Nanocomposites

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Sonication amplitude and processing time

influence the cellulose nanocrystals morphology
and dispersion

Jamileh Shojaeiarani, Dilpreet Bajwa & Greg Holt

To cite this article: Jamileh Shojaeiarani, Dilpreet Bajwa & Greg Holt (2020): Sonication
amplitude and processing time influence the cellulose nanocrystals morphology and dispersion,
Nanocomposites, DOI: 10.1080/20550324.2019.1710974

To link to this article: https://doi.org/10.1080/20550324.2019.1710974

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NANOCOMPOSITES
https://doi.org/10.1080/20550324.2019.1710974

RAPID COMMUNICATION

Sonication amplitude and processing time influence the cellulose

nanocrystals morphology and dispersion
Jamileh Shojaeiarania , Dilpreet Bajwab and Greg Holtc
a
Department of Mechanical Engineering, Western New England University, Springfield, MA, USA; bDepartment of Mechanical and
Industrial Engineering, Montana State University, Bozeman, MT, USA; cCotton Production and Processing Research Unit,
USDA-ARS, USA

ABSTRACT ARTICLE HISTORY

The application of bio-based materials is becoming impellent owing to the increasing Received 1 November 2019
demand for alternatives to petroleum-based analogs. In this regard, cellulose nanocrystals Accepted 27 December 2019
(CNCs) with unique properties have received a significant interest, while their hydrophilic
KEYWORDS
character poses a challenge to their commercial applications. Ultrasonication treatment is
Sonication amplitude;
one of the most commonly used methods to improve CNCs’ dispersion in different solvents sonication time; cellulose
and polymer matrices. In this work, the effectiveness of ultrasonication treatment in the dis- nanocrystals; dispersion;
persion of CNCs in a water-soluble polymer (polyvinyl alcohol, PVA) was studied. An aqueous particle size
suspension of polyvinyl alcohol and CNCs was prepared using different ultrasonication times
and amplitudes. The morphology, particle size and dispersion of CNCs were studied using
X-ray diffraction, transmission electron microscopy, and dynamic light scattering. The results
indicated that with increase in the sonication amplitude, there was a substantial decrease in
nanoparticle length, while long sonication times gently affected the nanoparticle length.
Furthermore, improved dispersion was observed in samples prepared using longer sonic-
ation time.

GRAPHICAL ABSTRACT

1. Introduction
the world which can be isolated from a wide range
During the last decade, numerous studies have been of renewable resources such as algae, bacteria,
focused on the development and implementation of plants, and tunicates.
biopolymers owing to an increased concern over Cellulosic materials with different shapes, sizes
environmental sustainability and biocompatibility. and crystallinity can be produced through different
Among different biopolymers, cellulose is one of the treatments including acid hydrolysis, mechanical
most abundant and naturally occurring polymers in shearing and enzymatic hydrolysis [1–5]; cellulose

CONTACT Jamileh Shojaeiarani [email protected] Department of Mechanical Engineering, Western New England University,
Springfield, MA 01119, United States
ß 2020 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
2 J. SHOJAEIARANI ET AL.

high-pressure (compression) and low- pressure (rar-

efaction) cycles, with rates depending on the
frequency [10]. In the low-pressure cycle, small vac-
uum bubbles or voids are formed in sonicated liquid
as a result of high-intensity ultrasonic waves. These
bubbles reach a maximum volume at which they
can no longer absorb energy and then violently
breakdown during a high-pressure cycle (Figure 1).
The bubbles breakdown, which is called cavita-
tion, creates dramatic effects in the sonicated liquid
and give rise to pressures up to 1000 atm and tem-
Figure 1. Ultrasonication mechanism involving compression
peratures of up to 5000 K [11]. Acoustic cavitation
and rarefaction cycles, and bubble formation within a
liquid medium. impact is strong enough to split up the fine particle
agglomerates and disperse them more uniformly in
nanocrystals (CNCs) are rod-like shaped structures liquids [12]. In the sonication process, sonication
containing only crystalline domains of cellulose. power, amplitude, time, and probe surface area
They can be extracted from cellulose through two describe the amount of energy delivered to the sus-
steps; the first step includes the complete or partial pension, and inconsistent application of ultrasonic
removal of matrix materials such as hemicelluloses treatment is more likely to contribute towards vari-
and lignin [6]. In the second step, which is a con- ability in the results. Although sonication is a well-
trolled acid hydrolysis, the amorphous regions of introduced technique to promote the dispersion of
the cellulose polymer are removed which results in nanofillers in different solvents, there are very few
single and highly crystalline nanofibers. CNCs are of reports explaining the effects of sonication inputs
highly desirable due to their unique features, such such as power and time on the dispersion of CNCs
as high aspect ratio of 10-70, high surface area of in an aqueous medium.
150 m2/g, and high strength and modulus (10 and In this study, an aqueous suspension of polyvinyl
150 GPa, respectively), depending on the method of alcohol (PVA) and CNCs was prepared using differ-
isolation and the source of cellulose [7]. ent ultrasonic treatments to investigate the disper-
The presence of a large number of hydroxyl sion of CNCs in a polymeric matrix as a function of
groups on the surface of the CNCs and intermolecu- different energy input and sonication time.
lar and intramolecular hydrogen bonding creates the Polyvinyl alcohol (PVA) is a biocompatible and bio-
challenge of utilizing CNCs as advanced materials degradable non-toxic synthetic polymer with appli-
for commercial applications. The abundant hydro- cation in diverse fields such as biomedical, food
gen bonds of cellulose draw the cellulose nanocrys- packaging and absorbents. To the best of our know-
tals together and result in the high tendency to ledge the ultrasonic treatments of CNCs in the pres-
form bundles or aggregates [8]. So far, several modi- ence of aqueous solutions of dilute PVA has not
fication techniques have been proposed for altering been described previously. Due to the large number
the hydrophilic character of CNCs and improving of hydroxyl groups in PVA, strong interfacial hydro-
their dispersion in different solvents and polymer gen bonds can be formed between PVA and CNCs,
matrices. In addition to chemical surface modifica- making a completely miscible polymeric nanocom-
tion treatments, the application of mechanical tech- posite. However, the high tendency in forming
niques has been reported to improve the dispersion aggregates in CNCs still required the application of
of CNCs in different media [9]. different methods such as ultrasonic treatment to
Among different mechanical pre-processing tech- improve their dispersion quality even in a water sol-
niques, ultrasonication has been widely employed as uble polymer.
a practical step for improving the dispersion of
CNCs in polymer matrices. In the ultrasonication 2. Experimental
process, the sonic waves are applied to a CNC sus-
2.1. Materials
pension to break apart and de-agglomerate the CNC
bundles. In the sonication process, ultrasound waves Unmodified freeze-dried cellulose nanocrystals
are applied to specimens with frequencies in the extracted from pine wood fibers were supplied by
non-audible range (>20 kHz, 20,000 cycles per Forest Product Society (Madison, WI, USA).
second) and as frequency increases the strength of Polyvinyl alcohol (PVA) with the molecular weight
the agitation increases. of 89,000-98,000 and the degree of hydrolysis of
In the ultrasonication process, the sound waves 99% was purchased from Sigma Aldrich (St. Louis,
that propagate into the liquid generate alternating MO, USA).
 NANOCOMPOSITES 3

Table 1. Codification and combinations of time and ampli- Table 2. DLS measurements of CNCs in different PVA-CNCs
tude of ultrasoniction force applied on PVA-CNC samples. suspensions.
Sample code Time (min) Amplitude (mm) Sample code Length (nm) Aspect ratio
T4-A60 4 60 Unmodified CNCs 175.2 ± 5.4 27.5 ± 6.3
T4-A90 4 90 T4-A60 169.0 ± 11.8 25.9 ± 8.1
T7-A60 7 60 T4-A90 151.5 ± 8.9 24.2 ± 9.4
T7-A90 7 90 T7-A60 165.4 ± 11.8 24.4 ± 7.3
T10-A60 10 60 T7-A90 135.3 ± 11.1 20.6 ± 8.8
T10-A90 10 90 T10-A60 139.6 ± 6.5 21.7 ± 6.2
T10-A90 116.6 ± 7.3 17.9 ± 8.0

2.2. CNC suspension and ultrasonication process

aqueous suspension on carbon-coated copper grids
Aqueous PVA-CNCs suspension was prepared by under suitable conditions.
dispersing equal amounts of 1% wt. of PVA and
CNCs powder in distilled water using a homogen- 2.3.3. X-ray diffraction (XRD)
izer (IKA, Ultra-turrax T25, Germany) at room tem- Crystallinity index (CrI) is a parameter commonly
perature (23
C). An ultrasonic processor (Hielscher used to calculate the percentage of crystallinity in cel-
UIP1000hd, 20 kHz, Germany) with a 19 mm diam- lulosic materials. X-ray diffraction analysis is an ana-
eter probe was used to obtain a dispersion contain- lytical method which can quantify CrI using Segal’s
ing individual CNC nanoparticles. PVA-CNCs method, as shown in the following equation [13]:
suspension (100 ml) was processed at a constant fre- 
CrI ¼ ðI002 Iam Þ I002
quency of 20 kHz and two different levels of ampli-
tude (60 and 90 mm) and three time periods (4, 7, where I002 is the maximum intensity of the peak for
10 min) in order to study the effect of sonication the crystalline material at 2h ¼ 22.5
and Iam is the
time and amplitude on CNCs dispersion in polymer intensity at 2h of 18.5
, which represents amorphous
matrix. The ultrasonication energy input was con- material.
trolled by adjusting the amplitude of the sonicator In this study, X-ray diffraction analysis was used to
probe. During the sonication process, samples were evaluate the effect of sonication times and amplitudes
kept in an ice bath to ensure that the PVA-CNC on the crystal structure of CNCs in PVA-CNCs suspen-
suspension did not heat up and degrade the matrix. sions. XRD data were explored using a Rigaku Smartlab
The ultrasound probe was submerged to a depth of X-ray diffractometer equipped with Cu Ka radiation
20 mm in the samples. The sample codifications and source (k ¼ 0.154 nm) at 40 kV and 40 mA from 10-50

preparation conditions are shown in Table 1. (2h angle range) and 1
/min of scanning speed.

2.3. Characterization of CNCs 3. Results and discussion

2.3.1. Dynamic light scattering (DLS) 3.1. Dynamic light scattering (DLS)
It is a non-invasive method which measures the In this work the effect of sonication treatment on
translational diffusion coefficient of dispersed par- the CNCs morphology and dispersion characteristics
ticles, undertaking Brownian motion. The mean par- in a water-soluble polymer matrix were studied. The
ticle size and particle size distribution for the particle size distribution of CNCs as a function of
dispersed cellulose nanocrystals were determined ultrasonication treatment was evaluated using DLS
using a dynamic light scattering instrument (DLS- and the mean values of hydrodynamic length of par-
ZP/Particle Sizer NicompTM 380 ZLS). The detec- ticles are summarized in Table 2. DLS analysis
tion was made at a scattering angle of 90
and the shows that the hydrodynamic length values of CNCs
viscosity value for water was used in all measure- obtained ranges from 116.6 to 169.0 nm, depending
ments. Each measurement was performed in tripli- on the time and the amplitude of ultrasonication
cate, and mean values are reported. process. When the amplitude of the sonication pro-
cess increases, the particle size of the CNCs substan-
2.3.2. Transmission electron microscopy (TEM) tially decreases. Amplitude represents the distance
The morphology and the crystalline nature of CNCs that sonicator tip can longitudinally fluctuate and by
were further studied using high-resolution transmis- increasing the amplitude, cavitation intensity within
sion electron microscopy (HRTEM) using JEOL liquid is also increased.
JEM-100 CX II transmission electron. The suspen- The reduction in the particle size of CNCs was
sions were diluted 50x with distilled water and the mainly as a result of fiber breakage due to particle
nanofillers were stained with positively charged dye agitation [14] which happened at higher ultrasonica-
uranyl acetate prior to imaging. The sample for tion amplitude known as harsh condition. Time of
HRTEM was prepared by placing a drop of the sonication was another factor which governed the
4 J. SHOJAEIARANI ET AL.

Figure 2. Representative TEM images of PVA-CNCs suspensions prepared at different times (T, min) and ultrasonication ampli-
tudes (A, mm).

amount of acoustic energy delivered to the suspen- microparticles after ultrasonication processing was
sion and higher sonication times slightly degraded studied using HRTEM images. Figure 2 illustrates
the structure of the CNCs and this in turn, reduced the TEM images of PVA-CNCs suspensions after
the length of the CNCs. ultrasonication treatments. As expected, more CNC
Beside the length of individual CNCs, the effect bundles were observed in the sample which was
of time and the amplitude of ultrasonication process treated for 4 min (T4-A60 and T4-A90). However,
on aspect ratio of CNCs was also studied and the the presence of individual CNC particles in the
results are summarized in Table 2. The aspect ratio PVA-CNCs suspension showed evidence of
of CNCs displays a similar trend as CNCs’ length is improved dispersion of CNCs in T7-A90, in fact,
more vulnerable than the diameter of individual the longer sonication time in T10-A60 and T10-A90
fibers [15]. Cellulose nanocrystals subjected to delivered greater ultrasound energy input, and this
higher ultrasonication amplitude for the same time resulted in a more uniform dispersion of CNC in
had lower aspect ratio than their counterpart proc- the polymer matrix. The results are in agreement
essed at lower amplitude. The relatively high stand- with another study on particle size analysis using
ard deviation in aspect ratio of CNCs confirmed the DLS and image processing software confirmed
polydispersity of CNCs. decreasing nanocellulose length in suspensions
which were subjected to ultrasound wave for 10 min
[16, 17]. As it was reported elsewhere, the long and
3.2. Transmission electron microscopy (TEM)
aggressive ultrasonic treatment could destroy nano-
The extraordinary tendency of cellulose nanopar- fiber structure and consequently damaging its crys-
ticles to form aggregates which result in sediment as tallinity and mechanical properties [18].
 NANOCOMPOSITES 5

Figure 3. X-ray diffractograms of PVA-CNCs prepared at different time and amplitude ultrasonication treatments.

3.3. X-ray diffraction (XRD) Table 3. Crystallinity index of CNCs in different PVA-
CNCs suspension.
The application of ultrasonication treatment on
Sample code CI
crystallinity index of CNCs was studied using XRD Unprocessed CNCs 68.6
and the representative XRD diffraction pattern of T4-A60 67.8 ± 1.5
each formulation is shown in Figure 3. PVA is T4-A90 62.1 ± 1.7
T7-A60 66.1 ± 1.9
known to be a semi-crystalline polymer in nature T7-A90 60.5 ± 1.1
and the diffractogram exhibited a characteristic peak T10-A60 65.6 ± 2.1
T10-A90 56.3 ± 1.3
at 2h ¼ 19.5
assigned to the (101) crystallographic CI: Crystallinity Index.
plane for semi-crystalline PVA [19]. A well-defined
CNCs diffraction peak at 22.5
was observed for sonicated for longer time (10 min) and higher
samples sonicated for 4 min, while peak intensity amplitude (90 mm) was significantly lower than the
decreased as ultrasonication treatment time and rest of the samples. Moreover, high amplitude
amplitude increased. The XRD curve of T10-A60 (90 mm) reduced the length of CNCs by 17% in
and T10-A90 showed a broad and weak peak in the comparison with lower levels of amplitude (60 mm)
22–25 2h region indicating that crystalline structure for samples sonicated for equal time. By increasing
of CNCs altered as a result of harsh ultrasonica- the sonication time and amplitude the crystallinity
tion treatment. index of CNC decreased by 12% as ultrasound
The crystallinity index (CI) calculated for the energy destroyed the crystalline structure of CNC.
samples prepared using different preparation meth- The results of this study can be helpful in optimiz-
ods is summarized in Table 2. In the crystallinity ing the ultrasonication treatment process for pro-
determination, using the Segal method, the intensity moting uniform dispersion of CNCs and
Iam at 18.5
was overlapping with the tail of the controlling their morphology.
PVA peak. Therefore, to remove the PVA compo-
nent diffractograms were deconvoluted. It can be
Acknowledgement
observed that by increasing the sonication time and
amplitude the crystallinity index of CNC decreased. The authors would like to thank to the USDA-ARS,
Ultrasound energy transferred to the CNC destroyed Cotton Production and Processing Research Unit in
Lubbock, TX for their financial supports.
the crystalline structure of CNC and lowered the
crystallinity index (Table 3).
Disclosure statement
4. Conclusion No potential conflict of interest was reported by
the authors.
This study evaluated the effect of ultrasonication
amplitude and time on cellulose nanocrystals
Notes on contributors
morphology and dispersion in a water-soluble poly-
mer. The particle size, crystallinity, morphology, Dr. Jamileh Shojaeiarani is currently working as an
and dispersion of CNCs were studied using Assistant Professor in the Department of Mechanical
Engineering at Western New England University,
dynamic light scattering (DLS), X-ray diffraction Springfield MA, USA. Prior to joining Western New
(XRD), and transmission electron microscopy England University, she worked as a research fellow at
(TEM). The results confirmed that ultrasonication North Dakota University under the supervision of Dr.
time and amplitude had considerable impact on Bajwa. She graduated from North Dakota University,
cellulose nanocrystals morphology, crystallinity, and Fargo, ND in 2018 with doctorate in Mechanical
Engineering. Her research interests lie in the area of poly-
their dispersion throughout the PVA matrix, while mer-based high performance nanocomposites, cellulose
the amplitude effect was very profound. As nanocomposite hydrogels, sustainable production of mate-
expected, the measured particle size of CNCs rials from renewable resources, water cleaning
6 J. SHOJAEIARANI ET AL.

membranes, and conversion of biomass into bio-based water resistance properties of injected wood–high
industrial products. She has presented her research in sev- density polyethylene composite. Wood Fiber Sci.
eral national and international conferences and meetings 2015;47:365–374.
and has authored numerous research papers and technical 4. Siqueira G, Tapin-Lingua S, Bras J, et al.
reports, in various journals and books. Morphological investigation of nanoparticles
obtained from combined mechanical shearing, and
Dr. Dilpreet Bajwa is currently working as a Professor in enzymatic and acid hydrolysis of sisal fibers.
the Department of Mechanical and Industrial Engineering Cellulose 2010;17:1147–1158.
at Montana State University, Bozeman MT, USA. Prior to 5. Wang Q, Zhao X, Zhu JY. Kinetics of strong acid
joining the academia, he worked in the engineered wood/ hydrolysis of a bleached kraft pulp for producing
polymer composites industry (International Paper, cellulose nanocrystals (CNCs). Ind Eng Chem Res.
Masonite Corp., Greenland Composites) for 13 yrs. in 2014;53:11007–11014.
various R&D roles and served as an Adjunct Professor in 6. Moon RJ, Martini A, Nairn J, et al. Cellulose nano-
the Department of Agriculture and Biological Engineering materials review: structure, properties and nano-
at the University of Arkansas, Fayetteville, AR. He grad- composites. Chem Soc Rev. 2011;40:3941–3994.
uated from University of Illinois at Urbana-Champaign in 7. Yin Y, Tian X, Jiang X, et al. Modification of cellu-
2000 with doctorate in Wood Science and Engineering. lose nanocrystal via SI-ATRP of styrene and the
Dr. Bajwa’s area of research focuses on development of mechanism of its reinforcement of polymethylme-
novel, sustainable, multifunctional materials from renew- thacrylate. Carbohydrate Polym. 2016;142:206–212.
able feedstocks, functionalization of nanocellulosic materi- 8. Ye D, Yang P, Lei X, et al. Robust anisotropic cellu-
als for developing safe fire-retardant system for polymer lose hydrogels fabricated via strong self-aggregation
composites, processing and characterization of biopoly- forces for cardiomyocytes unidirectional growth.
mers, carbon fiber and natural fiber composites. He has Chem Mater. 2018;30:5175–5183.
presented his research in various international conferen- 9. Jonoobi M, Harun J, Mathew AP, et al. Mechanical
ces and meetings and has authored over 88 research properties of cellulose nanofiber (CNF) reinforced
papers, technical articles, in various journals and books polylactic acid (PLA) prepared by twin screw extru-
and holds a patent. sion. Compos Sci Technol. 2010;70:1742–1747.
10. Zhao S, Yao C, Dong Z, et al. Role of ultrasonic
Dr. Greg Holt is Research Leader of the Cotton oscillation in chemical processes in microreactors:
Production and Processing Research Unit in Lubbock, A mesoscale issue. Particuology 2019. In press.
Texas. He leads a team of engineers addressing issues fac- 11. Azmir J, Zaidul ISM, Rahman MM, et al. Techniques
ing cotton breeders, producers, ginners, and spinners. for extraction of bioactive compounds from plant
The five main areas of research for the Unit include: 1) materials: A review. J Food Eng. 2013;117:426–436.
Preservation of fiber quality, 2) Cotton harvester improve- 12. Yang Y, Lan J, Li X. Study on bulk aluminum
ments, 3) Ginning processes and machinery development, matrix nano-composite fabricated by ultrasonic dis-
4) Quantification of particulate matter emissions from persion of nano-sized SiC particles in molten alumi-
agricultural sources, and 5) Value-added processing of num alloy. Mater Sci Eng A. 2004;380:378–383.
agricultural substrates. Dr. Holt’s research contributed to 13. Wang D, Yu H, Guan Y, et al. A novel chemical.
establishment of two commercial cotton-based hydro- Mater Lett. 2018;230:44–47. reduction method to
mulch manufacturing facilities in the United States. His fabricate tunable selenium nanosphere and nanobelt
work, on composites, with collaborator Ecovative Design, based on cellulose nanocrystals.
LLC, led to the launch of a 100% biodegradable molded 14. Sayyed AJ, Mohite LV, Deshmukh NA, et al. Effect
packaging material in commercial production. He collabo- of ultrasound treatment on swelling behavior of cel-
rates in research efforts with numerous industry and uni- lulose in aqueous N-methyl-morpholine-N-oxide
versity partners in the development of natural solution. Ultrasonics Sonochem. 2018;49:161–168.
fiber composites. 15. Shojaeiarani J, Bajwa D S, Stark N M.Spin-coating:
A new approach for improving dispersion of cellu-
lose nanocrystals and mechanical properties of poly
ORCID (lactic acid) composites. Carbohydrate Polym. 2018;
Jamileh Shojaeiarani http://orcid.org/0000-0002- 190:139–147. doi:10.1016/j.carbpol.2018.02.069.
1882-0061 16. He P, Gao Y, Lian J, et al. Surface modification and
Dilpreet Bajwa http://orcid.org/0000-0001-9910-8035 ultrasonication effect on the mechanical properties of
Greg Holt http://orcid.org/0000-0001-6421-118X carbon nanofiber/polycarbonate composites. Compos
Part A Appl Sci Manuf. 2006;37:1270–1275.
17. Lee H-J, Lee H-S, Seo J, et al. State-of-the-Art of
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