sweeps of regenerated cellulose and sodium alginate suspensions varying weight ratios of RC and sodium alginate, wherein the total solid content was fixed at 1 wt%. The
viscoelastic suspensions underwent a transition from “solid-like” behavior to “liquid-like” behavior when the RC: sodium alginate weight ratio is b3:7.

of a commonly used rheological modifying agent, sodium alginate, on recoverability than increasing RC concentration, as Coulombic repulsion
the resulting colloid's rheological properties. As shown in Fig. 6, for all between the alginate's charged moieties prevents their aggregation,
tested RC concentrations the total solid content was fixed to be 1 wt%, thereby diminishing network formation in suspension, thus decreasing
and in this configuration an increasing concentration of sodium alginate their viscosity [42,43]. Compared with the fully dissolved alginate mol-
(decreasing RC content) resulted in a decrease in the gels' strength, as ecules, aqueous RC forms fiber flocs and adopts an entangled 3D net-
indicated by the decrease values of G′ and G″, explained by both the dis- work configuration which required more time for self-assembly into
ruption of the RC network in the bulk phase and by the lubricating effect their thermodynamically favored extended network state [19], thus
of sodium alginate as reported by Bououa et al [39,40]. In short, Bououa increasing the time required for complete viscosity recovery. Our ability
et al. found that charged polymers tend to separate solid particles from to tune RC suspensions' viscosity, storage and loss moduli and viscosity
each other due to electrostatic repulsive force, thereby decreasing the recovery time increases the potential applied scope of RC colloidal prod-
extent of interaction between neighboring solid particles, thus lowering ucts, enabling their use in previously inaccessible applications.
the RC network's strength. When the RC: sodium alginate weight ratio is As shown in Fig. 8, the addition of sodium alginate has a dramatic
N3:7, the RC sodium alginate suspensions exhibited “solid-like” behav- effect on the yield stress of RC suspensions upon the addition of sodium
ior. This is intuitive as such suspensions feature storage modulus larger alginate the yield stress of the suspension first decreased and then
than their loss modulus. However, when the RC: sodium alginate vanished below the 1:1 RC: sodium alginate weight ratio, due to RC
weight ratio was b3:7, we observed G′ values less than their G″ values, being unable to adopt an extended 3D network. The impact of de-
indicating dominance of “liquid-like” viscous behavior of the viscoelas- creased RC concentration was also observed in the varying shear fre-
tic samples, due to both the lowered concentration of cellulose, thus quency sweeps of the suspension. With higher RC content, the
weakening of RC network, as well as the increased concentration of suspension displayed “solid-like” behavior. This means energy can
sodium alginate, which exhibits viscous behavior [41]. store in the elastic deformation of suspension, which exhibits higher
Addition of sodium alginate also affects the structural recovery prop- yield stress. When the RC content was low, the suspension changed to
erties of RC suspensions. As shown in the Fig. 7a, an increase in sodium “liquid-like” behavior and had a higher loss modulus than the storage
alginate concentration (with total solid content again being fixed at 1 wt modulus. Sodium alginate's ability to modify RC suspensions' yield
%) resulted in a decrease of the suspensions' viscosity. This decrease of stress and to change “solid-like” behavior into “liquid-like” behavior
viscosity is partially due to the lessened RC concentration, which leads expands their scope of use, as processes such as flow-leveling tend to
to less network entanglement and thus less intermolecular interactions scratch and streak if the colloidal yield stress is too high, while too
between RC fibers; however, our data (Table 2) shows that the sodium low of a yield stress leads to dripping and loss of vertically applied coat-
alginate concentration plays a greater role in the observed viscosity ing products.

Fig. 7. Time-dependent fluid behavior of regenerated cellulose and sodium alginate suspensions of varying weight ratios, where the total solid content was fixed to be 1 wt%. Introduction
of sodium alginate to RC suspensions improved their viscosity recoverability.
816 Y. Jiang et al. / International Journal of Biological Macromolecules 148 (2020) 811–816

Table 2 Acknowledgements
Effect of regenerated cellulose and sodium alginate suspensions of varying weight ratios
on viscosity at lower and higher shear rates (0.1 s‐1 and 10 s‐1).
This work was financially supported by the Fundamental Research
RC:SA 0.1 s‐1 (mPa·s)a 10 s‐1 (mPa·s) 0.1 s‐1 (mPa·s)b Funds for the Central Universities (grant numbers: 2232019A3-06).
10:0 84,991 84 22,182
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Fig. 8. Yield stress of regenerated cellulose and sodium alginate suspensions at different
weight ratios, where the total solid content was fixed to be 1 wt%. Yield stress of
suspensions upon the addition of sodium alginate decreased and then vanished below
the 1:1 RC: sodium alginate weight ratio, due to RC being unable to adopt an extended
3D network.