J Therm Anal Calorim (2017) 127:2005–2012

DOI 10.1007/s10973-016-5813-z

Study on thermal degradation of cattlehide collagen fibers

by simultaneous TG–MS–FTIR
Pengyuan Yang1,2 • Xichan He1 • Wenjuan Zhang3 • Yuxuan Qiao1 •

Fang Wang1 • Keyong Tang1

Received: 17 March 2016 / Accepted: 3 September 2016 / Published online: 13 September 2016
Ó Akadémiai Kiadó, Budapest, Hungary 2016

Abstract Leather was useful materials since dawn of that some organic fragments were decomposed above
human history for excellent properties, but thermal degra- 1073 K which confirmed that thermal degradation of lea-
dation mechanism was not very clear yet. In this paper, ther is more than three steps.
much progress has been made in elucidating the thermal
stability and thermal degradation mechanism by thermo- Keywords Thermal analysis
Degradation
Mechanism

analytical study in argon. Thermogravimetric analysis Cattlehide collagen fibers
simultaneously coupled with mass spectrometry and
Fourier transform infrared spectrometry was employed to Abbreviations
study the thermal degradation of cattlehide collagen fibers TG Thermogravimetric analyzer
through in-depth analysis of the evolved gas. Thermo- MS Mass spectrometer
gravimetry analyses carried out on sample, deprived from FTIR Fourier transform infrared
any residual catalyst and highlighted a two-step thermal DSC Differential scanning calorimetry
degradation. New evidence demonstrates that the process NCCF Native cattle skin collagen fibers
during temperature range from 373 to 513 K was phase EGA Evolved gas analysis
transformation. Photographs of polarizing microscope DTG Differential thermogravimetric
confirmed the conclusion. The decomposition of cattlehide
collagen fibers starts at about 523 K. The cattlehide col-
lagen fibers may undergo the process of melting, oxidation Introduction
and decomposition. In decomposition, more than three
steps take place. The mass spectra and Fourier transform Leather is an excellent material used in a variety of appli-
infrared spectrometry stated clearly that double bond of cations due to its durable and flexible properties [1]. The
carbon to oxygen, carbon to sulfur and carbon to nitrogen leather products (heavy leather: for soles and belts; collagen,
were destroyed firstly because the carbon dioxide, carbon parchments and clay light leather: tanned skin of footwear,
monoxide and ammonia evolved simultaneously. The garments and book-binding leathers) have been useful
second peak of carbon monoxide in mass spectra indicated materials since the dawn of human history [2, 3]. Most of the
antiques in museums are produced by leather [4]. They are
valuable treasures due to the history they represent, and their
& Keyong Tang preservation challenges museum custodians and private
[email protected]
collectors alike [2, 5, 6]. Collagen is the main component of
1
College of Materials Science and Engineering, Zhengzhou leather, and it is responsible for its thermal stability, vis-
University, Zhengzhou 450001, China coelastic properties and mechanical strength. Collagen has
2
College of Materials Science and Engineering, Beifang always been considered to be a crystalline material with
University of Nationalities, Yinchuan 750021, China defined sequences of amino acid residues, but sometimes it
3
Zhengzhou Tobacco Research Institute of CNTC, was regarded as semicrystalline material due to the presence
Zhengzhou 450001, China of disordered regions, revealed by X-ray diffraction. Leather

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2006 P. Yang et al.

may show thermal properties associated with both crystalline (600–4000 cm-1). Temperature calibration was carried out
and amorphous materials [7]. with indium. Baseline curves were measured under the
There are reviews focusing on the chemical deteriora- same experimental conditions. The FTIR spectrometer
tion of leather, according to which the degradation of obtained spectra every 7 s to determine the evolution rate
leather consists in two main processes: moisture loss and and composition of several compounds quantitatively.
decomposition [8, 9]. In general denaturation, it is gener- Some experiments were repeated three times to determine
ally believed that heat induced kinetic energy disrupts the their reproducibility, which was found to be good. Species
secondary interactions between macromolecules, which in identification and analysis were discussed in some detail
turn denatures the secondary and tertiary structures [10], below. The components of released gaseous mixtures had
but there is no direct identification on this phenomenon. Up been monitored and identified mostly on the basis of their
to now, some works have been done on the thermal FTIR and MS reference gas spectrum available on NIST
denaturation of leather [11], while less is known about the mass spectrometry library and EPA.
degradation mechanism of leathers [2, 12–15]. The present
paper is focused on the evolved gaseous products to
explore the leather thermal degradation mechanism. The Results and discussion
combination of TG with a mass spectrometer (MS) or a
Fourier transform infrared spectrometer (FTIR) allows the Simultaneous TG/DTG curves of NCCF measured
nature of the gaseous reaction products formed in the TG to in argon
be investigated online. The MS or FTIR can track their
evolution profiles when compounds are evolved. We can The simultaneously recorded TG and DTG curves are
know the thermal degradation mechanism of leathers by shown in Fig. 1a indicating two significant mass loss steps
characterizing the substance or substance class through during decomposition in argon. Typical mass loss data for
spectral interpretation and comparison with database ref- the thermal decomposition of leather in inert argon atmo-
erence spectra. Decomposition pathways can thereby be sphere are shown in Fig. 1b. The first stage occurred
elucidated. between ambient temperature and 393 K, indicating about
4.8 % loss in mass, denoted by step I. The mass loss in this
stage is because of the loss of moisture. The second step
Experimental appeared to be more complex with a major peak observed
at 503 K. The mass loss between 493 and 923 K was
The native cattlehide collagen fibers (NCCFs) provided by 61.79 % of the original mass. This step was denoted by II.
Sichuan University, China were subjected to thermal The maximum mass loss is because of the thermal
analysis as received. Open platinum crucible, a heating rate decomposition of hide powder that happen within tem-
of 10 K min-1, sample size of 10–20 mg, and flowing perature ranging from 593 to 823 K. This decomposition
argon atmosphere (20 mL min-1) were used for purging curve is formation and evaporation of some volatile com-
the thermoanalytical furnaces during the evolved gas pounds from the hide powder.
analysis measurements. Figure 1a, b shows cattlehide collagen fibers heated in
The changes in structure of the cattlehide collagen fibers argon atmosphere. Figure 1c shows the TG–DSC curves of
were monitored using an Olympus BX-51 polarizing cattlehide collagen fibers obtained by analysis in N2. The
microscope. Samples were placed between two thin glass samples exhibited three endothermic peaks and two
slides and heated on a programmable hot stage at a heating exothermal peaks. The peak at 481 K corresponds to the
rate of 5 K min-1 to 513 K. Subsequently, the samples crystallinity of the sample, which could be explained by the
were kept at temperature 303, 373, 423, 473, 488, 493, 503 biphasic amorphous–crystalline structure of leather,
and 513 K for about 5 min to eliminate heat history and according to which the crystalline triple helix is embedded
observe the structure modification. into an amorphous matrix [12, 16]. The peak at 573 K
The TG–EGA–MS–FTIR apparatus consists of a SET- corresponds to the decomposition of hide powder. The
SYS Evolution 16/18 Thermogravimetric Analyzer decomposition does not occur at a uniform rate, and thus
(SETRAM Instrumentation Inc.), OmniStar (Pfeiffer) and a some leathers are degraded during early decomposition,
Tenso27 (Bruker) FTIR spectrophotometer equipped with a while others are degraded later. The mass loss of this
TG/IR Accessory gas cell. The furnace and the gas cell process was up to 61.79 %. The peak at 710 K, suggesting
were coupled through a heated (T = 553 K) 0.8-m stain- a highly destabilized structure with a large distribution of
less steel tube with diameter of 3 mm. The OPUSTM components, corresponds to the decomposition of some
software accumulated 40 interferograms in every second, organic fragment. A further support for this explanation is
and they were transformed to one IR-spectrum the mass spectrometric evidence of the m/z = 28, 30 amu

123
Study on thermal degradation of cattlehide collagen fibers by simultaneous TG–MS–FTIR 2007

(a) The photographs confirmed that there are two phases in

110 leather. Nearly all the bright area disappeared when the
0.0
100 temperature rose up to 513 K. The endothermic peak in
90 Mass (mg) Fig. 1c at 481 K demonstrates that the process is melting.
I –0.2
DTG The 61.79 % mass loss in TG curve started at about 523 K.
80

DTG/% K –1
In conclusion, the above results confirmed that the structure
Mass/%

70 –0.4

60
of leather was transformed from crystalline or semicrys-
–0.6 talline to amorphous. It is obviously that only phase
50
transformation happened when the temperature ranges
40 –0.8
from 373 to 513 K. So the decomposition of leather was
30
–1.0
happened above 513 K, we can infer from Fig. 1 that the
20
II decomposition of leather started at about 523 K.
200 400 600 800 1000 1200 1400
Temperature/K Evolved gas analysis of NCCF by online coupled
(b)
110 TG–EGA–MS–FTIR
100

4.8 %
A limited number of mass units (m/z \ 100) were selected
90
to analyze in this paper. The selected mass spectrometric
80
evolved gas has helped us to observe evolution of leather
Mass/%

70
decomposition. Beyond the known H2O and CO2, there are
61.79 %
60
some new gaseous species represented by m/z = 30,
50 assigned to NO, CH2O, C2H6 and 67 to C4H5N, respec-
40 tively [18].
30 The first mass loss (step I) in the decomposition curves
20 of cattlehide collagen fibers in inert atmosphere occurred
200 400 600 800 1000 1200 1400
around 373 K, and 18 amu peak assigned to the loss of
Temperature/K water, notably molecular adsorbed water. It is obviously
(c) that 18 amu peak is below 373 K and, therefore, at slightly
110 1 higher temperature than the step I of DTG peak. There may
100 573 K TG
be a delay in transfer from the capillary to the MS. These
DSC 0
90 335 K
new species evolved at step II, and a number of m/z peaks
–1 were chosen as representative of the decomposition prod-
80
710 K
Mass/%

ucts observed in this step. Peaks chosen for analysis were at

DSC/mW mg –1 Exo

70
481 K
–2 28, 30, 32, 44, 54, 64, 67, 70, 72, 78, 81 and 91 amu.
60 Further heating results in the thermal decomposition of the
–3
50 leather in step II were observed in the DTG as a peak at
908 K 573 K. The most of decomposition products were evolved
40 –4
–1
at stage II. The 28 amu fragment has two peaks in the
30 Vh=10 C min
°

–5 curve. First one appeared simultaneously with 32 amu and

300 400 500 600 700 800 900 1000 1100 44 amu, and the second one come into sight above 1000 K.
Temperature/K
The 32 amu fragment was assigned to oxygen, which
Fig. 1 a TG and DTG curves of cattlehide collagen fibers, b Mass decreased from step II, because oxygen might react with
loss for the decomposition of cattlehide collagen fibers and c TG– nitrogen or carbon monoxide. The 44 amu curve decreased
DSC curves of cattlehide collagen fibers sharply at around 553K, there are some carbon dioxide in
the beginning, and part or most of carbon monoxide in the
early stage was oxidized to carbon dioxide, while oxygen
peak appeared at 743 K, as shown in Fig. 3. The peak at was used up in the later. At step II, the peak in the 44 amu
908 K corresponds to the carbonization of tar. According curve was observed to begin at around 593 K. There are
to our previous results obtained by TG analysis of hide two peaks in 18 amu curve. The first one is water des-
powder, no mass loss occurred above 908 K [17]. orption, and the second peak may be oxidation product.
The photographs in Fig. 2 showed that there is no The 44 amu curve was assigned to predominantly carbon
obvious change below 473 K. The bright area is ordered dioxide, and the 30 amu curve assigned to nitric oxide. The
structure of leather, and dark one is amorphous structure. 64 amu curve was associated with a series of organic

123
2008 P. Yang et al.

Fig. 2 POM photographs of

cattlehide collagen fibers at
different temperature: a 303 K,
b 373 K, c 423 K, d 473 K,
e 488 K, f 493 K, g 503 K and
h 513 K

products. Possible molecular identities and assignments of most possible. As the N2 was not absorbed by FTIR, and
these evolved species were based on the molecular mass, there is no peak in the FTIR curve at 1173 K. Among the
and the peaks were reported in the literature for the organic fragment curves, the 70, 72 and 78 amu curves (as-
pyrolysis of a variety of organic matters and are listed in signed to benzene) show a distinct broad peak in this region.
Table 1. Although the data in Fig. 3 were recorded in an inert
The 12, 16 and 18 amu fragments were evolved below atmosphere, the purge gas still contains a small amount of
573 K. Above 593 K, the rest of the selected fragments oxygen (\10 ppm). That small contamination in the purge
appeared, which shows that the small molecules evolved at gas can be used to aid the identification of the origin of
first, and the decomposition happens higher than 573 K. The CO2 evolution in step II due to the decomposition of the
28 amu fragment (Fig. 3a) was assigned to CO and N2, organic pyrolysis products. The peaks in the 44 amu curve
respectively, which evolved continuously and had two peaks should be CO2. Peaks are observed in the 32 amu curve,
at 593 and 1173 K. The mass peak coanalyzed with FTIR corresponding to oxygen, suggesting that a significant
spectroscopy of the evolved product at 1173 K was N2 the portion of mass loss in step II associated with the removal

123
Study on thermal degradation of cattlehide collagen fibers by simultaneous TG–MS–FTIR 2009

Table 1 Evolved gas analysis

Fragment/amu Molecular formula Molecule References

16 CH4 Methane [19]

18 H2O Water [19]
28 N2, CO Nitrogen, carbon oxide [20]
30 CH2O, C2H6 Formaldehyde, ethane [20]
32 O2 Oxygen
44 CO2 Carbon dioxide
54 C4H6, Butadiene, cyclobutene, butyne [21]
HCCCHO Propynal
C3H5N Propane nitrile
64 SO2 Sulfur dioxide
67 C6H10 Crotonitrile, allyl cyanide, methacrylonitrile [21]
70 C5H10, C4H6O Pentene, cyclopentane
72 C5H12, C3H4O, Pentane, acrylic acid
78 C6H6 Benzene
81 C5H7N, C7H12 Methyl pyrrole, methyl cyclohexane
91 C2H5NO3, 2-nitroethanol, ethyl nitrate
C6H5CH3, Toluene
C6H4(CH3)2, 1,4-, 1,3- and 1,2-dimethyl benzene
C6H5–C2H6 ethylbenzene

of the organic phases. Carbon monoxide loss was observed described by means of online coupled FTIR gas cell and
at a high temperature, probably attributed the decomposi- spectrometer.
tion of the organic phase. TG–FTIR and TG–MS extend the thermal analysis by
Figure 4a shows that there are two major peaks in additional monitoring and identification of the pyrolysis
28 amu fragment curve. The first peak started at about gases, comparing TG illustrates the thermal decomposition
513 K, decreased about half at 658 K and decreased totally in terms of the mass loss. It is obvious that such a char-
at 713 K. The second peak started at 1033 K and end at acterization of the decomposition profits greatly with this
1373 K. The result demonstrated that carbon monoxide additional information and delivers a detailed insight into
evolved continuously and was the major pyrolysis product. the decomposition processes. However, the interpretation
Figure 4b shows the mass spectroscopy of 30 amu frag- of the FTIR is often difficult since a superposition of the
ment. The 30 amu curve has been tentatively assigned to various signals from the different gases can lead to com-
both the production of nitric oxide (NO) and formaldehyde. plex spectra. In the case of TG–MS, the ionization of the
Both are possible products of the pyrolysis of proteins and decomposition fragments can result in ambiguous mass
amides. Ethylene with the m/z of 30 amu and could, signals. By using both methods, unambiguous interpreta-
therefore, also contribute to this evolution. The 30 amu has tions of the data were obtained without using further
a number of peaks at around 598, 748 K with a series of assumptions on the material or the active decomposition
shoulders associated with each peak. pathway. Figure 5a is a three-dimensional plot of the FTIR
It is also interesting to note the continuous evolution of spectrometry response during such a heating experiment to
30 amu. That may due to the occurrence of gas phase 1473 K at 10 K min-1. A characteristic spectrum obtained
reactions, although it is notable that the DTG curve in this at 673 K is shown in Fig. 5b. The decomposition processes
region does not return to 0 % min-1, a significant and finite of leather have occurred in our simultaneous and online
minimum indicates that material is continually lost measurements resulting in two mass loss stages at 363 and
throughout this region. Without further analysis, however, 593 K, respectively, producing in both cases H2O, NO,
identification of the species responsible for this peak can- CH2O, C4H5N and C2H6. The first stage corresponding to
not be made with certainty. Identity and evolution moisture (series of narrow bands at 4000–3500 and
dynamics of the evolved gaseous species have also been 2000–1300 cm-1) is evident. On subsequent heating, a

123
2010 P. Yang et al.

(a) (a)
100 28
c 16 1.0
90 18
28
80 30
32 0.8
70
44

Absorbance
60 54
Mass/%

64
50 67 0.6
70
40 72
78
30 81 0.4
91
20

10
0.2
0
400 600 800 1000 1200 1400
Temperature/K 200 400 600 800 1000 1200 1400 1600
Temperature/K
(b) (b)
100
c 1.1
28
90
30
30
32 1.0
80

70 0.9

60 0.8
Absorbance
Mass/%

50
0.7
40

30
0.6

20 0.5
10
0.4
0
400 600 800 1000 1200 1400 0.3
Temperature/K
200 400 600 800 1000 1200 1400 1600
Fig. 3 Ion current, as a function of the m/z ratio in amu from 2 to Temperature/K
100 amu over the full temperature range (room temperature to
1373 K). a Only m/z ratios up to 100 are shown as no observable ion Fig. 4 Mass spectroscopy of 28 amu fragment (a) and 30 amu
current was measured above this value. b Mass spectroscopy of m/ fragment (b)
z = 28, 30 and 32 amu fragment and DTG curve of sample

minimum at 823 K, a slight increase is observed at 1273 K.

further and more intense evolution of H2O is observed, Carbon monoxide can originate from direct decarboxyla-
reaching a maximum at 556 K, due to condensation reac- tion of free –COOH groups from glutamic and aspartic
tions. Ammonia, with a characteristic bands at 964, 930 acids. We believe that this reaction is responsible for the
(main bands), 1626 and 3335 cm-1 starts to evolve above incipient release of CO. Afterward, CO may be produced
523 K. Between 523 and 503 K, its bands are the most by decomposition reactions involving peptide –CO–
intense, suggesting that deamination might be the dominant groups. The final slight increase in CO evolution must be
decomposition process in this temperature region. due exclusively to condensation reactions within the resi-
Ammonia originates from deamination reactions of colla- dues. The decomposition of sample at 593 K might be
gen involving free –NH2 groups from arginine and lysine either a breaking up process of macromolecule following
and peptide –NH– groups. After reaching a maximum gas phase oxidation or bulk catalyzed dissociation. The
release at 513 K, the intensity of NH3 bands diminishes catalyst itself is probably an in situ formed solid decom-
and then slightly decreases at high temperatures. It is position intermediate of leather.
noteworthy to mention that nitrogen can also be released A typical spectral output from the TG–FTIR is shown in
from leather as N2 which is not detectable by FTIR. The Fig. 5a, which was known as a stack plot, providing
most intense band in 3D FTIR plots is that of CO information both as a function of wavenumber and tem-
(2150–2300 cm-1) which becomes visible at around 523 K perature. Above 573 K, the evolution of HNCO
and sharply increases up to 613 K. After falling to a broad (2250 cm-1) can be detected (maximum at 613 K).

123
Study on thermal degradation of cattlehide collagen fibers by simultaneous TG–MS–FTIR 2011

band at 2850–3000 cm-1, with a highest peak at

(a) 2970 cm-1 reaching a maximum release at around 773 K,
was attributed to hydrocarbons, mainly ethane. The FTIR
results at 673 K in argon conditions, shown in Fig. 5b,
confirmed the presence of a second degradation step, dur-
ing which the characteristic narrow peaks of CH4
nce/%

(1304 cm-1) can be easily observed, which have a maxi-

mum intensity at around 493 K. Methane may form by
ta
Transmit

condensation reaction involving –CH3 and –CH2– groups.

It is interesting to note that the maximum CH4 release
coincides with a slight minimum in CO evolution. The
140
0
above-mentioned compounds (except pyrrole) were also
120
100
0 detected on thermal decomposition of another protein,
0
80 casein. Other compounds which were observed on thermal
00

K
10

00

e/
60 decomposition of bone collagen or biocollagenic wastes by
ur
0
15

00

Wa
t
40
ra
20

00

ven 0 MS [15, 23–26] could not be clearly distinguished in out

pe
25

um
00

20
m

b ers 0
30

FTIR study due to the fact that their absorption bands are
Te
00

/cm –
35

1
overlapped on the infrared bands of the above-mentioned
gases. As a matter of fact, a black solid residue was yielded
(b) during the pyrolytic degradation of the leather. Detailed
data about decomposition temperatures and volatile loss
could be obtained from the analysis of the experimental
runs performed. These uncertainties have been resolved by
Transmittance/%

FTIR spectroscopic gas cell (TG–FTIR), showing only

evolution of NO2 with two absorption bands positioned at
1616 and 2911 cm-1, and no bands of NO or N2O could be
detected, considering the expected nitrogen oxides.

Conclusions

In this preliminary study, TG–MS–FTIR was applied to the

4500 4000 3500 3000 2500 2000 1500 1000 500 characterization of leather fragments. The aim of this initial
Wavenumbers/cm –1 study was to characterize the decomposition evolved
products of the leather fragments and interpret the TG–
Fig. 5 a FTIR spectra collected during the online analysis of the
volatiles evolved in the decomposition of the hide powder, (b) FTIR MS–FTIR data. TG–MS–FTIR curves were collected by
spectrum of evolved gases from leather, decomposed in argon, heating leather samples to 1273 K in an argon atmosphere.
measured at 773 K by online coupled TG–EGA–FTIR system (initial Under these conditions, both the organic and inorganic
mass 12.96 mg, 20 mL min-1 argon flow, 10 K min-1 heating rate, phases decomposed and produced a variety of organic
open Pt crucible)
fragments and carbon monoxide. At first, water was lost at
about 373 K, and meanwhile, triple helix was destroyed.
Second, long chains were fracture. Long chains were
However, the corresponding band is partially superimposed decomposed to inorganic fragments and organic fragments,
on CO2 band, resulting in an augmented intensity. Pyrrole while some ring compounds were not decomposed at about
(C4H5N) was detected to evolved above 523 K, with a peak 593 K, because some fragment as pentene and cyclopen-
at 613 K, but its band (720 cm-1) partially overlaps with a tane were evolved in the later. It demonstrated that leather
minor band of CO. Pyrrole was previously detected by Py- was decomposed three or more steps. Pyrolysis of the
GC/MS as a major compound from pyrolysis of pig-skin organic phase, which is composed predominantly of col-
collagen, leathers and bones [22]. Pyrrole originates from lagen, resulted in the observation of ion fragments up to
proline, which is the second most abundant amino acid in 100 amu. Selected fragments were monitored and could be
collagen. At above 643 K, a band corresponding to HCN associated with the decomposition of the collagen phase.
(714 cm-1) appears, reaching a very broad maximum By targeting changes in particular decomposition frag-
between 573 and 773 K. At higher temperatures, a broad ments, it may be possible to determine thermal degradation

123
2012 P. Yang et al.

mechanism of leather. The method shows TG–MS–FTIR 11. Carşote C, Badea E, Miu L, Gatta GD. Study of the effect of
as an approach to the study of leather degradation in a tannins and animal species on the thermal stability of veg-
etable leather by differential scanning calorimetry. J Therm Anal
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atmospheres in order to gain a more detailed understanding thermal analysis techniques complemented by SEM, FTIR, UV-
Vis-NIR and unilateral NMR investigations. J Therm Anal
of the decomposition processes of forensic leathers. The Calorim. 2008;91(1):17–27.
TG–FTIR technique proved to be a straightforward 13. Budrugeac P, Cucos A, Miu L. Use of thermal analysis methods
experimental methodology to achieve efficient data on the to asses the damage in the bookbindings of some religious books
nature of the evolved gas products generated in specific from XVIII century, stored in Romanian libraries. J Therm Anal
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Acknowledgements This research was financially supported by the Anal Calorim. 2008;94(2):335–42.
National Natural Science Foundation of China (No. 51373158) and K. 15. Budrugeac P, Miu L, Bocu V, Wortman FJ, Popescu C. Thermal
C. Wong Education Foundation, Hong Kong. Beifang University of degradation of collagen-based materials that are supports of
Nationalities, China (No. 2014XBZ12). cultural and historical objects. J Therm Anal Calorim.
2003;72(3):1057–64.
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