Original article

Preliminary evidence of oxidation in

standard oven drying of cotton:
attenuated total reflectance/Fourier
transform infrared spectroscopy,
colorimetry, and particulate matter
formation

Textile Research Journal

84(2) 157173
! The Author(s) 2014
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DOI: 10.1177/0040517513487785
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Chanel Fortier, Joseph Montalvo, Terri Von Hoven,

Michael Easson, James Rodgers and Brian Condon

Abstract
Currently, oven drying in air is often utilized to generate the percentage of moisture in cotton fibers. Karl Fischer
Titration, another method for cotton moisture measurement, has been compared to the oven drying method. The
percentage of moisture as generated by the oven method tracks those of Karl Fischer Titration, but there are differences
between the two. In fact, a bias exists in the measured moisture loss employing the standard oven drying method. In
addition, the moisture data collected via Karl Fischer Titration demonstrates smaller variances than those data collected
in the oven. The aim of this study is to determine what is causing those differences. In the current report, particulate
matter formation and browning of oven-treated cotton samples have been observed, suggesting visible indirect evidence
that cotton oxidation may be occurring. It is noteworthy that three types of oxidation processes may be occurring during
the current study: heating in air, scouring and bleaching, and periodate-driven processes. The first two oxidative
processes yield non-specific products, whereas the periodate-driven oxidative products are well-defined in the literature.
Thus, a method was needed to gain direct evidence for this postulated cotton oxidation that may be contributing to the
bias in the standard oven drying method used to calculate moisture loss in cotton. Thus, this preliminary study employed
Attenuated Total Reflectance/Fourier Transform Infrared spectroscopy to determine if direct evidence for oxidation can
be observed for oven-treated cotton samples.

Keywords
cotton, oxidation, color

Two American Society for Testing and Materials

(ASTM) standard test methods to measure moisture
in lint cotton are available to the industry. One is standard oven drying (SOD) in air at 105110 C; all of the
weight loss is attributable to moisture.1 However, not
all of the water is removed; there is loss of non-aqueous
volatiles (NAVs) and indirect evidence suggests sample
oxidation.2,3 The other standard method is based on
oven drying in nitrogen combined with Karl Fischer
Titration (KFT) of the water vapor removed from the
sample.4 In the latter method there are no known
biases; all of the water in the sample is available for
titration and sample oxidation does not occur. Based

on the data to date, the dierence in results between

SOD and KFT is about 0.20.7% water. Thus, there is
a need to understand further the biases in SOD.

Agricultural Research Service, U.S. Department of Agriculture, Southern

Regional Research Center, USA
Corresponding author:
Chanel Fortier, Agricultural Research Service, U.S. Department of
Agriculture, Southern Regional Research Center, 1100 Robert E. Lee
Boulevard, New Orleans, Louisiana, USA.
Email: chanel.fortier@ars.usda.gov

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Studies of NAVs by complementary thermal methods at SOD conditions included changing the gaseous
atmosphere from air to nitrogen; thermogravimetric
analysis; distillation of cotton samples; and colorimetry.2,3 In collaborative studies performed in
Germany, no specic volatile organics were detected
at SOD conditions by thermogravimetric analysis
quadrupole mass spectrometry (TGA-QMS).2 Sample
weight loss and weight gain, not attributable to water,
was found in the TGA-QMS studies; this was also
reported by meticulous SOD studies in our laboratory.
Distillation of cotton in a glass apparatus with air carrier gas conrmed the presence of volatile organics;
NAV material of very low volatility and/or particulate
matter was visible on the inside walls of the apparatus.
Colorimetry after heating cotton at 105 C correlated
with treatment at 150 C where the browning was visible
with the eye.
The mechanism proposed for SOD is complex.3 Two
competing events, other than loss of moisture, occur:
the loss of NAVs and the oxidation of cellulose. The
former causes additional weight loss, while the latter
results in weight gain and weight loss. During oven
drying in air these three processes occur at dierent
rates.
Direct evidence of cellulose oxidation in SOD to
carbonyl products would support the proposed mechanism. Fourier Transform Infrared (FT-IR) spectroscopy has been previously used to study cellulose
oxidation with the identication of carbonyl and carboxyl products being reported.510 In addition,
Attenuated Total Reectance/Fourier Transform
Infrared (ATR/FT-IR) spectroscopy accessories have
been widely used, which greatly simplies sample preparation compared to traditional FT-IR samples
employing KBr pellets.
Thermal oxidation of cellulose may give a broad
range of cellulose derivatives compared to cellulose oxidized using periodate, which is highly specic to the
formation of 2,3-dialdehyde cellulose.5,8 The latter has
been extensively characterized by FT-IR. The objective
of the current study is to use ATR/FT-IR spectroscopy
as a primary method to help explain the dierences
between moisture contents determined by the SOD
and KFT methods by the detection of cotton oxidation
products.

Both of the AMS cottons had micronaires of approximately 4.5. For the oxidation studies, a 50 g portion of
the 2007 raw cotton was also cleaned using two passes
on the Shirley Trash Analyzer. Commercially available
scoured and bleached cotton (cotton balls) was
obtained from a national retailer and used as control
cottons. The cottons were labels as CB for the control
cotton balls and 2001 for the crop year, with 2007 and
2007 SH designating the crop year and the Shirleycleaned cotton.

Oven drying: air

The Curtin Matheson Equatherm D 1580 gravity convection oven was used with an approximate capacity of
72.75 L and a ow rate of approximately 0.25 L/s and
set to 105 C. The sample size used was approximately
1 g for easier comparison with the KFT data. A test run
consisted of ten 1 g samples that had been subjected to
standard textile testing conditions for at least 24 h.
Samples were placed in pre-weighed glass weighing bottles, capped, and weighed again to obtain preheated
mass. Open bottles were placed in a wire basket and
into a 105 C or a 150 C oven for 24 h. When drying
was completed, each bottle was capped and placed in
individual mini-desiccators to cool, as seen in Figure 1.
The individual mini-desiccators contained anhydrous
calcium sulfate covered with steel wool and a mesh
screen to house the weighing bottles. This experimental
set up prevented any additional moisture from permeating the cotton samples. After being allowed to
acclimate in a conditioned lab for at least 15 min, the
weighing bottles were removed from the mini-desiccators and immediately weighed to determine oven-dried
weight.11

Material and methods

Cottons
The cottons used in this study were commercial cottons
obtained from the Agricultural Marketing Service
(AMS). One was mechanically cleaned from the 2001
crop year, and one was raw from the 2007 crop year.

Figure 1. Mini-desiccator (left) used to transport 1 g standard

oven-dried samples (right).

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159

Oven drying: N2
For this procedure, a VWR 1310 Economy oven was
used due to its 1 ft3 size. Dry nitrogen (<1 ppm water,
vol./vol.) was preheated to approximately 100 C and
piped into the oven at 180 mL/min through a central
copper tube of one-fourth in diameter in the center of a
9-in diameter cake pan. The cotton samples were in
weighing bottles arranged around the outer edge of
an 8-in diameter cake pan. In the center of the
bottom pan, a crystallizing dish was placed upside
down to reduce any dead space. Both cake pans were
lined with a silicone mat, the top to provide a better
seal when the system was closed, and the bottom to
keep the weighing bottles from sliding. The top pan
was outtted with magnets, so when it was time to
cap the weighing bottles containing the cotton samples,
the lid could be stored on the top of the oven and the
procedure could take place quickly. The 9-in diameter
cake pan was placed over the 8-in diameter cake pan
containing the samples. Above each of the weighing
bottles in the top pan were exit tubes to allow the
moist air to escape. The nitrogen was to blanket the
cotton samples to limit the amount of air available for
oxidation. The oven was set at 105 C, 125 C, or 150 C
for the various experiments. The nitrogen delivery
system can be seen open in Figure 2(a) and closed in
Figure 2(b).

Figure 2. Nitrogen delivery system used to dry samples in the

oven: (a) open; (b) closed.

Particulate matter
A Curtin Matheson Equatherm D 1580 oven was used
to study if any particulate matter was being released in
oven drying of cotton samples.11 This was a gravity
convection oven with an approximate capacity of
72.75 L and a ow rate of approximately 0.25 L/s and
set to 105 C. It is noteworthy that a mechanical oven
was not used during this investigation, since the ow
was too high and the vent was smaller. Ten 1 g replicates of the cotton balls, the 2001 cotton and the 2007
cotton, were placed in weighing bottles. On top of the
weighing bottles, a microscope slide with high-temperature grease lightly smeared on one side was placed with
the greased slide down to catch any particulate matter
being released during the 24 h oven drying procedure,
as shown in Figure 3. The microscope slide did not
cover the entire weighing bottle so that water vapor
could escape. After 24 hours, the slides were cooled,
removed from the oven, and studied with a Nikon
light microscope tted with a 20  objective with an
eyepiece of 1.75, which yielded a magnication of
35. Images of the bers were captured using the
Image Pro Plus. The microscope slides were then studied under a microscope. Due to the volatility of the
grease, no quantitative data was generated.

Figure 3. Slide with grease to capture particulate matter on

top of weighing bottle.

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Textile Research Journal 84(2)

In an attempt to quantify particulate matter, hightemperature double-sided tape was the next choice.
Thus, two microscope slides with high-temperature
double-sided tape, called Loctite Power Grab, were
placed on top of the vent on the top of the oven, as
shown in Figure 4. The tape did not cover the entire
vent so that water vapor could still escape. The tape
could be measured to exact lengths, weighed, and was
more stable than the grease. Preliminary tests, with no
cotton in the gravity convection oven, revealed that
there was a constant oset that could be subtracted
for the particular length of tape being used. Ten 1 g
cotton ball samples were placed in the 105 C oven
with the taped microscope slides over a portion of the
vent hole of the oven. The weights of the slides were
taken before and after the oven drying with the oset
subtracted. Again, these preliminary data were
acquired with the aim at elucidating some of the moisture weight dierences noted between the KFT and the
SOD techniques.

Color
Oven-dried cotton samples of the cotton balls and raw
bers from 2001 and 2007 (both with and without being
Shirley cleaned) in both nitrogen and air atmospheres
at 105 C and 150 C were analyzed for color data. The
spectrophotometric color data were generated on the
Gretag Macbeth Color-Eye 7000A unit, with D65
Illuminant, 10 observer, large area of view, and
Specular Component Included (SCI). The samples
were then ued and accumulated into 1 g samples,
placed in a pressured cell and run in ve replicates on

the spectrophotometer with constant pressure of 30 lbf/

in2. The samples were run with the caramel-colored side
of the cottons facing the instrument, since this is where
evidence of oxidation may be easily observed to generate color data in CIE L*a*b* space in the wavelengths
from 360 to 750 nm.

Karl Fischer Titration

The KFT procedure uses a Metrohm 770 oven sample
processor at 150 C, with a 35-glass vial carousel, an 800
Dosino with an electronic buret, an 801 stirrer, an 803
Ti stand for the titration cell and platinum electrode,
and the Tiamo 1.2 titration software. Hydranal composite 5 K was used as the titration reagent and
Hydranal medium K was the solvent in the titration
cell. For each cotton sample used, three 0.1 g replicates
that had been subjected to standard textile testing conditions for at least 24 h were used. These samples were
placed in the sample vial and crimped closed in the
conditioned air right before KFT testing. The samples
were then placed on the KFT carousel and run between
two sets of three blank vials, one set prior to the cottons, and one set after. The blanks serve as a quality
control measure. The fully automated instrument analyzed all samples for percentage of moisture. In this
process, each vial is heated under a stream of dry nitrogen owing through the cotton sample that is contained
in the sealed vial. This removes the released water,
transporting it to the titration cell. Mean moisture content and standard deviation were calculated from these
replicates per cotton.

Attenuated Total Reflectance/Fourier Transform

Infrared spectroscopy

Figure 4. Slides with tape to capture particulate matter on top

of oven vent.

For the ATR/FT-IR measurements, a Bruker Vertex 70

bench top instrument was employed. Cotton samples
were exposed to air for less than a minute before analysis. The cotton samples were placed on the diamondZnSe ATR crystal and then secured using a high-pressure clamp to ensure consistent intimate contact of the
sample with the crystal during surface analysis. Five
aliquots were run at each temperature then averaged
spectrally using the Bruker OPUS version 6.5 software.
There were 32 interferograms collected for each sample
before the average spectrum was generated. The resolution was maintained at 8 cm1. All spectral measurements were done at room temperature over the spectral
region of 15001900 cm1 using a DTGS detector and
KBr beam splitter. Data were pre-processed using
Bruker OPUS software applying baseline correction
against an air background, 25-point smoothing, and
derivative math.

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161

Synthesis of cellulose 2,3-dialdehyde

In an eort to conrm the identity of the oxidation
product in the thermal treatment of cotton samples,
cellulose 2,3-dialdehyde was synthesized as described
previously.12 Briey, a 0 mL round bottom ask was
charged with 50 mg (1.00 eq) of Wiley-milled cotton cellulose, 2.50 mL deionized water, 83 mg sodium periodate (1.66 eq), and stirred for 18 h in the dark at room
temperature. Afterwards, the reaction was quenched
with three drops of ethylene glycol and diluted with
5 mL of deionized water. The insoluble bers were centrifuged and decanted and were then washed and decanted twice with 5 mL of absolute ethanol. The bers
were dried under high vacuum to obtain the partially
oxidized 2,3-dialdehyde cellulose product in quantitative yield. The synthetic scheme is given in Figure 5.

Results and discussion

As reported in previous research, dierences were noted
between moisture measurements determined by KFT
and oven drying methods.2,3 In order to understand
these dierences, several avenues were explored. One
such technique was determining if particulate matter
was released during SOD. A second approach was measuring the color change in oven-dried cotton samples.
Another was indicating whether or not oxidation could
be occurring in the air atmosphere of SOD using ATR/
FT-IR spectroscopy. None of these conditions occurred
in the closed system nitrogen environment employed by
the KFT.

Particulate matter
Some indirect evidence to explain the 0.4% dierence
between moisture measurements by SOD and KFT was
needed. It is important to note that the inside of the
gravity convection oven was noticeably dirty in appearance after SOD of the cotton samples. It was

subsequently cleaned and appeared dirty again. It is

also signicant that when a slightly positive pressure
was applied, a 12% higher weight loss was observed,
also suggesting that brous or particulate matter may
be released during SOD. In addition, cottons when
heated become brittle, break apart, and are permanently changed. Consequently, during the SOD procedure, some brous matter may be released. The authors
wanted to capture some evidence whether or not additional matter was being released when the water was
being removed during SOD. Thus, microscope slides
with high-temperature grease were placed atop the
weighing bottles leaving ample space for water vapor
to be released. The weighing bottle and sample were
placed in the oven at a 105 C temperature and
heated. After 24 h, the slides were cooled, removed
from the oven, and studied with a microscope tted
with a 20 objective. This method was employed
since the greased slides aorded viewable images.
These images were selected to include in the paper for
their clarity and to visually demonstrate that particulate matter is indeed being released during the SOD
process. The cotton balls, the 2001 crop year cleaned
cotton, and the 2007 raw cotton were used in this portion of the study. The images were quite revealing, as
shown in Figures 68, with particulate and brous
matter easily detected. Although there are some clear
dierences between Figures 6, 7, and 8 regarding the
brous lengths and particulate matter observed, the
authors feel they are only incidental and a function of
the independent cotton samples. Thus, to quantify the
particulate matter being released, microscope slides
with high-temperature double-sided tape called
Loctite Power Grab were used. The tape was placed
on two microscope slides at the vent in the top of the
oven that contained ten 1 g cotton ball samples. The
tape was measured to exact lengths, weighed, and was
more stable than the greased microscope slides. A 2-in
long, three-fourths inch wide piece of tape was used on
each slide. Preliminary tests, with no cotton in the

Figure 5. Synthetic scheme of 2,3-dialdehyde cellulose.

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Textile Research Journal 84(2)

Figure 6. Particulate and fibrous matter captured on a greased

slide placed on top of cotton balls contained in a weighing bottle
placed in an airflow oven heated to 105 C.

Figure 8. Particulate and fibrous matter captured on a greased

slide placed on top of cotton from crop year 2007 contained in a
weighing bottle placed in an airflow oven heated to 105 C.

methods, although the quantitative amounts of each

of these contributors are still unknown.

Color results

Figure 7. Particulate and fibrous matter captured on a greased

slide placed on top of cotton from crop year 2001 contained in a
weighing bottle placed in an airflow oven heated to 105 C.

gravity convection oven, revealed that there was a constant oset that could be subtracted for the particular
length of tape being used. When this constant oset was
applied, a total net weight of 0.0018 g was measured
from the two slides. It is important to note that only
the ten 1 g cotton ball samples were analyzed for these
results. Considering the amount of weight loss of ovendried cottons is approximately 7.5% for 10 g of cotton,
the average weight lost is 0.75 g. The weight loss
observed on the taped slides amounts to approximately
0.24% of the 0.75 g of cotton weight loss, or roughly
half of the dierence seen between KFT and the oven as
has previously been reported.2,3 In addition, NAV components observed in earlier studies2,3 and cellulose oxidation may also contribute to the observed bias in
moisture contents determined by the KFT and SOD

Upon investigation of the cottons samples, those at the

higher temperature in the oven appeared more brownish in color. The idea of measuring color data was a
means of quantifying the dierences seen, as well as to
serve as visible evidence of the possibility of oxidation
and that more than moisture is removed during oven
testing. The data were intriguing. In CIE Lab space, the
greater the L* value, the whiter the sample. The redness
value is indicated by a*. The more positive the value the
more red the cotton color, the more negative the value,
the more green the cotton color. The yellowness value is
indicated by b*. The more positive the value the more
yellow the cotton color, the more negative the value,
the more blue the cotton color. The
E*AB was calculated to reveal the change in color of the oven-treated
samples relative to the control. All of the data are
shown in Tables 14. The
E*AB value was calculated
according to Equation (1) below:

EAB
L2
a2
b2

1=2

For lightness, L*, all of the control samples were whiter

than those heated in both the air and nitrogen atmospheres, as expected. What is surprising is that for the
cotton ball samples, the change in color is greater for
the nitrogen-dried samples as opposed to the air-dried
samples at 105 C. At 150 C, the samples have a greater
color change in air than in nitrogen for the cotton balls,
as expected.
For the 2001 cottons, the change in color pattern
was similar to that of the cotton balls, where there

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Table 1. Color data for the cotton ball samples

Control
105 C air
150 C air
105 C N2
150 C N2

L*

a*

b*

L*

a*

b*

EAB

94.502
93.647
82.937
93.300
88.010

0.300
0.287
3.537
0.157
1.563

1.942
4.470
18.797
5.850
11.770

0.855
11.565
1.202
6.492

0.013
3.837
0.143
1.863

2.528
16.855
3.908
9.828

2.669
20.798
4.091
11.925

Table 2. Color data for the 2001 cotton fiber samples

Control
105 C air
150 C air
105 C N2
150 C N2

L*

a*

b*

L*

a*

b*

EAB

87.640
87.243
66.040
85.283
74.760

0.902
1.393
8.620
2.213
4.843

11.148
12.630
23.690
14.577
17.893

0.397
21.600
2.357
12.880

0.491
7.718
1.311
3.941

1.482
12.542
3.429
6.745

1.611
26.142
4.362
15.064

Table 3. Color data for the 2007 cotton fiber samples

Control
105 C air
150 C air
105 C N2
150 C N2

L*

a*

b*

L*

a*

b*

EAB

88.114
87.373
76.200
84.747
72.967

0.448
1.407
5.033
2.340
5.237

8.956
12.890
19.643
15.010
18.590

0.741
11.914
3.367
15.147

0.959
4.585
1.892
4.789

3.934
10.687
6.054
9.634

4.116
16.649
7.181
18.579

Table 4. Color data for the 2007 Shirley-cleaned cotton fiber samples

Control
105 C air
150 C air
105 C N2
150 C N2

L*

a*

b*

L*

a*

b*

EAB

90.248
88.113
75.970
86.247
75.597

0.376
1.340
5.720
2.383
5.167

10.076
13.073
21.570
15.873
18.787

2.135
14.278
4.001
14.651

0.964
5.344
2.007
4.791

2.997
11.494
5.797
8.711

3.804
19.093
7.325
17.706

was a greater change in the color of the cotton balls in

nitrogen than air at 105 C. However, as expected, the
color changes for the 2011 cottons at 150 C was greater
in air than in the nitrogen atmosphere. In the case of
the 2007 raw cotton, the color change for these cottons
in the nitrogen atmosphere was greater at both 105 C
and 150 C. Finally, for the Shirley-cleaned cottons the
color change at 105 C in nitrogen was greater than that
calculated for the oxygen atmosphere. Presently, the
reason for these observed anomalies is unclear. One
plausible assumption that may be mentioned is that
another reaction scheme is taking place concurrently

with the oxidation, since it was not expected that the

color change in the nitrogen atmosphere would be
greater than in the oxygen atmosphere. This may be
due to the heterogeneity of the 2007 cottons as natural
bers. Representative reectance spectra are included
as Figures 9 and 10. Indeed, when examining Figures
9 and 10, which compare the reectance spectra of
cotton balls, 2001, 2007, and 2007 Shirley-analyzed cottons in nitrogen and oxygen atmospheres at both 105 C
and 150 C, there appears to be dierent mechanisms
taking place in the two environments. In addition, analysis of variance (ANOVA) statistical treatment was

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Spectra of samples in air

100
90
80
70
60
50
40
30
20
10
0
360
White Tile

410
CB 105

460

510

CB 150

01 105

560
01 150

610
07 105

660
07 150

710
07 SH 105

07 SH 150

Figure 9. Reflectance spectra of oven-treated cotton samples in air for the white tile black diamond; cotton ball at 105 C gray
square; cotton ball at 150 C gray triangle; 2001 cotton at 105 C light blue X; 2001 cotton at 150 C dark blue square; 2007
cotton at 105 C light green square; 2007 cotton at 150 C green diamonds; 2007 Shirley-analyzed cotton at 105 C red square;
and 2007 Shirley-analyzed at 150 C purple triangle. (Color online only).

Figure 10. Reflectance spectra of oven-treated cotton samples in nitrogen for the white tile black square; cotton ball at
105 C gray square; cotton ball at 150 C gray triangle; 2001 cotton at 105 C light blue double line; 2001 cotton at 150 C dark
blue X; 2007 cotton at 105 C green square; 2007 cotton at 150 C green line; 2007 Shirley-analyzed cotton at 105 C red
square; and 2007 Shirley-analyzed at 150 C purple square. (Color online only).

applied to the samples. Typically, p values less than

0.05 are considered signicant. The statistical data are
shown in Table 5. Thus, the 2007 and 2007 Shirleyanalyzed cottons at 150 C demonstrate no signicant
dierences between nitrogen and air. In addition, some
air may have contaminated the nitrogen atmosphere

during the opening and closing of the oven door.

Also, acid hydrolysis is possible in the 2007 and 2001
cottons, since metal ions have been reported to exist on
the surface of cottons and, thus, could catalyze these
types of reactions. In addition, reactions with non-cellulosics (waxes, proteins, pectic substances, etc.) may

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165

Table 5. Analysis of variance statistical data comparing nitrogen

to air environments
Samples

p values

Cotton balls 105 C

Cotton balls 150 C
2001 105 C
2001 150 C
2007 105 C
2007 150 C
2007Sh 105 C
2007Sh 150 C

0.004821
0.002415
0.000215
0.0000981
0.000215
0.369269
0.00033
0.072733

compete with the ber for oxidation, although these

studies were not the focus of this investigation and
were not directly studied.

Attenuated Total Reflectance/Fourier Transform

Infrared spectroscopy
The visible observations of cotton browning and particulate and brous matter captured on the greased
slides and double-sided tape propelled the need for further investigation, since these studies only yielded indirect evidence of the possible causes for bias in the SOD
method. To gain direct evidence for the oxidation of
oven-dried samples as a possible contributor to the
moisture content bias observed when comparing the
KFT and SOD methods, ATR/FT-IR spectroscopy
was used.
Effect of air atmosphere on absorbance spectra. The progression of cellulose oxidation is highly inuenced by
temperature, pH, metal ions, and the concentration and
type of oxidizing agents.6 Previously, it was discovered
that periodate oxidation of cellulose yielded the formation of 2, 3-dialdehyde.7 However, the detection of this
aldehyde by FT-IR spectroscopy was strongly dependent upon the presence of moisture. Thus, drying the
oxidized sample was vital to observing the aldehyde
products. In the present study, thermal oxidation of
cotton cellulose in both cotton balls and raw cotton
bers were examined. It should be noted that the
dried cottons are exposed to the environment in a
non-conditioned lab for approximately 30 s while
being tested. To quantify this, two 1 g cotton ball samples were oven dried in 105 C air for 24 h and allowed
to re-equilibrate for 30 s to mimic the ber testing.
When measured, this moisture averaged 4.2 mg, or
approximately 0.04% of the original sample weight.
Figure 11(a) depicts the eect of varying the oven
temperature of the scoured and bleached cotton balls
on their FT-IR absorbance spectra. A control at room

temperature is also included. Although temperatures

greater than 105 C may not resemble standard oven
conditions, oven-treated cotton samples were observed
at 150 C to examine the spectra at KFT conditions and
to more easily observe the carbonyl peak intensities,
since they were nominal at 105 C. It can be easily
observed that at the highest temperature studied,
150 C, a peak exists at 1728 cm1 in the FT-IR spectra.
A minimal peak exists at this wavelength for the lower
temperatures studied (105 C and 125 C) as well. The
FT-IR spectral region of 15001900 cm1 has been previously dened by earlier literature ndings to represent
the carbonyl functional group frequency range.8
Specically, the peak area ranging from 1720
1740 cm1 has been described as the cellulose aldehyde
region.6,810 The spectral region around 1640 cm1 has
been previously attributed to the symmetric deformation vibration of absorbed water molecules.6
Although this region is not shown in our study, it
was also ascertained that upon oven treatment, the
water deformation band intensity weakens and concurrently shifts toward the lower FT-IR spectral region. It
has been reported earlier that at 60 C, the moisture
band weakens and reaches water desorption completion.10 However, the presence of this moisture peak
after drying at 150 C suggests that some water is still
present with the carbonyl oxidized moieties where the
carbonyl and moisture bands are not baseline resolved.
In addition, the widening and shifting of the water
deformation FT-IR spectral bands towards lower frequency with oven treatment of the samples may be due
to the rearrangement in hydrogen bonding, which is not
associated with the cellulose crystal lattice.7
In contrast to the cotton ball data, higher carbonyl
peak intensities were normally observed for the raw
cotton bers from crop years 2001 and 2007, as
shown in Table 6, Figure 11(b), and Figures 12(a)
and 12(b). This may be due to the bleaching and scouring of the cotton balls before oven treatment. When
comparing peak intensities for the two 2007 crop year
samples, the Shirley-cleaned sample revealed a higher
peak intensity in the carbonyl region. This suggested
that the ber content in the raw 2007 cotton ber
sample was diluted by the impurities present and,
thus, may have competed with oxidation of the
cotton ber yielding a lower carbonyl peak intensity
relative to the Shirley-cleaned 2007 cotton ber.
Tables 6(a) and (b) include the peak maxima and
intensity for carbonyl oxidation compounds and moisture while varying temperature. For all samples studied,
the spectra for non-dried specimens were not subtracted
from that of dried specimens. In terms of the large peak
intensities for moisture for the oven-dried cottons, the
relative humidity in the oven may not have been zero
during drying and, thus, all of the water was not

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Figure 11. Averaged Fourier Transform Infrared absorbance spectra in air for (a) cotton balls and (b) 2001 cotton fiber dried at
105 C, 125 C, and 150 C. Spectra were baseline corrected with 25-point smoothing.

Table 6(a). Carbonyl and moisture absorbance peak maxima while varying temperature
Carbonyl peak maxima (cm1)

Moisture peak maxima (cm

1

Temperature

Cotton ball

CY 2001

CY 2007

CY 2007 SH

Cotton Ball

CY 2001

CY 2007

CY 2007 SH

150 C
125 C
105 C
23 C

1728
1728
1728
0

1720
1736
1736
0

1723
1734
1734
0

1720
0
1730
0

1629
1635
1632
1639

1611
1621
1608
1640

1614
1615
1608
1614

1610
1616
1607
1619

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Table 6(b). Carbonyl and moisture absorbance peak intensity while varying temperature
Carbonyl peak intensity

Moisture peak intensity

Temperature

Cotton ball

CY 2001

CY 2007

CY 2007 SH

Cotton ball

CY 2001

CY 2007

CY 2007 SH

150 C
125 C
105 C
23 C

6.86E-04
1.42E-04
1.10E-04
0.00E + 00

3.80E-03
8.48E-05
5.45E-05
0.00E + 00

1.19E-03
5.70E-05
3.15E-04
0.00E + 00

1.37E-03
0.00E + 00
3.39E-04
0.00E + 00

1.05E-03
6.86E-04
9.80E-04
6.70E-03

5.76E-03
6.15E-03
7.73E-03
6.70E-03

5.36E-03
7.41E-03
7.76E-03
1.28E-02

5.60E-03
6.72E-03
7.77E-03
1.18E-02

SH: Shirley Analyzer cleaned cotton fiber; CY: crop year.

Figure 12. Averaged Fourier Transform Infrared absorbance spectra in air for (a) 2007 cotton fiber and (b) 2007 Shirley Analyzer
cleaned cotton fiber dried at 105 C, 125 C, and 150 C. Spectra were baseline corrected with 25-point smoothing.

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removed as postulated earlier.2 In addition, the ovendried cottons took up moisture from the atmosphere
during the spectral acquisitions even though ATR/
FT-IR analyses were achieved at under 1 minute per
sample. For both the oven-dried cotton ball and 2001
cotton ber samples, the carbonyl peak intensities
increased monotonically with temperature. However,
for the 2007 cotton ber samples (both with and without Shirley-cleaning) the carbonyl peak intensities do
not follow this pattern. The dierences observed may
be due to the heterogeneity of the surface of natural
raw cotton samples and the dierent amounts and susceptibility of non-cellulosics to oxidation as a function
of temperature. The dierences may also be due to the
rates of reactions for oxidation and loss of NAVs,
which may dier with temperature. In all cases the carbonyl peak maxima for the oven-treated samples are
quite broad. This may be explained by production of
a variety of products upon cotton oxidation by thermal
treatment or a variety of environments for a single type
of functional group.9 In an earlier study, partial oxidation of cellulose products was dened based on the
frequencies of their vibrations.9 Specically, Table 2 is
given from this earlier reference to display the possible
variety of products created during cellulose oxidation
where the carboxyl vibration signies the nal oxidation stage and the lower wavenumber vibrations represent oxidation intermediates.9 According to Table 2
and Figure 13, showing the cotton samples at 150 C

with the synthesized partially oxidized cellulose product, the most prominent carbonyl oxidation product
observed in our study was cellulose aldehyde. In addition, the requirement for Wiley milling of the cotton
sample during the synthesis of the cellulose 2,3-dialdehyde drastically increased the surface area of the
sample leading to signicant absorption of moisture,
as depicted in Figure 13.
Effect of nitrogen atmosphere absorbance spectra. Next, the
eect of the gas atmosphere was observed for all the
cotton samples in a nitrogen atmosphere. Figure 14
depicts the absorbance results of this study. As to be
expected, minimal peak maxima in the carbonyl infrared region suggests that cellulose oxidation as observed
in the current study requires a dry oxygen-rich atmosphere at 150 C. Data were collected at 105 C as well,
but only the data at 150 C are shown to illustrate what
happens at the KFT temperature. As can be observed
in Figure 12, the baseline shifts signicantly due to the
high sensitivity of the spectra shown, as would be
expected.
Effect of air atmosphere on second derivative spectra. First or
higher derivatives of absorbance with respect to wavelength are used in derivative spectroscopy to improve
resolution in qualitative analysis. If the absorbance
band wavelength maximum (max) points upward or
positive (x- axis is ), then a second-order derivative

Figure 13. Averaged Fourier Transform Infrared absorbance spectra of 2001, 2007, and 2007 Shirley Analyzer cleaned cotton fibers
dried at 150 C compared with the synthesized cellulose 2,3-dialdehyde. Spectra were baseline corrected with 25-point smoothing.

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is a negative band pointing downward with minimum

at the same wavelength as max. In addition, it shows
one weaker positive satellite band on either side of the
main band. A fourth-order derivative shows a positive
main band at the same wavelength as max and two
weaker satellite bands on either side (one positive and
one negative) of the main band.
The number of bands observed (main and satellite) is
generally equal to the derivative order plus one. For
poorly resolved bands, especially if one band is sharper
or narrower than the others, then the second and fourth
derivative main band can be many times greater in
amplitude than the remaining main bands. Thus,
great care is necessary in interpretation of derivative
spectra in qualitative analysis.
Second derivative spectra for the oven-treated samples and their respective controls were also examined,
as shown in Figures 15(a) and (b) and Figures 16(a) and
(b). This was carried out to further resolve the overlapping peaks postulated to exist in the broad oxidized
carbonyl peak range for the cotton samples. When
comparing both the oven-treated cotton ball and raw
cotton ber data, the second derivate carbonyl band
shifts to a lower wavenumber at the highest temperature studied, 150 C, in all cases. Again, the broadness
of the absorbency bands for the oven-treated data suggests the presence of multiple oxidation products. The
shifts in the second derivative bands at the isosbestic

point (marked with a vertical line) may be indicative of

a shift in the equilibrium of the various oxidative carbonyl species present.
The eect of Wiley milling on the oxidation of the
cotton samples was also investigated, as shown in
Figure 17, since this treatment was necessary in the
synthetic development of cellulose 2,3-dialdehyde. The
oxidized synthetic sample without Wiley mill treatment
depicted the smallest extent of oxidation, signied by its
lower wavelength carbonyl band maxima at nearly
1660 cm1, suggesting the formation of enols, compared to samples that had been Wiley milled and oxidized. In contrast, bandwidth of the Wiley-treated
samples seemed to be larger and shifted to higher carbonyl peak maxima wavelengths, suggesting a greater
extent of oxidation. The cotton ber sample control,
which had not been subjected to thermal or chemical
treatment but had been Wiley milled, was shown for
reference. This control sample was shifted farthest to
the left for the oxidized carbonyl peak maxima and,
surprisingly, had a higher band shift, which was taken
to indicate a greater extent of oxidation. This may be
because the cotton ball used as this control was
bleached and scoured and did undergo some oxidation
during the bleaching treatment. It has been previously
reported that the compression milling of cotton samples
decreases the crystallinity index and degree of polymerization, and increases accessibility to water vapor.13

Figure 14. Averaged Fourier Transform Infrared absorbance spectra showing effect of nitrogen oven atmosphere on oxidation
of cotton balls and 2001, 2007, and 2007 Shirley Analyzer cleaned cotton fibers dried at 150 C. Spectra were baseline corrected with
25-point smoothing.

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Figure 15. Averaged Fourier Transform Infrared second derivative spectra for (a) cotton balls and (b) 2001 cotton fiber dried at
105 C, 125 C, and 150 C. Spectra were baseline corrected with 25-point smoothing.

However, for untreated cellulose in this same study,

non-linearity in the correlation between the crystallinity
index and water accessibility was observed. Based on
the presence of amorphous and crystalline regions in
the cotton samples examined in the current study,
these structural characteristics may also contribute to
the data observed, further complicating the interpretation of formation of oxidation products with temperature. Moreover, additional time was required to test the
Wiley-milled samples due to their powder-like characteristics making these samples more susceptible to

water uptake. Thus, the presence of this moisture may

serve as a source for oxidative damage of the cotton.
These previously observed reported changes should
lead to more diversity in oxidation products generated
due to physical and mechanical changes of the cotton
samples aorded by Wiley milling.
Effect of air atmosphere on fourth derivative spectra. With
the oxidized carbonyl peak maxima still observed to
be broad, the fourth derivative pre-processing was
formed to yield even more specic information about

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Figure 16. Averaged Fourier Transform Infrared second derivative spectra of cotton fiber samples for (a) 2007 cotton fiber and
(b) 2007 Shirley-cleaned cotton fiber dried at 105 C, 125 C, and 150 C. Spectra were baseline corrected with 25-point smoothing.

the carbonyl oxidized products at the highest temperature studied, 150 C. As can be observed from
Figure 18, the oxidized peak maxima for all cotton
samples only varied by 5 cm1, centered around
1725 cm1, and the overlap of these bands with the
synthesized cellulose 2,3-dialdehyde band (non-Wiley
milled) suggested again that the cellulose aldehyde oxidation product may have been formed through the
oven treatment of the cotton samples in this study. In
addition, a doublet peak is observed for the synthesized
cellulose 2,3-dialdehyde around 1725 cm1. This may
be explained by the presence of unoxidized cellulose

or other carbonyl oxidized products that may be in

equilibrium with the free dialdehyde. What is interesting to note is the peak associated with moisture.
Indeed, for the synthesized cellulose 2,3-dialdehyde
sample, three peak maxima are observed at 1592,
1616, and 1647 cm1. The peak at 1647 cm1 may represent the remaining presence of the water deformation
band due to the binary existence of the water molecules
with the oxidized cotton. The peaks at 1592 cm1 and
at 1616 cm1 may indicate the presence of residual carbonyl groups that had been previously observed at
1610 cm1.10

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Figure 17. Averaged Fourier Transform Infrared second derivative spectra of cotton ball and cotton fiber samples dried at 150 C,
synthesized cellulose 2,3-dialdehyde with and without Wiley milling, and Wiley-milled cotton fiber control subjected to no heat or
chemical treatment. Spectra were baseline corrected with 25-point smoothing.

Figure 18. Averaged Fourier Transform Infrared fourth derivative spectra of cotton balls, 2001, 2007, and 2007 Shirley Analyzer
cleaned cotton samples dried at 150 C compared to synthesized cellulose 2,3-dialdehyde (non-Wiley milled). Spectra were baseline
corrected with 25-point smoothing.

Conclusions
According to the particulate matter and color data,
there is visible indirect evidence that oxidation products
are being formed in the oven-treated cotton samples.
However, some unexpected color changes were

observed in the nitrogen atmosphere versus the

oxygen atmosphere, possibly due to dierent mechanisms taking place and, thus, require further study. To
continue this research, the authors are looking into a
more air-tight nitrogen delivery system that employs
smaller vials. By eliminating any air permeating the

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sample, the color change should be minimal. It is

important to note that these color changes were not
observed during KFT testing. The ATR/FT-IR data,
along with the spectra of the synthetic standard of cellulose 2,3-dialdehyde, strongly suggest that the
observed oxidation product of thermal treatment of
cotton samples in this study is at least partly cellulose
aldehyde and may yield preliminary evidence of the
nature of the bias in the determination of moisture content comparing the KFT and SOD method. The second
derivative spectra gives a view of the extent of oxidation
products being formed in addition to the aldehyde
products with band shifts being observed. The fourth
derivative spectra shed light on the carbonyl products
that exist along with the clear evidence of the formation
of cellulose aldehyde.

Disclaimer
Mention of a trade name, proprietary product, or specic equipment does not constitute a guarantee or warranty by the United States Department of Agriculture
(USDA) and does not imply approval of a product to
the exclusion of others that may be suitable.
Funding
This research received no specic grant from any funding
agency in the public, commercial or not-for-prot sectors.

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