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TEMPO-oxidized cellulose nanofibers
Akira Isogai,* Tsuguyuki Saito and Hayaka Fukuzumi
Received 11th August 2010, Accepted 2nd September 2010
DOI: 10.1039/c0nr00583e
Published on 19 October 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00583E

Native wood celluloses can be converted to individual nanofibers 3–4 nm wide that are at least several
microns in length, i.e. with aspect ratios >100, by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl
radical)-mediated oxidation and successive mild disintegration in water. Preparation methods and
fundamental characteristics of TEMPO-oxidized cellulose nanofibers (TOCN) are reviewed in this
paper. Significant amounts of C6 carboxylate groups are selectively formed on each cellulose
microfibril surface by TEMPO-mediated oxidation without any changes to the original crystallinity
(74%) or crystal width of wood celluloses. Electrostatic repulsion and/or osmotic effects working
between anionically-charged cellulose microfibrils, the z-potentials of which are approximately
75 mV in water, cause the formation of completely individualized TOCN dispersed in water by gentle
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mechanical disintegration treatment of TEMPO-oxidized wood cellulose fibers. Self-standing TOCN

films are transparent and flexible, with high tensile strengths of 200–300 MPa and elastic moduli of
6–7 GPa. Moreover, TOCN-coated poly(lactic acid) films have extremely low oxygen permeability. The
new cellulose-based nanofibers formed by size reduction process of native cellulose fibers by
TEMPO-mediated oxidation have potential application as environmentally friendly and new bio-based
nanomaterials in high-tech fields.

1 Introduction
Nanofibers are defined as nano-sized fibers <100 nm wide or
Department of Biomaterial Sciences, The University of Tokyo, 1-1-1
Yayoi, Bunkyo-ku, Tokyo, 113-8657, Japan. E-mail: [email protected]. micron-sized fibers with nano-dimension cross sectional struc-
u-tokyo.ac.jp tures. Nanofibers have extremely large specific surface areas, the

Akira Isogai received his PhD in Tsuguyuki Saito received his

1985 for work on reactions of PhD from The University of
cellulose in non-aqueous and Tokyo in 2008 under the super-
homogeneous media from The vision of Prof. Akira Isogai for
University of Tokyo. As a post- TEMPO-mediated oxidation of
doc, he joined The Institute of native cellulose. Whilst a grad-
Paper Chemistry, Appleton, uate student he spent 2005 with
USA, working with Prof. Rajai Dr Michel R. Vignon in the
H. Atalla. In 1986, he returned CERMAV-CNRS, France as
to The University of Tokyo as an a Marie-Curie fellow. He
Assistant Professor, and started received President and Dean
polysaccharide and paper chem- Awards for his sophisticated
istry. He spent 1989 at Forest PhD thesis from The University
Akira Isogai Products Lab, USDA, Madison, Tsuguyuki Saito of Tokyo in 2008. After JSPS
USA as a visiting scientist. He postdoctoral study with Prof.
was promoted to Associate and Takashi Kato in the Graduate
full Professors in 1994 and 2003, respectively. Since 1996 he has School of Engineering, The University of Tokyo, he again joined
worked on TEMPO-mediated oxidation of cellulose and other Prof. Isogai’s group as an Assistant Professor in 2009. His
polysaccharides as the regioselective and effective chemical modi- research interests now involve construction of biomimetic materials
fication. using bio-based nanofibers by hierarchical self-assembly.

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properties of which are sometimes significantly different from celluloses as well as the original cellulose fibers in various fields
those of the bulk materials; therefore, the research and devel- from commodities such as paper and textile to high-tech mate-
opment of nanofibers has been extensively promoted by both rials such as flat panel components in liquid crystal displays,
academia and industry in the nanotechnology field. Potential hollow fibers for artificial kidney dialysis, components of medi-
applications of nanofibers include efficient catalysts, electro- cines, and food additives.
optical films, nanofiber-reinforced composites, microelectronics, Partially or significantly fibrillated cellulose fibers have been
gas-barrier films, cosmetics, flame-resistant materials and other used as beaten pulps in papermaking and micro-fibrillated
high-tech and high-performance materials.1–4 Recent environ- celluloses (MFC), respectively. MFC has been produced from
mental issues and the creation of recycle-based and sustainable wood pulp/water slurries at the industrial level by repeated high-
societies has driven the fundamental research and application of pressure homogenization treatment,5,6 and has been used as
bio-nanofibers in this decade. a filter aid and thickener. Generally, high energy consumption is
Cellulose is one of the crystalline structural polysaccharides, unavoidable for nanofibrillation of wood and other plant cellu-
that accumulates as the most abundant biopolymer present loses by partial cleavage of numerous numbers of inter-fibrillar
Published on 19 October 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00583E

primarily in wood biomass. The architecture of the unique hydrogen bonds, and complete individualization of wood cellu-
hierarchical structures of cellulose, i.e. linear glucan chains / lose fibers to 3–4 nm wide fibril elements (Fig. 1) without
crystalline cellulose microfibrils 3–4 nm wide consisting of 30–40 damages has not yet been achieved. Mechanical fibrillation of
cellulose chains / bundles of microfibrils / cell walls / fibers wood cellulose/water slurries by grinder treatment at the labo-
/ plant tissue / trees or other plants, comprises hemicellulose ratory level has been found to be more effective in both terms of
and lignin to reinforce the plant living bodies (Fig. 1). Humans nanofibrillation and energy consumption.79 Wood cellulose
have long history of using chemically and mechanically modified fibers for papermaking have been converted to 20–100 nm in
wide nanofibers by treatment with a grinder.7–9 Other than wood
cellulose fibers, agricultural waste and never-dried wood hol-
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ocelluloses were studied as resources for the nanofibrillation

of cellulose.10–14
Chemistry-assisted nano-fibrillations of various materials,
such as wood, cotton, ramie, and bacterial and tunicate cellu-
loses, have been extensively studied at the laboratory level. In
most cases, anionically charged functional groups are introduced
on the cellulose microfibril surfaces to form strong electrostatic
repulsion between cellulose microfibrils in water. A traditionally
significant and representative method to introduce charged
groups onto cellulose microfibril surfaces is acid hydrolysis with
64% H2SO4 at 45  C for 1–4 h.15–19 Successive mechanical
disintegration of the acid hydrolyzed residues in water using, for
example, an ultrasonic homogenizer, provides cellulose nano-
Fig. 1 Hierarchical structure of wood biomass and the characteristics of
crystals. When wood celluloses are subjected to acid hydrolysis
cellulose microfibrils.
followed by sonication, cellulose nanocrystals or nanowhiskers
5–10 nm wide and 50–200 nm long, a part of which form spindle-
like bundles, are obtained. However, weight recovery ratios are
low at only 30–50%.16 Cellulase-pretreatment or partial carboxy-
Hayaka Fukuzumi received her methylation of wood celluloses enabled a reduction in energy
Bachelor and Master degrees in consumption for nanofibrillation processes in water using refiner
Biomaterial Sciences from The and high-pressure homogenizer treatments.20–22 Graft-polymeri-
University of Tokyo in 2007 and zation of acrylonitrile onto wood celluloses and successive
2009, respectively. She is mechanical treatment seems to cause dispersion of partially
currently pursuing a PhD at the anionic groups-grafted nanocellulose in water.23 MFC, enzy-
Graduate School of Agricultural matically or chemically modified MFCs, and acid-hydrolyzed
and Life Sciences, The Univer- cellulose nanocrystals thus obtained have been studied primarily
sity of Tokyo, under the super- for applications as fillers in nanocomposites and electro-optical
vision of Prof. Isogai. She films, and related reviews have been recently published.24,25
received Dean Awards for her Plant cellulose microfibrils can be regarded as bio-based
Bachelor and Master theses nanofibers with uniform widths, high crystallinity and high
from the University of Tokyo. In aspect ratios originally present in the plant cell walls. However, it
Hayaka Fukuzumi 2009 she received a Research has been impossible to isolate completely individualized cellulose
Fellowship for Young Scientists microfibrils from plant cellulose fibers without serious damage or
from the Japan Society for the yield losses, because numerous hydrogen bonds are present
Promotion of Science (JSPS). Her research is focused on estab- between cellulose microfibrils in cellulose fibers (Fig. 1).
lishing clear relationships between the nano-sized structures in the We have developed a new method to prepare completely
film and gas-barriers of cellulose and chitin nanofiber films. individualized cellulose nanofibers 3–4 nm wide and at least a few

72 | Nanoscale, 2011, 3, 71–85 This journal is ª The Royal Society of Chemistry 2011
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microns long from wood cellulose fibers by 2,2,6,6-tetrame-

thylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation
under moderate aqueous conditions.26–29 In this paper, funda-
mental characteristics and applications of TEMPO-oxidized
cellulose nanofibers (TOCN) are reviewed with some recently
obtained data.

2 TEMPO-mediated oxidation of celluloses

TEMPO and its analogues are water-soluble, commercially-
available and stable nitroxyl radicals, most of which have
a negative result to the Ames test. Catalytic oxidation using
Published on 19 October 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00583E

TEMPO has opened a new field of efficient and selective

conversion chemistry of alcoholic hydroxyl groups to aldehydes, Fig. 3 Regioselective oxidation of C6 primary hydroxyls of cellulose to
ketones and carboxyl groups under mild conditions. Many C6 carboxylate groups by TEMPO/NaBr/NaClO oxidation in water at
related studies have been extensively carried out in the last two pH 10–11.
decades, and have been reviewed in detail.30,31 Particularly, de
Nooy et al. first applied TEMPO-mediated oxidation to water-
soluble polysaccharides such as starch, amylodextrin and pul- to native celluloses such as cotton linters, bleached kraft pulps
lulan for regioselective conversion of C6 primary hydroxyls to and bacterial cellulose, even under harsh oxidation conditions or
carboxylate groups.32 In this system, catalytic amounts of for extended reaction times, almost no or only small amounts of
TEMPO and NaBr were dissolved in polysaccharide solutions at water-soluble products were obtained.37 On the other hand,
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pH 10–11, and oxidation was started by the addition of NaClO slurries of regenerated and mercerized celluloses, and ball-milled
solution as a primary oxidant. The efficient conversion of and liquid NH3-treated native celluloses became clear solutions
primary hydroxyl groups to carboxylates via aldehydes is as the oxidation proceeded; water-soluble oxidized products were
hypothesized to proceed according to the mechanism shown in obtained in these cases.37–39 The oxidized products had almost
Fig. 2.33,34 Various TEMPO-mediated oxidation reactions of homogeneous chemical structures of sodium (1 / 4)-b-D-poly-
mono-, oligo- and polysaccharides for regioselective conversion glucuronate or Na salt of cellouronic acid (CUA) consisting of
D-glucuronosyl units alone. Hence, the C6 primary hydroxyls of
of primary hydroxyls to carboxylate groups have been reviewed
elsewhere.35,36 celluloses can be entirely and selectively converted to C6 sodium
According to the scheme shown in Fig. 3, the C6 primary carboxylate groups by TEMPO-mediated oxidation.37–39 It was
hydroxyls of cellulose are expected to be oxidized to C6 confirmed that C6-carboxylate groups are formed by not only
carboxylate groups by TEMPO/NaBr/NaClO oxidation in water the oxidized TEMPO but also NaBrO and/or NaClO present in
at pH 10–11. The oxidation process can be monitored from the the TEMPO/NaBr/NaClO system at pH 10 (Fig. 3).40
pattern of aqueous NaOH consumption, which is continuously
added to the reaction mixture to maintain the pH at 10 during the
oxidation. When TEMPO/NaBr/NaClO oxidation was applied

Fig. 4 Selective oxidation of C6 primary hydroxyls of cellulose to

Fig. 2 TEMPO-mediated oxidation of primary hydroxyls to carboxyl carboxylate groups by TEMPO/NaClO/NaClO2 oxidation in water at
groups via aldehydes.32 pH 4.8–6.8.

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suspended in a buffer at pH 4.8–6.8. CUAs with DPw values

higher than 490 were quantitatively obtained as water-soluble
products in this case.47 Almost pure CUA was obtained by the
TEMPO/NaClO/NaClO2 oxidation at pH 4.8, according to the
nuclear magnetic resonance (NMR) spectrum (Fig. 5).47 CUA is
significantly resistant to acid hydrolysis, but susceptible to b-
elimination under alkaline conditions. These properties are
opposite to those of the original celluloses, which are susceptible
to acid hydrolysis, but are relatively stable under alkaline
conditions.48
When a thin CUA film was formed on a poly(ethylene tere-
phthalate) (PET) film by a coating method, the oxygen perme-
ability at 30  C and 70% relative humidity decreased from
Published on 19 October 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00583E

15000 mL m 2 day 1 kPa 1 for the base PET film to 100–300 mL

m 2 day 1 kPa 1 (Table 1).49 Thus, oxygen barrier properties
appear on the thin CUA layer-containing PET films.
Various TEMPO-mediated oxidation systems and conditions
have been applied to cellulose, chitin, curdlan and other mono-
Fig. 5 13C NMR spectra of (a) cellulose oligomers dissolved in DMSO-
and polysaccharides in terms of regioselectivity at the C6 primary
d6 and (b) CUA with DPw 490 dissolved in D2O. CUA was prepared by
hydroxyls, oxidation efficiency, suppression of depolymerization
TEMPO/NaClO/NaClO2 oxidation in water at pH 4.8.47 Reproduction
of the lower NMR spectrum from ref. 47 with permission from Elsevier
or side reactions, and utilization of non-chlorine primary
(ª Elsevier 2009). oxidants.50–71
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However, weight-average degrees of polymerization (DPw) for 3 Biodegradation of TEMPO-oxidized cellulose

CUA prepared by TEMPO/NaBr/NaClO oxidation at pH 10
Even though CUA is a new sodium polyglucuronate artificially
ranged from 40 to 80, and were far lower than those of the
prepared from cellulose by TEMPO-mediated oxidation, depo-
original celluloses (DPw 380–1200) used as starting materials.38,41
lymerization of CUA occurs by commercial crude cellulase
Two routes for the depolymerization of CUA are plausible. One
treatment. Because pure endo- or exo-type cellulases cannot
route is b-elimination due to C6 aldehyde groups formed as
depolymerize CUA at all, some enzymes present as contaminants
intermediate structures (Fig. 3) under alkaline conditions,42–44
in the commercial cellulases may participate in the depolymer-
and another is cleavage of the (1 / 4)-b-glycoside bonds of
ization of CUA.72,73 Moreover, CUA is easily metabolized to
CUA by hydroxyl and/or other active radical species formed
in situ as side reactions during TEMPO-mediated oxidation.45
TEMPO/NaClO/NaClO2 oxidation systems in aqueous–
organic solvents have been proposed as an alternative, where
catalytic amounts of TEMPO and NaClO are combined with
NaClO2 as the primary oxidant.46 This TEMPO/NaClO/NaClO2
oxidation system (Fig. 4) was applied to a commercial regen-
erated cellulose with a viscosity average DP (DPv) of 680

Table 1 Oxygen permeability of various polysaccharides 1 mm thick

coated on PET film 12 mm thick, measured at 30  C and 70% relative
humidity.49

2 1
O2 permeability/mL m day
kPa 1

PET film (Blank) 15000

PET film coated with:
CUA-COONa 240
CUA-COOH 120
Sodium alginate 4190
Pectin 1520
Carboxymethyl cellulose Na salt 10000
Hydroxyethyl cellulose 1430
Chitosan 11200
Water-soluble starch 3000
Poly(vinylidene chloride) 200–1000
Ethylene vinyl alcohol copolymer 100
Fig. 6 Schematic degradation system of CUA by endo- and exo-type
Poly(vinyl alcohol) <100
Nylon 4000 CUA lyases (CUL-I and CUL-II, respectively).74,75 Reproduction of
illustration from ref. 75 with permission from Springer (ª Springer 2008).

74 | Nanoscale, 2011, 3, 71–85 This journal is ª The Royal Society of Chemistry 2011
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Fig. 7 Overall structure of TrCUL-I. (a) Front and (b) side view of the
ribbon representation.77 Reproduction of images from ref. 77 with
Published on 19 October 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00583E

permission from Elsevier (ª Elsevier 2009).

Fig. 8 Relationships between the amount of NaClO added in the
TEMPO/NaBr/NaClO oxidation of bleached softwood kraft pulp at pH
CO2 and water by microorganisms present in natural soils, and 10 and room temperature, and either carboxylate and aldehyde contents
both endo- and exo-type CUA lyases (CUL-I and CUL-II, or degree of polymerization of the oxidized pulps.
respectively) have been isolated and purified from a bacterial
strain Brevundimonas sp. SH203 present in nature (Fig. 6).74,75
The cDNA encoding CUA lyase produced by Trichoderma Because the TEMPO-oxidized celluloses containing both glu-
reesei, a filamentous fungus, was cloned and the recombinant cosyl and glucuronosyl units are totally soluble in 0.5 M copper
enzyme was heterologously expressed in Pichia pastoris. The ethylenediamine hydroxide (cuen) solution, DPv values can be
roughly estimated by calculation from the intrinsic viscosities
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recombinant Trichoderma CUA lyase (TrCUL-I) degrades CUA

endolytically by b-elimination.76 The three-dimensional structure using the conventional Mark–Houwink–Sakurada equation.92 If
of TrCUL-I was defined from its crystals (Fig. 7), showing that small amounts of C6 aldehyde groups are present in the
a calcium ion is bound to the site far from the cleft and appears to TEMPO-oxidized celluloses, the viscosity method would provide
contribute to the stability.77 lower DPv values than the accurate values by b-elimination,
CUAs are both biodegradable and metabolizable, and have which takes place at the C6 aldehyde groups in the alkaline cuen
relatively low-molecular weights, so they have potential appli- solution. Thus, additional oxidation with NaClO2 in water at pH
cation as new biodegradable polymeric builders in detergents to 4–5 for selective conversion of C6 aldehydes to C6 carboxyl
capture calcium ions in laundry water.78 groups is required before the viscosity measurement to obtain
more accurate DPv values. Fig. 8 shows that the DPv values
decreased from 1200 to approximately 600 by TEMPO-mediated
4 TEMPO-mediated oxidation of native celluloses oxidation with NaClO of 5–10 mmol g 1 pulp. Thus, significant
When TEMPO/NaBr/NaClO oxidation at pH 10 and room depolymerization is inevitable during the TEMPO/NaBr/NaClO
temperature is applied to native celluloses with the cellulose oxidation of native celluloses in water at pH 10.
I crystal structure, such as cotton linters, bleached kraft and Moreover, trace amounts of C2 or C3 ketones are formed as
sulfite pulps (wood celluloses), softwood thermomechanical side reactions, depending on oxidation conditions and reactivity
pulp, bacterial cellulose and ramie fiber, the original fibrous of TEMPO derivatives used. The ketone and aldehyde groups
morphologies are unchanged even after oxidation with sufficient formed in the TEMPO-oxidized celluloses cause brown
amounts of reagents. However, significant amounts of sodium
carboxylate groups and small amounts of aldehyde groups are
formed in the products by oxidation of a part of C6 primary
hydroxyls.26–29,79–90 The carboxyl content of the TEMPO-
oxidized celluloses has been determined by the electric conduc-
tivity titration method.80,84 Aldehyde groups are selectively
converted to carboxyl groups by NaClO2 treatment in water at
room temperature and pH 4–5 for 1 day, and carboxyl groups
additionally formed by NaClO2 oxidation are regarded as alde-
hyde groups in the TEMPO-oxidized celluloses.80,83,86,91
A bleached softwood kraft pulp for papermaking, one of the
wood celluloses that contains approximately 90% cellulose and
10% hemicelluloses, was oxidized using the TEMPO/NaBr
system in water at pH 10 with various amounts of NaClO as the
primary oxidant (Fig. 8). The sodium carboxylate content
increased from 0.01 to 1.70 mmol g 1, i.e. a 170-fold increase, Fig. 9 Relationships between the reaction time of bleached softwood
by the oxidation with NaClO of 10 mmol g 1-pulp, while kraft pulp under TEMPO/NaClO/NaClO2 oxidation at pH 6.8 and 60
small amounts of aldehyde groups were present in the oxidized 
C, and either carboxylate and aldehyde contents or degree of polymer-
celluloses. ization of the oxidized pulps.

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discoloration by heating, though the amounts are quite small.

Relationships between oxidation conditions and side reactions
have been studied for mono- or disaccharides,36,51–53 but not yet
for cellulose. These issues are now under investigation.
Oxidation using another system, TEMPO/NaClO/NaClO2, in
water at pH 6.8 and 60  C suppressed the depolymerization of
the oxidized celluloses to some extent (Fig. 9).29,93 DPv values of
more than 1000 were obtained from the oxidized celluloses from
the same bleached softwood kraft pulp in Fig. 8. Even though no
aldehyde groups were present, carboxylate contents were lower
than 1 mmol g 1; the efficiency for the formation of carboxylate
groups by this oxidation system is somewhat lower than for
TEMPO/NaBr/NaClO oxidation at pH 10.
Published on 19 October 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00583E

Fig. 8 and 9 show that significant amounts of carboxylate

groups were formed in the TEMPO-oxidized wood celluloses. Fig. 11 Relationships between the microfibril width of various native
Nevertheless, the original crystal structure of cellulose I, the celluloses and the total content of carboxylate and aldehyde groups
crystallinity indices and the crystal sizes were unchanged after formed in the corresponding TEMPO-oxidized native celluloses. The
the oxidation (Fig. 10).27,29,80 These results indicate that the dashed line shows the relationship between microfibril width and the
carboxylate groups formed by TEMPO-mediated oxidation are content of C6 primary hydroxyls exposed on the surfaces of cellulose I
selectively present on cellulose microfibril surfaces without any crystallites.95 Reproduction of the figure from ref. 95 with permission
from American Chemical Society (ª American Chemical Society 2010).
internal cellulose crystallites. Solid-state 13C NMR spectra of
TEMPO-oxidized celluloses also support the hypothesis that
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only C6 primary hydroxyls exposed on the original cellulose

microfibrils are converted to carboxylate groups by oxida-
tion.29,94
When various native celluloses having different microfibril
widths were treated with an excess amount of NaClO in the
TEMPO-mediated oxidation, the maximum contents of C6-
oxidized groups (both carboxylate and aldehyde groups) that
were formed varied depending on the cellulose I crystal widths.
The relationship between the microfibril width of various native
celluloses and either calculated content of C6 primary hydroxyls
exposed on the microfibril surfaces or the experimentally-
obtained maximum content of C6-oxidized groups are plotted in
Fig. 11.95 The dashed line is calculated from the crystal widths of
cellulose I determined from X-ray diffraction patterns.
The results in Fig. 11 reveal that the calculated amounts of Fig. 12 Schematic model for the oxidation of C6 primary hydroxyls on
surface C6 primary hydroxyls were in good agreement with the native cellulose microfibril surfaces to C6 carboxylate groups using the
total contents of C6-oxidized groups experimentally determined; TEMPO/NaBr/NaClO system.95 Reproduction of illustration from ref.
smaller microfibril widths of the native cellulose resulted in more 95 with permission from American Chemical Society (ª American
Chemical Society 2010).

oxidized groups being formed on the microfibril surfaces by

TEMPO-mediated oxidation. Thus, TEMPO-mediated oxida-
tion selectively converts C6 primary hydroxyls exposed on the
surfaces of crystalline cellulose microfibrils to sodium carboxy-
late groups. Every one of two glucosyl units in the cellulose
chains on the microfibril surface are converted to C6 carboxylate
groups by oxidation (Fig. 12).27,29,80,94,95
Thus, TEMPO-mediated oxidation is a type of regioselective
surface modification of crystalline native cellulose microfibrils,
and allows the formation of anionic carboxylate groups with
quite high densities on the microfibril surfaces. Moreover, when
the TEMPO-oxidized native celluloses with maximum carboxy-
Fig. 10 X-ray diffraction patterns of (a) the original wood cellulose with late contents were extracted with aqueous NaOH, regularly
carboxylate content of 0.01 mmol g 1 and (b) TEMPO-oxidized wood alternating copolysaccharides consisting of glucosyl and glu-
cellulose with carboxylate content of 1.70 mmol g 1.29 Reproduction of curonosyl units were obtained as water-soluble fractions by
this figure from ref. 29 with permission from American Chemical Society surface-peeling. This result also justified the surface structures of
(ª American Chemical Society 2009). TEMPO-oxidized native celluloses shown in Fig. 12.96

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In the case of the TEMPO/NaBr/NaClO oxidation of lignin- cellulose/water slurries were mostly converted to transparent and
containing samples such as softwood thermomechanical pulp highly viscous dispersions by mechanical disintegration treat-
(TMP), lignin and hemicelluloses in TMP were removed as ment using a household blender, double-cylinder-type homoge-
water-soluble degraded fractions as NaClO consumption pro- nizer or ultrasonic homogenizer for 2–10 min.26,27,29,90,95
ceeded.89,90 TEMPO-oxidized cellulose was then obtained from Transmission electron microscopy (TEM) observation revealed
TMP as a water-insoluble fraction by filtration of the oxidation that the dispersions consisted of mostly individualized TOCN of
mixture. Even though additional amounts of NaClO and 3–4 nm in width and a few microns long (Fig. 13a–c). This was
extended oxidation times were required for complete TMP the first time that wood cellulose fibers 20–40 mm in width were
oxidation, compared with the oxidation of wood celluloses such fined down to the smallest elements next to cellulose molecules,
as bleached kraft pulps, TEMPO-oxidized native celluloses with consisting of approximately 30–40 cellulose chains, i.e. individual
carboxylate contents of 1–1.5 mmol g 1 were obtained as water- cellulose nanofibers with high aspect (length/width) ratios of
insoluble products, the weight recovery ratios of which were more than 100 and in high yields (>90%), were found by
approximately 40%.90 TEMPO-mediated oxidation followed by mild mechanical
Published on 19 October 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00583E

Significant amounts of sodium carboxylate groups are present disintegration of the oxidized wood celluloses in water.
in the TEMPO-oxidized native celluloses, which is different from The nanofiber widths are almost constant, irrespective of
the original native celluloses, so that the hydrophilic nature, wood species examined so far, whereas the lengths are widely
thermal degradation behavior and other properties of TEMPO- distributed and varied depending on the oxidation and disinte-
oxidized celluloses can be controlled to some extent by various gration conditions. Even though no intrinsic differences were
metal-ion exchange, methyl esterification and other chemical found between never-dried and once-dried wood pulps for the
modification of the carboxylate groups.81,97,98 preparation of nano-dispersions, never-dried wood pulps were
converted to transparent dispersions within shorter times and in
5 Preparation of TEMPO-oxidized cellulose higher yields when the amount of NaClO added was reduced to
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3 mmol g 1 pulp or lower.27 The presence of birefringence

nanofibers dispersed in water
(Fig. 13e) is usually taken as an indication of individual nano-
When the carboxylate contents formed from the C6 primary fiber dispersion.99 Other native celluloses such as cotton linters,
hydroxyl groups of bleached hardwood and softwood kraft pulps ramie, and bacterial, tunicate and algal celluloses were also
were more than approximately 0.8 mmol g 1, the oxidized converted to individual nanofibers by TEMPO-mediated oxida-
tion, while the optimum oxidation conditions to provide nano-
fibers in high yields varied between the original celluloses used as
the starting materials.26,95

Fig. 13 TEM images (a–c) of a dried dispersion of TEMPO-oxidized

hardwood cellulose with carboxylate and aldehyde contents of 0.8 and
0.0 mmol g 1, respectively, observed by diffraction-contrast method in
the bright-field mode using a low-dose exposure. The insets show Fig. 14 Dispersion states and UV-vis transmittance of TEMPO oxidized
a typical dispersion (d) and (e) that observed between cross polarizes.29 hardwood celluloses with different carboxylate contents.27 Reproduction
Reproduction of image a from ref. 29 with permission from American of both photograph and figure from ref. 29 with permission from
Chemical Society (ª American Chemical Society 2009). American Chemical Society (ª American Chemical Society 2007).

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When the amount of NaClO added to the TEMPO/NaBr/ Fig. 15 shows TEM images of hardwood TOCN with
NaClO oxidation of a bleached hardwood kraft pulp at pH carboxylate contents of 1.0 and 1.5 mmol g 1. The former
10 varied from 2.5 and 5 mmol g 1-pulp, the carboxylate content cellulose nanofibers clearly formed aggregates, resulting in low-
formed was correspondingly varied from 1.0 to 1.5 mmol g 1. light transmittance of the dispersion. In contrast, the TEMPO-
The transmittance of the aqueous dispersions prepared under the oxidized cellulose with a carboxylate content of 1.5 mmol g 1 was
same moderate mechanical disintegration conditions varied from mostly converted to individual nanofibers with almost uniform
translucent to highly transparent (Fig. 14). Hence, carboxylate widths of 3–4 nm. Nanofiber widths that are smaller than the
content is the key factor influencing the degree of nanofiber wavelength of visible light cause the dispersion to be almost
conversion of TEMPO-oxidized celluloses. The UV-vis trans- transparent. The large amounts of anionically charged sodium
mittance spectrum in Fig. 14a shows that the transmittance is carboxylate groups present in high densities on the TOCN
wavelength-dependent and related to the nanofiber widths.100–102 surfaces may cause the formation of such sufficiently individu-
Unfibrillated and partly fibrillated fractions, if present, can be alized and long cellulose nanofibers by electrostatic repulsion
removed from the dispersions at approximately 0.1% consistency and/or osmotic effects in water.27
Published on 19 October 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00583E

by centrifugation at 12,000 gravity for 20 min. The degrees of Fig. 16 shows z-potentials and carboxylate contents of the
individualization or yields of individual TOCNs are thus esti- various TEMPO-oxidized native celluloses presented in Fig. 11.
mated from the weight ratios of the precipitates separated from Although the oxidized celluloses had clearly different carboxy-
dispersions by centrifugation. In the case of TEMPO/NaBr/ late contents that were dependent on the crystalline microfibril
NaClO oxidation at pH 10, yields of individual hardwood widths of the native celluloses, all the TOCNs had similar z-
TOCN were slightly lower than those for softwood TOCN with potentials of approximately 75 mV. This indicates that all the
the same carboxylate contents of approximately 1 mmol g 1. TEMPO-oxidized celluloses have almost the same density of
Relatively hydrophobic xylan, which has no C6 primary carboxylate groups on the surfaces of crystalline cellulose
hydroxyls and may be present to some extent in the TEMPO- microfibrils, because the z-potentials are directly related to the
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oxidized hardwood celluloses, would probably lead to the lower surface density of dissociated carboxyl groups. The average
nanofiber yields. When carboxylate content was more than 1.5 density of C6 primary hydroxyls exposed on the crystallite
mmol g 1, the nanofiber yields for both hardwood and softwood surfaces was calculated to be approximately 1.7 groups nm 2
TEMPO-oxidized celluloses prepared using the TEMPO/NaBr/ from the surface structures of cellulose I crystallites.103
NaClO system at pH 10 were more than 95%. The nanofiber yield, light-transmittance and viscosity of the
TEMPO-oxidized cellulose/water dispersions were dependent on
the apparatus and conditions used during mechanical treatment.
In small-scale experiments at the laboratory level, one of the
following apparatus, or a combination of two or three apparatus,
can be used for mechanical disintegration of TEMPO-oxidized
celluloses in water: magnetic stirrer, household mixer, double-
cylinder-type homogenizer and ultrasonic homogenizer. For any
of these disintegration methods, nanofiber yields of more than
95% were achieved for TEMPO-oxidized celluloses having
carboxylate contents greater than a necessary level, although the
time required for disintegration to achieve the maximum nano-
fiber yield was significantly different.
The TOCN/water dispersions had similar shear-thinning
behavior, irrespective of the mechanical disintegration methods

Fig. 15 TEM images of dried dispersions of TEMPO-oxidized hard-

wood celluloses with carboxylate contents of 1.0 and 1.5 mmol g 1,
observed by negative staining with uranyl acetate. The insets show the Fig. 16 Carboxylate contents of various TEMPO-oxidized celluloses
corresponding aqueous dispersions.27 Reproduction of images from ref. and z-potentials of the individualized TOCNs dispersed in water.95
27 with permission from American Chemical Society (ª American Reproduction of figure from ref. 95 with permission from American
Chemical Society 2007). Chemical Society (ª American Chemical Society 2010).

78 | Nanoscale, 2011, 3, 71–85 This journal is ª The Royal Society of Chemistry 2011
 View Article Online

used. However, the viscosities of the obtained dispersions were TEMPO-mediated oxidation, it is difficult and costly to separate
different and dependent on the disintegration methods, and were the nanofibers from the chemicals and other contaminants
generally in the order, magnetic stirring > household mixer present in the aqueous oxidation mixtures. Moreover, the
treatment > ultrasonic homogenizer treatment. Probably, the transportation of aqueous TOCN dispersion with quite low solid
ultrasonic homogenizer treatment efficiently converts TEMPO- consistencies would be costly and energy-consumptive.
oxidized celluloses to individual nanofibers in the shortest The other advantageous point is that inexpensive wood
disintegration time. Mechanical disintegration times for celluloses such as bleached kraft and sulfite pulps are the most
magnetic stirring, household mixer and ultrasonic homogenizer suitable resources for the efficient production of TOCNs. These
treatments to reach nanofiber yields of more than 95% were, for pulps have been produced on a large scale from wood chips at the
example, ca. 10 days, 4 min and 2 min, respectively. TOCN/water industrial level using environmentally friendly, effective and
dispersions prepared by ultrasonic homogenizer treatment lower energy consumptive pulping and bleaching processes.
generally had the highest nanofiber yields, although the viscosi- These pulps generally contain 85–95% cellulose and corre-
ties were relatively low. The rheological properties of TOCN/ spondingly 15–5% disordered hemicelluloses, which are present
Published on 19 October 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00583E

water dispersions have been studied in detail.27,104 in the spaces between cellulose microfibrils. During the TEMPO-
Once such transparent dispersions of TOCNs in water were mediated oxidation of wood celluloses, the oxidized TEMPO
obtained, the transparencies were maintained for more than 6 molecules or nitrosonium ions should penetrate into the spaces
months at approximately 4  C in a refrigerator. However, between cellulose microfibrils and oxidize every one of two glu-
because TOCNs are biodegradable, the viscosities of dispersions cosyl units in the cellulose chains present on the microfibril
without small drops of ethanol or the addition of a suitable surfaces. The hemicelluloses present between cellulose microfi-
fungicide may decrease to some extent with increasing storage brils form sponge-like layers, into which the oxidized TEMPO
time. Transparent TOCN/water dispersions sometimes turn to molecules can easily penetrate during oxidation (Fig. 18).
mould within several days when exposed to air at room A representative TEMPO/NaBr/NaClO oxidation process
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temperature. performed at pH 10 for the preparation of TEMPO-oxidized

There are two advantageous key points to produce TOCNs at wood celluloses is illustrated in Fig. 19. The expensive TEMPO
the industrial level for future utilization as new bio-based used as the catalyst can be recycled and reused by desalination of
nanofibers in high-tech fields. One is that the original fibrous the washing effluent. Thus, it is possible to significantly reduce
morphologies of wood celluloses such as bleached kraft and the production cost of TEMPO-oxidized celluloses. The reuse of
sulfite pulps are maintained at the micron level without serious once-used TEMPO in washing effluents was studied to establish
swelling in water before and after TEMPO-mediated oxidation, a TEMPO-recycling system.105
even though significant amounts of hydrophilic sodium carboxy-
late groups are formed in the TEMPO-oxidized wood celluloses
(Fig. 17).27 Thus, after TEMPO-mediated oxidation, the oxidized
wood cellulose fibers can be thoroughly washed with water by
simple suction filtration, and then squeezed to high solid
consistencies for transportation to a mill, where mechanical
disintegration of the TEMPO-oxidized cellulose in water is
available on site to produce nanofiber/water dispersions. If
partial dispersion to individual nanofibers takes place during the

Fig. 17 Optical micrographs of the (a) original and (b) TEMPO-

oxidized hardwood celluloses with carboxylate contents of 0.05 and 1.5
mmol g 1, respectively. Images were taken with or without cross polar- Fig. 18 Schematic model of sponge-like hemicelluloses present in the
izers.27 Reproduction of images from ref. 27 with permission from spaces between cellulose microfibrils, and their role in the TEMPO-
American Chemical Society (ª American Chemical Society 2007). mediated oxidation of wood celluloses.

This journal is ª The Royal Society of Chemistry 2011 Nanoscale, 2011, 3, 71–85 | 79
 View Article Online

TOCN/water dispersions by mild mechanical disintegration

treatment of the oxidized celluloses in water. TEMPO-electro-
mediated oxidation without the use of any chlorine-containing
chemicals is also applicable to the preparation of individualized
TOCNs, although longer oxidation times are required.40 Other
TEMPO-mediated oxidation systems, such as TEMPO/peroxi-
dase/H2O2 and TEMPO/laccase/O2 systems,37,65 are ineffective
for the oxidation of wood celluloses, and the resulting carboxy-
late contents in the oxidized products were lower than
0.3 mmol g 1, even after oxidation for more than 4 days.
Commercially available MFC has been produced from wood
cellulose/water slurries by repeated high-pressure homogenizer
treatments.5,6 Cellulose nanocrystals (CNC) or cellulose nano-
Published on 19 October 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00583E

whiskers (CNW) have been prepared from wood and other

native celluloses by acid hydrolysis using, for example, 64%
Fig. 19 Representative process to prepare TEMPO-oxidized wood H2SO4, and successive mechanical disintegration of the
celluloses by the TEMPO/NaBr/NaClO system in water at pH 10.

Fig. 20 shows the relationships between carboxylate content

and nanofiber yield of TEMPO-oxidized hardwood celluloses
prepared using TEMPO and its analogues by TEMPO/NaBr/
NaClO oxidation in water at pH 10. From the catalyst
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compounds examined to date, TEMPO, 4-acetamido-TEMPO

and 4-methoxy-TEMPO provide high and similar carboxylate
contents and nanofiber yields.106 The stability of the TEMPO
analogues to NaClO is one of the factors that influenced the
results shown in Fig. 20,107 while the redox potentials of the
TEMPO analogues seem to have no correlation to the results.
1) TEMPO/NaBr/NaClO oxidation in water at pH 10 and
room temperature and 2) TEMPO/NaClO/NaClO2 oxidation in
water at pH 6.8 and 60  C yield mostly individualized wood

Fig. 20 Relationship between carboxylate content and nanofiber yield Fig. 21 Optical micrograph of MFC, and TEM images of wood TOC-
of TEMPO-oxidized hardwood celluloses prepared using TEMPO and its N27and CNC.16 Reproduction of the TOCN image from ref. 27 with
analogues by TEMPO/NaBr/NaClO oxidation in water at pH 10.106 permission from American Chemical Society (ª American Chemical
Reproduction of figure from ref. 106 with permission from Elsevier (ª Society); reproduction of the CNC image from ref. 16 with permission
Elsevier 2010). from Springer (ª Elsevier 1998).

80 | Nanoscale, 2011, 3, 71–85 This journal is ª The Royal Society of Chemistry 2011
 View Article Online

hydrolyzed residues in water.15–19 Small amounts of sulfate ester

groups (<0.3 mmol g 1) are formed on the CNC surfaces, so that
electrostatic repulsion formed between CNC whiskers leads to
partial nano-dispersion in water. An optical micrograph of
MFC, and typical TEM images of wood TOCN27 and CNC16 are
depicted in Fig. 21.
Significant amounts of clearly unfibrillated bundles and fibers
are still present in MFC. CNC whiskers have spindle-like
morphologies due to the partial removal of cellulose molecules
by acid hydrolysis. The TEM image of CNC shows that CNC
whiskers form some bundles by incomplete individualization of
cellulose microfibrils, which is probably due to an insufficient
sulfate ester content of less than 0.3 mmol g 1.16 Differences in
Published on 19 October 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00583E

the preparation method, yield and other properties and factors of Fig. 22 UV-vis transmittance of nanofiber films prepared from
MFC, TOCN and CNC (or CNW)16 are summarized in Table 2. TEMPO-oxidized softwood and hardwood celluloses. The photograph
shows the light transmittance behavior of the nanofiber film prepared
The high aspect ratios, uniform widths and complete nano-
from TEMPO-oxidized softwood cellulose.28 Reproduction of image and
dispersion of individual TOCNs are different from the others,
figure from ref. 28 with permission from American Chemical Society (ª
which clearly indicates the advantages of TOCN for applications American Chemical Society 2009).
as new bio-based nanofibers in high-tech fields.

6 TEMPO-oxidized cellulose nanofiber films and Therefore, distribution control of individualized TOCN to
obtain more homogeneous distribution in a composite is
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composites
important to achieve the effect of high aspect ratio TOCNs on
Self-standing films with sufficient light transparency and flexi- the mechanical properties.
bility were prepared from softwood and hardwood TOCN/water Moreover, because sodium carboxylate groups abundantly
dispersions. UV-vis transmittance in Fig. 22 show that the film present on the TOCN surfaces cannot form hydrogen bonds, it
prepared from hardwood cellulose had lower transmittance, may be possible to further improve the mechanical properties of
probably due to the presence of a small amount of hydrophobic TOCN films by converting the sodium carboxylate structures to
xylan in the film.28 The refractive index of the TOCN film was free carboxylate groups by, for example, gaseous acid treatment.
1.545  0.002 at room temperature, and this value is consistent Self-standing films prepared from TEMPO-oxidized wood
with those previously reported for cellulose.108 celluloses by TEMPO/NaClO/NaClO2 oxidation in water at pH
The densities and moisture contents of TOCN films condi- 6.8 had higher tensile strength than those prepared from
tioned at 23  C and 50% relative humidity were approximately TEMPO/NaBr/NaClO oxidation in water at pH 10, probably
1.45–1.47 g cm 3 and 13–15%, respectively. The tensile strengths because the former had higher DP values.29 However, the elastic
and elastic moduli of the films were 200–300 MPa and 6–7 GPa, moduli of the films were similar, despite the different TEMPO-
respectively,28 which were higher than those of cellophane films mediated oxidation methods employed. TOCN/ethylcellulose
(Fig. 23). Both the tensile strength and elastic modulus of and TOCN/phenol resin composites have been studied to
a poly(vinyl alcohol) (PVA) film were remarkably improved by improve mechanical and thermal properties of the matrix
20% TOCN addition. However, similar results would be expec- materials.109,110
ted by the addition of only a few % TOCN if each TOCN is The highly hydrophilic nature of TOCN films leads in turn to
present individually in the TOCN/PVA composite film.1 low contact resistance to water. The contact angle of a water

Table 2 Differences between TOCN, MFC and CNC/CNW

TOCN MFC CNC or CNW

Preparation method TEMPO-mediated oxidation of Repeated high-pressure Acid hydrolysis of wood cellulose
wood cellulose, and mild homogenizer treatment of wood with 64% H2SO4, and
disintegration of the oxidized cellulose/water slurry disintegration of the residues in
cellulose in water water
Yield >90% 100% <50%
Morphology Uniform width of 3–4 nm, <2–3 mm Uneven width of 10–2000 nm Uneven width of 5–10 nm, <300 nm
in length forming bundles in length, spindle-like whiskers
forming partial bundles
1 1
Energy consumption in nano- <7 MJ kg 700–1400 MJ kg <7 MJ kg 1
conversion
Potential applications High gas-barrier films for Filter aid nanofiber for composites, Nanofiller for composites
packaging & display, fine thickeners
separation filters, health care
materials, nanofibers for
composites

This journal is ª The Royal Society of Chemistry 2011 Nanoscale, 2011, 3, 71–85 | 81
 View Article Online

the TOCN film are likely to behave as adsorption sites for

cationic AKD-dispersed particles.28
Thermal degradation of both the TEMPO-oxidized softwood
cellulose and TOCN films started to occur at approximately 200

C in a nitrogen atmosphere, while for the original cellulose,
degradation began at 300  C. Thus, the formation of sodium
carboxylate groups from the C6 primary hydroxyls of cellulose
microfibril surfaces by TEMPO-mediated oxidation leads to
a significant decrease in the thermal degradation point
(Fig. 25).28,60,98,111 The thermal expansivity of TOCN films was
measured in a nitrogen atmosphere after heating the film at 120

C for 10 min to remove residual moisture. The coefficient of
Fig. 23 Tensile strength and elastic modulus of TOCN film, 20% thermal expansion (CTE) of the TOCN film was approximately
Published on 19 October 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00583E

TOCN/PVA composite film and others. 2.7 ppm K 1, which is much lower than that of glass (ca. 9 ppm
K 1). The extremely low CTE is caused by the high crystallinity
of the nanofibers comprising the TOCN film.28
Atomic force microscopy (AFM) observation of TOCN films
showed that the film surface consists of randomly assembled
nanofibers (Fig. 26).28 The nanofiber widths were estimated to be
3–4 nm from the height of the AFM images, which is in good
agreement with TEM measurements.27,29 The elastic modulus of
single TEMPO-oxidized tunicate cellulose nanofibers was
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measured by three-point bending test using an AFM cantilever to

be approximately 145 GPa.112

Fig. 24 Change in the contact angle over time of a water droplet on

a nanofiber film prepared from TEMPO-oxidized softwood cellulose
before and after treatment with a 0.05% alkyl ketene dimer dispersion.28
Reproduction of images and figure from ref. 28 with permission from
American Chemical Society (ª American Chemical Society 2009).

droplet placed on a TOCN film decreased from 47 over time as

a result of partial penetration of water into the film. Alkyl ketene
dimer (AKD) is a typical hydrophobizing chemical used in
papermaking processes. TOCN film treated with a 0.05% AKD
dispersion had a water-contact angle of 94 , and this value was Fig. 26 AFM image of the surface of a nanofiber film prepared from
maintained for 10 s (Fig. 24). Therefore, hydrophilic TOCN films TEMPO-oxidized softwood cellulose.28 Reproduction of image from ref.
can be hydrophobized using a simple soaking method with 28 with permission from American Chemical Society (ª American
a cationic AKD dispersion. The abundant carboxylate groups in Chemical Society 2009).

Fig. 25 Thermogravimetric curves of the original cellulose, TEMPO- Fig. 27 Light transparency and flexibility of poly(lactic acid) (PLA) film
oxidized cellulose and TOCN film.98 Reproduction of figure from ref. 98 coated with softwood TOCN film, and oxygen permeability values of the
with permission from Elsevier (ª Elsevier 2010). base PLA and TOCN/PLA films.

82 | Nanoscale, 2011, 3, 71–85 This journal is ª The Royal Society of Chemistry 2011
 View Article Online

The oxygen permeability of a poly(lactic acid) (PLA) film Acknowledgements

surface-coated with TOCN was examined under dry conditions.
The original PLA film had an oxygen permeability of approxi- This research has been continuously supported by Grants-in-Aid
mately 7.4 mL m 2 day 1 kPa 1. Surprisingly, the oxygen for Scientific Research from the Japan Society for the Promotion
permeability was decreased to <0.001 mL m 2 day 1 kPa 1 of Science (JSPS) from 1996 to 2013. The TOCN Nanotech
(Fig. 27) by the thin TOCN layer.28 The oxygen permeability of Challenge Project has been supported by NEDO from 2007 to
the TOCN-coated PLA film was close to that for typical 2012.
synthetic polymer films such as poly(vinylidene chloride) and
poly(ethylene)-poly(vinyl alcohol) copolymer that have high
oxygen barrier functionality. The refractive index of PLA (1.48– References
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