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Cellulose polymorphs and physical properties of cotton fabrics processed with

commercial textile mills for mercerization and liquid ammonia treatments

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DOI: 10.1177/0040517514527379

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Original article
Textile Research Journal
2014, Vol. 84(16) 1692–1699

Cellulose polymorphs and physical ! The Author(s) 2014

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properties of cotton fabrics processed DOI: 10.1177/0040517514527379
trj.sagepub.com
with commercial textile mills for
mercerization and liquid ammonia
treatments*

Kabindra Kafle1, Kenneth Greeson2, Christopher Lee1

and Seong H Kim1

Abstract
We report the detection of cellulose polymorphs, using spectroscopic and diffraction techniques, in cotton fabrics
treated with commercial textile mill processes designed for better dyeing and mechanical properties. Vibrational sum
frequency generation (SFG) spectroscopy analysis of cotton is known to be selective and sensitive to the crystalline
cellulose portion in the sample. The SFG analysis results were compared with the results from conventional analytical
techniques such as X-ray diffraction (XRD) and infrared (IR) spectroscopy. The XRD detection of a small fraction of
cellulose II present in the partially-mercerized fabric was difficult, while SFG and IR analysis indicated the partial con-
version of cellulose I to II without significant reduction of the cellulose crystallinity. Processing the cotton fabric with the
liquid-ammonia treatment mill caused partial conversion of cellulose I to III and significant reduction of the overall
crystallinity of cellulose. All XRD, SFG, and IR techniques were able to monitor this conversion. When the cotton fabric
was treated with the partial mercerization process first and then the liquid-ammonia process, both cellulose II and
cellulose III were produced and identified with SFG. But XRD and IR failed to detect the presence of cellulose II in the
mercerized and ammonia-treated fabric. The polymorphic changes found in the SFG, XRD, and IR analyses provided
insights into the physical property changes of cotton fabric after commercial mercerization and liquid-ammonia treatment
processes.

Keywords
cotton fabric, mercerization, liquid ammonia treatment, cellulose polymorphs, sum-frequency-generation spectroscopy,
X-ray diffraction

Physical and chemical properties of cotton fabrics are

of great interest for their commercial utilization in tex-
tile industry. Cotton fiber consists of highly crystalline
cellulose Ib. To improve the luster, dyeability, and *
This paper was presented at the 2013 Beltwide Cotton Conferences,
mechanical strength of cotton, several different chem- San Antonio, and is a part of the conference proceedings.
ical treatments are desired before generating a finished 1
Department of Chemical Engineering and Materials Research Institute,
product.1–3 Among them, sodium hydroxide and liquid The Pennsylvania State University, USA
2
ammonia treatments are routine methods used to Cotton Incorporated, USA
modify and improve various properties of cotton fab-
rics.4,5 The sodium hydroxide treatment, which is called Corresponding author:
Seong H Kim, Department of Chemical Engineering and Materials
mercerization, can improve the dye receptivity and Research Institute, The Pennsylvania State University, University Park,
luster of cotton fabrics. The liquid ammonia treatment PA 16802, USA.
is used to enhance the wrinkle resistance, hand and Email: shkim@engr.psu.edu
Kafle et al.
Figure 1. SEM images of cotton fibers. (a) Side view of cotton fibers from top to bottom: bleached, mercerized, and liquid ammonia
treated. Cross-section views of (b) bleached cotton, (c) mercerized cotton, and (d) liquid ammonia-treated cotton fabric. Reprinted
with the permission of Yuichi Yanai.6
drape of cotton fabrics. These treatments are also
known to alter the shape of the cotton fibers.6 The
bleached cotton fiber has a ribbon shape with many
twists along its length and kidney-shape cross-section
due to collapsed lumen (Figure 1(a) and (b)).7,8 After
the mercerization treatment, the walls of cotton fibers
become slightly swollen and thicker (Figure 1(c)). The
liquid ammonia treatment swells the cotton fibers so
that the fiber twists are hardly visible (Figure 1(a))
and the fiber cross-sections do not have the character-
istic kidney shape (Figure 1(d)). These morphological
changes in the cotton fibers after mercerization and
liquid ammonia treatments must be partially respon-
sible for changes in their mechanical properties.
In addition to the morphological changes, poly-
morphic changes in cellulose crystal structure are also
expected. Strong alkali treatments can convert cellulose
Ib into cellulose II, and liquid ammonia can change cel-
lulose Ib into cellulose III.9,10 It is sometimes desired to
treat the cotton fabrics with both methods consecu-
tively, which results in a mixture of three allomorphs
(Ib, II, III), to optimize various properties (enhanced
dyeability and softness of handle). The mercerization
and liquid ammonia treatment conditions used in textile
industry are mild or the treatment times are short, so the
conversions of Ib to II and III are incomplete. Thus, the
determination of the polymorphic structures of
1693
crystalline cellulose in the processed cotton fabric is
important to assess meaningful correlations between
the cellulose crystal structures and the fabrics properties.
X-ray diffraction (XRD) has been the most widely
used technique to analyze the cellulose crystal structure.
Based on the positions and relative intensities of dif-
fraction peaks, cellulose polymorphs can be identi-
fied.10 Cellulose Ib has unit cell dimensions of
a ¼ 7.84 Å, b ¼ 8.20 Å, c ¼ 10.38 Å, a ¼ b ¼ 90 , and
g ¼ 96.5 .11,12 Cellulose II produced by the merceriza-
tion has unit cell dimensions of a ¼ 8.10 Å, b ¼ 9.03 Å,
c ¼ 10.31 Å, a ¼ b ¼ 90 , and g ¼ 117.1 ; two chains in
the cellulose unit cell are antiparallel.13 Cellulose IIII
and IIIII are produced by liquid ammonia treatments of
cellulose Ib and II, respectively.14,15 Cellulose IIII has
unit cell dimensions of a ¼ 4.45 Å, b ¼ 7.85 Å,
c ¼ 10.31 Å, a ¼ b ¼ 90 , and g ¼ 105.1 and cellulose
IIIII has unit cell dimensions of a ¼ 4.45 Å, b ¼ 7.64 Å,
c ¼ 10.36 Å, a ¼ b ¼ 90 , and g ¼ 106.96 .14,16 Once
again, the main difference between these allomorphs
is that cellulose IIII has parallel glucan chains, while
the glucan chains in cellulose IIIII are antiparallel.15
When these allomorphs coexist in the cotton fabric,
the detection of each component with XRD could be
challenging especially when the cellulose crystallinity is
low.17,18 For low crystalline cellulose samples, the dif-
fraction peaks are broad and there is a large amorphous
1694
halo that overlaps with the broad diffraction peaks of
cellulose polymorphs. In addition, the main diffraction
peaks of cellulose polymorphs are close to each other.
Another routinely used technique for cellulose struc-
ture analysis is infrared (IR) spectroscopy.19 Cellulose
polymorphs can be identified from the OH stretch
peaks in the 3200–3600 cm1 region. The characteris-
tic peak of cellulose Ib is at 3270 cm1.20 Cellulose II
has two additional peaks at  3450 cm1 and
 3480 cm1.19,21 Cellulose III has one characteristic
peak at  3480 cm1.19 For cotton fabric analysis, atte-
nuated total reflectance (ATR)-IR is very convenient
since no sample preparation is required and intact
fabric samples can simply be pressed against an
ATR-IR crystal for this analysis. Considering mild or
short treatment conditions of commercial textile mills
used for mercerization and liquid ammonia processes,
one might expect that the cellulose crystals at the sur-
face of cotton fabrics are affected more severely than
the interior of the fibers. If this is the case, ATR-IR
could provide significant advantages over XRD since
the probe depth of ATR-IR is only 1–2 mm from the
surface.22,23
Recently, we have demonstrated that vibrational
sum frequency generation (SFG) spectroscopy can
selectively detect the crystalline cellulose in plant cell
walls and lignocelluloses.12,17,24–29 SFG is a nonlinear
optical process taking place when the sample is irra-
diated with high-intensity laser pulses. In this experi-
ment, two ultra-short laser pulses are overlapped on the
sample surface, and then new photons whose frequency
is the sum of two input laser frequencies are
detected.30,31 The sum-frequency photons can be pro-
duced only when molecules or functional groups are
arranged in a non-centrosymmetric environment.32
The cellulose crystals can meet this non-centrosymme-
try requirement, but other amorphous carbohydrate
polymers do not. This makes SFG possible to distin-
guish crystalline cellulose from amorphous polymer
matrices in which the cellulose crystals are dispersed.
When one of the input lasers is tuned to mid-IR range,
then SFG spectra can provide vibrational information
of specific functional groups in crystalline cellulose. The
crystal symmetries of cellulose polymorphs can be dis-
tinguished by SFG.15 The main differences among cel-
lulose polymorphs are the hydrogen bonding network
and the conformation of the exocyclic CH2OH group.15
In this study, we have compared these three tech-
niques, XRD, ATR-IR, and SFG, to identify the cellu-
lose polymorphs in cotton fabrics processed with
commercial textile mills designed for mercerization
and liquid ammonia treatments. Each technique is sen-
sitive to different aspects of the cellulose structure.12
Bleached twill fabrics were subjected to mercerization,
liquid ammonia treatment, and mercerization followed
Textile Research Journal 84(16)
by liquid ammonia treatments using the conditions typ-
ically used in textile industries. It was found that XRD
could not easily detect cellulose II in the fabric sample
treated with the commercial mercerization process,
while it showed good sensitivity to cellulose III in the
liquid ammonia treated sample. ATR-IR was able to
show the presence of cellulose II and III in the single-
treated samples; but it could not confirm the coexist-
ence of cellulose II and III in the sample treated
with both methods sequentially. SFG showed the best
sensitivity for all tested samples.
Materials and methods
Treatments of cotton fabric
The fabric used for this study was 100% cotton twill
(270 g/m2) fabric that had been commercially woven at
a mill in South Carolina. This fabric was subjected to
various treatments in order to generate different forms
of crystalline cotton cellulose. The ‘bleached-only
cotton (BC)’ was obtained by processing the twill
fabric on a jig in Cotton Incorporated’s pilot labora-
tory. In brief, the fabric was enzyme-desized to remove
starch, scoured to remove waxes, and bleached with a
hydrogen peroxide formulation to remove the colored
impurities. These processes were designed to remove
the impurities from the cotton fabric while maintaining
its natural crystalline structure as cellulose I.
The ‘mercerized cotton (BMC)’ fabric was processed
in a commercial textile mill in Georgia. Desizing, scour-
ing, bleaching, and mercerizing were performed using a
continuous open-width processing equipment. The
mercerization step was immersion in 20–25% (weight
basis) sodium hydroxide at 15–20 C under tension, fol-
lowed by washing and neutralization.33 The duration of
the mercerization process was approximately one
minute.
The BC and BMC fabric samples were taken to
Lafer SpA in Prato, Italy, for liquid ammonia treat-
ment on a new Permafix machine. Briefly, during the
liquid ammonia treatment, the fabric was passed over
drying and cooling cans to remove residual fabric mois-
ture. The fabric entered a sealed chamber in which the
fabric was immersed in chilled, liquefied ammonia at
38 C, and then the ammonia was removed by
vacuum and sent to a recovery system. The fabric was
then steamed to remove any traces of ammonia. The
‘liquid ammonia treated’ BC and BMC samples will be
designated hereafter as BAC and BMAC, respectively.
X-ray diffraction (XRD) measurements
The treated fabrics (BC, BMC, BAC, and BMAC) were
analyzed with a Scintag XDS 2000 X-ray diffractometer
Kafle et al.
equipped with a Cu Ka X-ray source (43 kV and 38 mA;
wavelength ¼ 1.54059 Å) and a goniometer. A piece of
the treated cotton fabric was mounted on a sample
holder using a double-sided tape. The fabric sample
was mounted at about 45 to the woven yarns; so
none of the yarns were aligned to the X-ray beam. A
zero background plate was used and the tape was only
applied to the edges of the fabric sample and not in
the X-ray beam path. The XRD diffractogram was
collected within a 2y range of 8–38 with a step size
of 0.03 .
Attenuated total reflection infrared (ATR-IR)
spectroscopy
ATR-IR spectra of cotton fabrics were collected using
a Nicolet 8700 FT-IR Spectrometer (Thermo
Scientific) equipped with a smart iTR diamond ATR
unit, a KBr beam splitter, and a deuterated triglycine
sulfate (DTGS) detector. The ATR-IR spectrum was
collected from the piece of fabric of a size of
1 cm  0.5 cm compressed against the ATR unit.
Each spectrum was recorded in the region
650–4000 cm1 with a 4 cm1 resolution and averaged
over 100 scans.
Vibrational sum frequency generation (SFG)
spectroscopy
Details of the SFG system was described in a previ-
ous publication.24 The system used a picosecond
Nd:YAG 1064 nm laser operated at a 10 Hz repeti-
tion rate. A 532 nm visible laser pulse was generated
through frequency doubling of the Nd:YAG output.
A tunable 2.3–10 mm infrared laser pulse was gener-
ated through optical parameter generation and amp-
lification processes. The infrared beam and visible
beam were temporally and spatially overlapped
at the treated cotton fabric at incidence angles of
56 and 60 with respect to the surface normal,
respectively. The input laser polarization was p- for
IR and s- for visible. The SFG signal with
s-polarization was detected in a reflection geometry.
A beam collimator was used to increase the SFG
signal collection efficiency. A monochromator was
used for filtering SFG signal which was recorded
with a photomultiplier. SFG spectra were taken at
4 cm1 interval in the C–H stretch vibration region
(2700–3050 cm1) and 8 cm1 interval in the O–H
stretch vibration region (3100–3800 cm1). The SFG
signal was averaged over 100 laser pulses at each
interval step and normalized with the IR and visible
input laser intensities. The SFG peaks were deconvo-
luted with the Lorenzian peak shape to find poly-
morphic components.
1695
Physical properties of the treated samples
Physical property tests were performed on the fabric
samples at various stages of treatment following stand-
ard protocols set by American Association of Textile
Chemists and Colorists (AATCC) and American
Society for Testing and Materials (ASTM). The
smoothness rating (AATCC TM 124) was performed
after the fabric was laundered and dried (in this case,
three home laundering and tumble drying cycles were
performed); the fabric specimens were then compared
to a visual scale (1 ¼ most wrinkled; 5 ¼ least wrinkled).
The wrinkle recovery rating (AATCC TM 128) was
performed by twisting and compressing a fabric speci-
men, then allowing the wrinkles to recover; this test was
rated to a 1–5 visual scale. Tensile strength, tear
strength, and flex abrasion were tested following the
ASTM D5034, ASTM D1424, and ASTM D3885
protocols, respectively.
Results and discussion
To investigate polymorphic changes of cellulose in the
treated cotton fabrics, it is important to recognize the
characteristic features of each allomorph. Figure 2 dis-
plays the SFG spectra, XRD diffractograms, and
ATR-IR spectra of reference samples of cellulose Ib,
II, and IIII prepared from a commercial microcrystal-
line cellulose (Avicel PH-101). The details of these ref-
erence samples were described in a previous
publication.15 In SFG, cellulose Ib shows characteristic
peaks at 2850 cm1 and 2944 cm1 assigned to the CH2
symmetric and asymmetric vibration modes, respect-
ively, of the exocyclic CH2OH group in the tg conform-
ation.15,25 The SFG peak at 3320 cm1 in the OH
stretch region is assigned to the hydroxyl groups
involved in intra-chain hydrogen-bonding along the
cellulose chain.24,25 In XRD (Figure 2(b)), the peaks
at 2y ¼ 14.7 , 16.5 , 20.6 , and 22.6 correspond to
the planes with Miller indices (110), (110), (102), and
(200) of cellulose Ib, respectively.34 In ATR-FTIR, the
3270 cm1 and 3340 cm1 peaks are the characteristic
peaks of cellulose Ib.12
The CH2 SFG peaks are shifted to 2890 cm1 and
2964 cm1 upon the conversion of cellulose Ib to cellu-
lose II and IIII (Figure 2(a)). This shift is believed to be
associated with the transition from the tg to gt con-
formation for the CH2OH group in cellulose II and
IIII.15 In the OH region, cellulose II shows a very
weak or negligible peak at 3450–3484 cm1, while cel-
lulose IIII gives a strong peak at 3484 cm1. These
changes are due to alterations of the hydrogen-bonding
networks upon polymorphic transitions. The peak pos-
itions of these OH SFG peaks are in good agreement
with the peaks in ATR-IR (Figure 2(c)).15 The absence
1696
Figure 2. Cellulose polymorphs can be identified from spectroscopic and diffraction techniques. (a) SFG, (b) XRD, and (c) ATR-FTIR
spectra of cellulose Ib, II, and IIII.
of strong OH peaks in SFG of cellulose II is attributed
to the antiparallel arrangement of cellulose chains in
the crystal; thus, the dipoles of the intra-chain
hydrogen-bonded hydroxyl groups are cancelled,
making them SFG-inactive.15 It is noted that for cellu-
lose IIII, the OH SFG intensity is stronger than the
CH2 SFG intensity, implying good coherence between
parallel cellulose chains in this allomorph. In XRD
(Figure 2(b)), cellulose II gives peaks at 2y ¼ 12.2 ,
19.9 , and 21.8 , which correspond to the (110), (110),
and (020) planes, respectively; cellulose IIII has a weak
diffraction peak at 2y ¼ 11.7 (010) and a strong peak
near 20.7 , which is a combination of contributions
from (100), (012), and (110).34–36 A small sharp peak
at 2y ¼ 17.2 is the (002) peak, corresponding to the
length of one glucan unit along the chain direction.34
The characteristic features of cellulose polymorphs
can be utilized to identify cellulose polymorphic struc-
tures in the treated cotton fabrics. Figure 3 compares
the SFG, XRD, and ATR-IR analysis results of the
BC, BMC, BAC, and BMAC fabrics. The BC sample
clearly shows the characteristic peaks of cellulose Ib in
SFG (2944 cm1 and 3320 cm1), XRD (14.7 , 16.4 ,
20.6 , and 22.6 ), and ATR-IR (3270 cm1 and
3340 cm1). The baseline between 16.4 and 20.6 is
quite low, indicating the highly crystalline nature of
cellulose Ib in the BC sample. Although it is known
that the peak height method is not accurate,12,17 we
used it as a convenient measure for qualitative compari-
son. The calculated crystallinity of cellulose in BC is
estimated to be  86%.
In the BMC sample, the partial conversion to cellu-
lose II can be confirmed from the 3450 cm1 and
3484 cm1 peaks in ATR-IR (Figure 3(c)) and the
increase in the 2964 cm1 component in SFG (Figure
3(a)). However, the presence of cellulose II (19.9 and
Textile Research Journal 84(16)
21.8 ) could not be determined unambiguously in XRD
(Figure 3(b)); this is mainly due to the low merceriza-
tion yield and the peak overlaps with the broad
amorphous background and the diffraction peaks of
cellulose I (20.6 and 22.6 ), which is still the dominant
component in the BMC sample. The XRD crystallinity
of cellulose in the BMC sample (84%) does not seem to
decrease significantly compared to the BC sample. The
SFG signal intensity can be related to the amount of
crystalline cellulose in the sample;12,17 the BMC SFG
intensities are almost the same as the BC intensities in
Figure 3(a). Thus, SFG also confirms that the cellulose
crystallinity does not decrease significantly upon the
commercial mercerization treatment. If the presence
of cellulose II is confirmed from ATR-IR and SFG
analyses, one could fit the XRD data with cellulose I,
cellulose II, and amorphous components and find a
small contribution from cellulose II. But, without
ATR-IR and SFG data, it would not be obvious to
include cellulose II component in the XRD peak fitting.
The BAC sample shows the characteristic OH peak
of cellulose IIII at 3484 cm1 in ATR-IR (Figure 3(c))
and SFG (Figure 3(a)) and the increase in the
2964 cm1 component in the CH2 region of the SFG
spectrum (Figure 3(a)). XRD also clearly shows the
formation of cellulose IIII component with the peaks
at 11.7 and 20.7 , in addition to the cellulose Ib peaks
at 14.7 , 16.4 , and 22.6 (Figure 3(b)). The small frac-
tion of the 20.7 peak must come from the cellulose Ib
component (20.6 ). It is also noted that the (110) and
(110) peaks of cellulose Ib are not well resolved and the
background between the 16.4 and 20.7 are much
higher than the BC sample. This implies the significant
decrease in the cellulose crystallinity (63%) upon the
liquid ammonia treatment. The broadening of the OH
peak in ATR-IR (Figure 3(c)) and the significant
Kafle et al.
Figure 3. (a) SFG spectra, (b) XRD diffractograms, and (c) ATR-IR spectra of the treated cotton fabrics: bleached (BC), bleached and
mercerized (BMC), bleached and liquid ammonia treated (BAC), and bleached, mercerized, and then liquid ammonia treated (BMAC).
decrease in the SFG intensity (Figure 3(a)) also support
the reduction of the cellulose crystallinity in the BAC
sample.
The BMAC sample is the most challenging to ana-
lyze since it can contain all forms including amorphous
cellulose. After the first mercerization step, cellulose Ib
would have been partially converted to II; the following
liquid ammonia treatment step could convert cellulose
Ib to cellulose IIII and cellulose II to IIIII. In XRD
(Figure 3(b)), cellulose I and IIII can be identified.
Cellulose IIIII has almost identical XRD peaks as cel-
lulose IIII, thus its presence cannot be confirmed in
XRD. Also, it is noted that the XRD crystallinity of
cellulose in BMAC (60%) is the lowest among four
treated samples. Since XRD crystallinity tends to over-
estimate the crystallinity, the true crystallinity would be
much lower.12,17 The low crystallinity means that there
are more water molecules in the amorphous portion of
the sample. Because of this high water content, the OH
peak in ATR-IR is very broad and makes it difficult to
identify characteristic peaks of cellulose polymorphs
(Figure 3(c)). In SFG, the clear peak at 3320 cm1
and 3484 cm1 confirms the presence of cellulose I
1697
and IIII in the BMAC sample. Cellulose II and IIIII
do not show strong OH peaks in SFG.15 The CH2
SFG peak shape is highly perturbed that the peak
center is now shifted to  2952 cm1. When this CH2
peak is deconvoluted with two components, it is clear
that the 2944 cm1 and 2964 cm1 components are
almost equal. It is noted that the relative intensities of
the 2964 cm1 component to the 3484 cm1 peak is
slightly higher for BMAC than BAC. This might be
due to the presence of cellulose II (and probably cellu-
lose IIIII), in addition to cellulose IIII, in BMAC.
However, the 2964 cm1/3484 cm1 ratio of the
BMAC SFG spectrum (Figure 3(a)) is still lower than
that of highly-crystalline cellulose IIII reference sample
(Figure 2(a)). This could be due to the low crystallinity
of cellulose in BMAC. In any case, this discrepancy
from the reference sample makes it difficult to accur-
ately determine the amount of cellulose II from the
2964 cm1/3484 cm1 intensity ratio of the MBAC
SFG data.
The polymorphic changes revealed by the SFG,
XRD, and ATR-IR analyses provide insights into the
physical property changes of cotton fabric after
1698 Textile Research Journal 84(16)

Table 1. Physical properties of cotton twill fabrics treated with bleach, mercerization, and liquid ammonia processes

Wrinkle Tensile Tear

Smoothness recovery strength, strength, Flex abrasion,
Rating rating filling, filling, lbs. cycles (ASTM
Sample (AATCC TM 124) (AATCC TM 128) lbs (ASTM D5034) (ASTM D1424) D3885)

BC 1.2 1.5 122 3.7 218

BMC 1.2 1.6 124 3.4 230
BAC 2.3 2.9 93 8.3 534
BMAC 1.5 2.3 90 8.9 377

commercial mercerization and liquid-ammonia treat-
ment processes. Table 1 compares the smoothness,
wrinkle recovery, tensile, strength, tear strength, and
flex abrasion properties of the BC, BMC, BAC, and
BMAC samples. For the mercerized samples (BMC),
the cellulose II conversion yield was very low
(Figure 3), and the physical properties showed little
change from the bleached-only samples (BC) in all
five properties tested in this study. This indicated that
the commercial mercerization process used in the
cotton textile industry has very marginal effects on
polymorphic changes and physical property improve-
ments. The largest effects on fabric properties occurred
after liquid ammonia treatment (BAC and BMAC sam-
ples). The BAC sample showed the most improvement
in smoothness and wrinkle recovery. Liquid ammonia
treatment also yielded substantial improvements on
tear strength and flex abrasion. Interestingly, the tensile
strength of the liquid ammonia fabrics decreased. These
changes could be attributed to some conversion to cel-
lulose III as well as the decrease in the overall crystal-
linity (Figure 3).
IIIII. ATR-IR is not effective to identify crystalline cel-
lulose components in the BMAC sample containing
a large amount of amorphous cellulose. SFG
has detected the presence of cellulose Ib, IIII, and
potentially II and IIIII in BMAC; but quantification
is difficult due to the low crystallinity nature of the
sample. The changes in physical properties reflect the
changes observed in the polymorphs.
Funding
This work was supported by Cotton Incorporated (for fabric
sample preparation and SFG data collection) and The Center
for Lignocellulose Structure and Formation, an Energy
Frontier Research Center funded by the US Department of
Energy, Office of Science and Office of Basic Energy Sciences
(grant number DE-SC0001090).
Acknowledgments
We acknowledge Pierre Burnside from Tulane University for
help with XRD measurements and Ashutosh Mittal and
David Johnson for supplying reference samples for cellulose
II and IIII.

Conclusions
The cellulose polymorphs (Ib, II, IIII, and IIIII) in
cotton fabrics processed with commercial textile mills
were analyzed with XRD, ATR-FTIR, and SFG. The
bleached cotton fabric (BC) contains highly crystalline
cellulose Ib. When the cotton fabric is treated with a
commercial mercerization process with a continuous
open-width mill (BMC), a small fraction of cellulose
Ib is converted to cellulose II, which can be detected
with ATR-IR and SFG. Due to the low conversion
yield, XRD could not detect cellulose II unambigu-
ously. The liquid ammonia treatment (BAC) converts
a fraction of cellulose Ib to cellulose IIII and reduces the
overall crystallinity. All three techniques can monitor
this polymorphic change. For the mercerized and then
liquid ammonia treated sample (BMAC), the presence
of all polymorphic species along with amorphous cellu-
lose is expected. XRD is able to detect cellulose Ib, IIII,
and amorphous components in BMAC, but not II and
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