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R. Aravindhan, J. R. Rao and T. Palanisamy, RSC Adv., 2015, DOI: 10.1039/C5RA11740B.
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DOI: 10.1039/C5RA11740B
1
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DOI: 10.1039/C5RA11740B
Summary
Approach towards waterless tanning is crucial to address present challenges faced by humanity
such as global warming and depletion of water resources. Here, green solvents alternate to water
such as ethanol, ethyl acetate and ethyl lactate were employed for both pickle-based and pickle-
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less chrome tanning. Results show that ethanol medium appears to be the best solvent for chrome
Extensive studies indicate that the chrome tanning in ethanol medium leads to higher exhaustion
(87% for pickle-based and 95% for pickle-less), better chromium content, distribution and
shrinkage temperature and low chromium leaching in tanned leathers compared to water
mediated tanning. Both visual and electron microscopic analyses demonstrate comparable grain
structure and fiber architecture in tanned and crust leathers. Similarly, strength and organoleptic
properties of crust leathers are also comparable between ethanol and water mediated tanning.
The process enables reduction of COD, BOD and TS loads in composite liquor by 14-26, 21-28
and 42-46%, respectively. The leather properties are not altered upon recycling of chromium
containing ethanol liquor up to two times. These results suggest that it is possible to replace
water by ethanol for chrome tanning, which offers great potential for sustainable leather
2
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Introduction
pollution, resource depletion and threats to food, water and energy securities require a paradigm
aforementioned factors are being scrutinized globally to ensure sustainable production 4. Chrome
tanning is a popularly employed process to convert the skins and hides into leather by stabilizing
the collagen matrix 4. Currently the process is carried out in aqueous medium. Aqueous medium
is helpful in solubilizing the tanning agent, basic chromium sulphate, and aiding the penetration
into the collagen matrix. Further, water is essential for hydrolysis and olation of chromium
molecules and to form various oligomeric species 5. Nevertheless, the conventional chrome
tanning process suffers from poor chromium uptake in the skin matrix and therefore significant
amount of chromium molecules remain in large amount of water and released as effluent 6. This
large amount of wastewater contains potentially toxic chromium molecules and the disposal of
the same remains as a major problem in leather industry. To address this issue, a number of
4, 7
researchers have developed various chromium management technologies . Chrome recovery
and reuse 8, direct chrome liquor recycling 9, high exhaust chrome tanning and tanning salts 6, 10,
5
closed loop aluminium-chrome combination tanning, pickle-basification free chrome tanning
11
and two-stage tanning are some examples of recent development in this area by our group as
well as others. Some advanced and futuristic clean chrome tanning systems have also been
12, 13 14, 15
developed by our group such as the three-step tanning and reverse tanning processes ,
16
which are now being further investigated globally . In addition to reducing the chromium
emission, these advanced processes also lead to other benefits such as reduced water
3
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consumption and discharge and reduction in the amount of use of chemicals, power, time and
cost compared to conventional tanning process. However, in view of the increased demand and
reduced supply of water coupled with projected global water scarcity, the development of
17-19
waterless tanning technology is need of the hour . Solvent based chrome tanning techniques
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20-23
have already been reported in the literature . Chagne et al. and Silvestre et al. employed
carbon dioxide as medium at high pressure (few experiments at supercritical fluid state) with
The present investigation aims to develop a chrome tanning process using green solvents
chosen from a set of GSK green chemistry principles such as LD50, environment and health
hazards 24. The approach relies on the fact that the free water present in the pelt is sufficient for
the diffusion and fixation of chromium in the skin matrix, which was recently established based
principles, we have shortlisted three solvents namely ethanol, ethyl acetate and ethyl lactate24.
Further, Capello et al. assessed substance-specific hazards with the quantification of emissions
and resource use over the full life-cycle of a solvent and found that ethanol was Greener in
comparison to other solvents25. Besides, ethanol and its derivatives are produced by fermentation
from petrochemical route leading to avoidance of fossil resource use and CO2 emission to the
environment. In this work, pickle-based and pickle-less chrome tanning5 processes have been
examined in non-aqueous medium such as ethanol, ethyl acetate and ethyl lactate. Based on the
results of these preliminary tanning experiments, ethanol medium was chosen for carrying out
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chrome tanning in matched pair experiments along with control followed by a conventional post
tanning process in aqueous medium. Detailed analysis on the quality of the wet blue leathers as
well as effluent characteristics and emission factors was carried out. Crust leathers were
Materials
Wet salted goat skins with an average area and weight of 4.51 sq.ft. were procured from local
suppliers at Chennai and conventionally processed into pickled/delimed pelts at the Pilot
Tannery, Central Leather Research Institute. For all the tanning trials, commercial grade
chemicals such as sodium formate, sodium bicarbonate, acetic acid, basic chromium sulphate, etc
were employed. Analytical grade ethanol was procured from M/s Hayman and used without
further purification. Analytical grade ethyl acetate and ethyl lactate were procured from M/s
Loba Chemicals Pvt. Ltd. and used without further purification. Tanning trials were carried out
Three solvents namely, ethanol, ethyl lactate, ethyl acetate were chosen for the preliminary
tanning trials. Pickled/delimed goat pelts were cut into small pieces measuring 10.2 sq.ft. and
used for the preliminary tanning trials. In the case of pickle-based chrome tanning, two pickled
pelt cut pieces (each measuring 10.2 sq.ft.) were treated with 7% basic chromium sulphate
(BCS) salt (percentage based on pelt weight) in stainless steel drums for 1 h. Then 100% v/w of
the chosen solvents (individually) was added as a medium and drummed for 30 min. After
5
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ascertaining the penetration of chromium, the pH was found to be 2.90.2. In the subsequent
basification step, pH of the tanning bath was increased to 3.70.2 using 1% sodium formate for
interval and finally drummed for 1 h. In the case of pickle-less chrome tanning, the pH of two
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delimed pelt cut pieces (each measuring 10.2 sq.ft.) was adjusted to 5.50.5 using 0.5% acetic
Then 100% v/w of the chosen solvents (individually) was added as a medium and drummed for 2
h. After ascertaining the penetration of chromium, the pH was found to be 4.00.2. The total
duration of both pickle-based and pickle-less chrome tanning was around 3 h. The tanned
leathers were assessed by experienced leather technologist for their quality through organoleptic
examination. The chrome content in the tanned leathers was also analyzed as described in the
forthcoming section.
Ethanol medium employed for tanning yielded good chrome tanned leather compared to its
counterparts such as ethyl lactate and ethyl acetate. Hence, ethanol was selected for further
experiments. Two pickled/delimed goat pelts were used for each experiment employing pickle-
based and pickle-less chrome tanning in ethanol medium as described in the previous section
along with control trials in water medium. The control and experimental chrome tanned leathers
were converted into crust upper leathers employing a conventional post tanning process in
aqueous medium.
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The shrinkage tester apparatus (SATRA STD 114, SATRA Technology Centre) was used for
determining the shrinkage temperature of chrome tanned leathers. The tanned leathers were
27
leathers were analysed for chromium content employing the standard procedure using a UV-
free basis. Triplicate measurements were carried out for each analysis and the average values
were calculated. Bulk properties of chrome tanned leathers such as fullness, grain smoothness,
color and wrinkles were assessed by experienced leather technologist through organoleptic
examination.
A known weight of experimental chrome tanned leather sample was placed in a beaker with 50
ml of distilled water and ethanol separately. In the case of control leathers (water mediated), a
known weight of tanned leather sample was placed in a beaker with 50 ml of distilled water. It
was agitated in a shaker at low rpm for 3 h. The chromium content in the solution was analyzed
using alkaline peroxide procedure and the concentration of chromium was determined at 372 nm
using a UV-Visible spectrophotometer (UV 1800, Shimadzu)28. The amount of chromium was
then calculated using molar absorption coefficient () value of 4.8 103 M-1cm-1 based on Beer-
Lambert law. Triplicate measurements were carried out and the average values were calculated.
Chromium leached from Cr-tanned leather sample (Cr2O3 %) was calculated by dividing the
amount of chromium in the leachate by the amount of chromium in the chrome tanned leather
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Spent chrome liquor was collected from both control and experimental pickle-based and pickle-
less chrome tanning processes. Liquors were acid digested and analyzed for chromium using
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alkaline peroxide procedure as described above28. The percentage exhaustion of chromium was
Composite liquors from control and experimental leather processing were collected from chrome
tanning up to post-tanning. The liquors were analyzed for chemical oxygen demand (COD),
26
biological oxygen demand (BOD), and total solids (TS) as per the standard procedures .
Emission loads were calculated by multiplying concentration (mg/L) with the volume of effluent
The chrome tanned leather samples were dehydrated gradually using acetone and methanol as
29
per standard procedure . Excess solvent was removed from the samples by placing them
between filter papers. Crust leathers were directly analyzed without dehydration. Samples were
then cut into specimens of uniform thickness and coated with gold using an ion-sputtering
device. The samples were mounted on aluminium stubs and analyzed using scanning electron
magnifications.
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Samples for various physical tests were obtained from control and experimental crust leathers as
per IUP method 30. Samples were conditioned at 804oF and 652% R.H. over a period of 48 h.
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Physical properties such as tensile strength, % elongation at break, tear strength and grain crack
crust leathers were assessed for softness, fullness, grain smoothness and general appearance by
organoleptic examination. The leathers were rated on a scale of 010 points for each property by
In order to find the feasibility of recovering and recycling the ethanol used in chrome tanning, a
limited study was conducted employing pickle-based chrome tanning. One pickled goat pelt was
used for each experiment employing pickle-based chrome tanning in ethanol medium as
described above. At the end of the chrome tanning process for the first batch, the spent ethanol
liquor was collected, filtered and analyzed for the chromium content as described above. In the
1st recycling process, BCS equivalent to the balance amount of the spent ethanol liquor was
added to the pelt and drummed for 1 h. Then the chromium containing spent ethanol liquor was
added and the total volume was adjusted to 100% v/w by the addition of fresh ethanol and
drummed for 30 min. After confirming the penetration of chromium, the pH was found to be
3.20.2. During basification, 0.5% sodium formate was added and drummed for 10 min followed
by the addition of 0.8% sodium bicarbonate in 3 installments at 10 min interval and finally
drummed for 1 h. The pH of the tanning bath was found to be 3.80.2. At the end of the chrome
tanning process for the second batch, the spent ethanol liquor was collected, filtered and
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analyzed for the chromium content. The collected spent ethanol liquor was reused in the third
Preliminary trials
lactate employing both pickle-based and pickle-less chrome tanning processes with pickled and
delimed pelts, respectively. Although chrome tanning is possible in all the selected solvents,
quality of the tanned leather depended on the solvent used for the process as shown in Table 1.
Visual assessment of chrome tanned leathers processed through pickle-based and pickle-less
chrome tanning in ethyl acetate and ethyl lactate medium shows slight swelling, coarse grain and
moderate penetration of chromium. Chrome tanned leathers processed through ethyl acetate did
not show significant color change from the conventional wet blue, however ethyl lactate medium
yielded bluish leathers with green tinge. On the other hand, chrome tanned leathers (pickle-based
and pickle-less) prepared using ethanol medium are bluish comparable to the conventional wet
blue without any coarse grain and swelling effect. Further, leathers prepared in ethanol medium
show high uptake of chromium compared to those prepared in ethanol derivatives. This could be
due to the fact that the dispersion and diffusion of BCS in the skin matrix is better in ethanol
medium compared to other two solvents assuming that the internal moisture present in the pelt is
constant for all the three systems. Therefore, ethanol was selected for further detailed analysis
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Digital images of control and experimental chrome tanned leathers and respective process liquors
(insets) are shown in Fig. 1. It is evident that the color of pickle-based chrome tanned leathers is
light blue for both ethanol and water mediated processes, whereas the pickle-less chrome tanning
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yields slightly dark blue leathers. Chromium exhaustion, distribution and shrinkage temperature
in Table 2. Exhaustion levels of chromium for both pickle-based and pickle-less chrome tanning
in ethanol medium are higher compared to similar processes carried out in water medium
(control). This may be due to the limited solubility of BCS in ethanol medium, which drives
more chromium in the skin matrix containing internal water. The color variations in the process
spent liquors (see insets of Fig. 1) also demonstrate the higher exhaustion in ethanol mediated
processes. The improved uptake of chromium is also reflected in the chromium distribution data.
It is seen that the leathers processed in ethanol medium possess higher amount of chromium in
all the regions of leather, namely butt, neck, and belly, compared to those processed in water
medium. Further, both ethanol and water mediated chrome tanning processes yield leathers with
reasonably uniform chromium distribution in all the regions of leathers. The shrinkage
temperature of leathers processed in ethanol medium is slightly higher than that of control
leathers (water mediated). These results suggest that replacing water with ethanol for chrome
The extent of chromium leaching and the amount of chromium present before and after
leaching in the tanned leathers processed through pickle-based and pickle-less chrome tanning in
ethanol and water medium are shown in Table 3. We observed lower leaching of chromium from
both control and experimental leathers when water and ethanol were used as leaching solvents. A
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maximum of 2% Cr2O3 was leached from chrome tanned leather when water was used as tanning
19
as well as leaching medium. This value is lower than those reported in the literature . This
indicates that the remaining chromium (~ 98%) is fixed chemically with the leather matrix. The
experimental leather shows fairly reduced chromium leaching when compared to control leather.
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In addition, the amount of chromium present in leathers after leaching is comparable to the
The organoleptic assessment data of both control and experimental chrome tanned leathers
prepared through pickle-based and pickle-less chrome tanning processes using ethanol and water
medium is given in Table 4. It is seen that leathers tanned in ethanol medium show either
comparable or even better color, grain smoothness and fullness in comparison to leathers tanned
in water medium. However, leathers tanned in ethanol medium through pickle-less chrome
tanning show slightly more wrinkles in comparison to their counterparts processed in water
Scanning electron micrographs showing the grain surface of control and experimental
chrome tanned leathers are given in Fig. 2. The grain surface of experimental leathers shows
clear hair pores without any deposition of chromium comparable to the control leather. The
cross-sectional images of control and experimental chrome tanned leather samples (Fig. 3) show
fiber bundles with comparable porosity and architecture. Similar observation has been made on
the surface and cross section of the control and experimental crust leathers (Fig. S1 and S2).
These results suggest that the microstructure of the leather is not altered significantly upon
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The chrome tanned leathers processed through pickle-based and pickle-less chrome tanning in
ethanol medium were post tanned in water medium. Composite liquors collected by mixing spent
liquors from chrome tanning, neutralization, washing, retanning, fatliquoring, dyeing and fixing
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process steps for both control and experimental processes, were analyzed for COD, BOD, and
based and pickle-less chrome tanning in ethanol medium lead to significant reduction in the
COD/BOD/TS loads by 14-26, 21-28 and 42-46%, respectively compared to control processes
carried out in water. The observed reductions in pollution loads could be due to the improved
The physical properties such as tensile, tear and grain crack strength of control and experimental
chrome tanned leathers processed through pickle-based and pickle-less chrome tanning were
analyzed and the values are given in Table 6. It is seen that the strength characteristics of
experimental leathers are comparable to that of control leathers. Hence, it is seen that the chrome
tanning process in ethanol medium did not critically affect the strength properties of leathers in
The organoleptic properties of control and experimental crust leathers processed through
pickle-based and pickle-less chrome tanning are given in Fig. 4. The properties of the leathers
made using chrome tanning in ethanol medium are comparable to those of leathers made using
the conventional chrome tanning process in water medium. The grain smoothness, softness and
general appearance of crust leathers processed through pickle-based and pickle-less chrome
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tanning in ethanol medium are comparable to the control leathers tanned in water medium. There
seems to be a slight decrease in the fullness of experimental leathers processed through pickle-
less chrome tanning in ethanol medium when compared to control leathers. In general, chrome
tanning in ethanol medium did not adversely affect the organoleptic properties of leathers in
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A paramount requirement of solvent based processes is the ability to recover and recycle the
used solvent in the subsequent processing, which would reduce the cost and environmental
burden. Here, the results of recycling of the spent ethanol liquor in the pickle-based chrome
tanning for two times are given in Table 7. It is seen that nearly 65% spent ethanol liquor can be
collected during recycling up to three batches. Therefore, the fresh solvent requirement during
recycling can be minimized significantly. As can be seen, the collected ethanol liquor contain
chromium equivalent to about 0.7 to 0.9% BCS, which means that the BCS offer can be reduced
from 7% up to 6.1% (for the 4th batch) leading to cost saving to some extent. Lower amount of
chromium in the spent ethanol liquor evidences higher uptake of chromium in the tanned leathers
as observed earlier. The color of chrome tanned leathers by recycling of spent ethanol liquor is
comparable to the first batch of ethanol-mediated pickle-based chrome tanning process. The
recycling of spent ethanol liquor does not seem to affect the thermal stability of the tanned
leathers. The results suggest that it is possible to recycle the used solvent up to two times
without affecting the properties of the tanned leathers, which can be beneficial in cost
effectiveness.
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Conclusions
In search of alternatives for water based chrome tanning, an attempt has been made in the present
study to perform chrome tanning in ethanol and its derivatives such as ethyl acetate and ethyl
lactate employing both pickle-based and pickle-less method. Although all the three solvents
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enabled the chrome tanning process, ethanol medium provided better chrome tanned leathers in
medium for chrome tanning show comparable shrinkage temperature, grain and fiber
architecture, strength and bulk properties and reduction in chromium discharge in contrast to
water mediated processing. The amount of leachable chromium in the tanned leathers is also low
compared to leathers tanned in water medium. Tanning in ethanol medium also helps in
minimizing waste generation such as chromium, TS, COD, and BOD loads. Further, we proved
that the ethanol liquor from chrome tanning can be recovered and recycled up to 2 times without
affecting the properties of the leathers. The results of this limited study show that ethanol
mediated chrome tanning is feasible and helpful in preventing the environmental pollution and
Acknowledgements
Financial support from CSIR under XIIth plan project Research Initiatives for Waterless
Engineering, Anna University for providing SEM facility. CSIR-CLRI Communication No.
1087.
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3. S. R. Wan Alwi, Z. A. Manan, J. J. Kleme and D. Huisingh, J Clean Prod, 2014, 71, 1-
4. P. Thanikaivelan, J. R. Rao, B. U. Nair and T. Ramasami, Crit. Rev. Env. Sci. Tec., 2005,
35, 37-79.
483-491.
7. V. J. Sundar, J. Raghava Rao and C. Muralidharan, J. Clean. Prod., 2002, 10, 69-74.
1-6.
9. J. R. Rao, B. Chandrasekaran, B. U. Nair and T. Ramasami, J. Sci. Ind. Res., 2002, 61,
912-926.
10. A. Bacardit, J. M. Morera, L. Oll, E. Bartol and M. Dolors Borrs, Chemosphere, 2008,
73, 820-824.
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13. P. Thanikaivelan, J. R. Rao, B. U. Nair and T. Ramasami, Environ. Sci. Technol., 2003,
37, 2609-2617.
16. C. Wu, W. Zhang, X. Liao, Y. Zeng and B. Shi, J Am Leather Chem As, 2014, 109, 176-
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17. O. Tnay, I. Kabdali, D. Orhon and G. Cansever, Water Sci. Technol., 1999, 40, 237-
244.
18. R. Bagatin, J. J. Klemes, A. P. Reverberi and D. Huisingh, J Clean Prod, 2014, 77, 1-9.
19. S. Silambarasan, R. Aravindhan, J. R. Rao and P. Thanikaivelan, J Clean Prod, 2015, 87,
567-572.
20. V. Chagne, F. Silvestre and A. Gaset, J Am Leather Chem As, 1993, 88, 426-439.
21. F. Silvestre, C. Rocrelle and A. Gaset, J. Am. Leather Chem. Assoc., 1993, 88, 440-452.
22. R. Manfred, W. Eckhard, J. Bjrn and G. Helmut, The Journal of Supercritical Fluids,
23. M. Renner, E. Weidner and G. Brandin, Chemical Engineering Research and Design,
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Table 1
Results of the preliminary trials using ethanol, ethyl acetate and ethyl lactate solvents employing
Chrome tanned
leather (Pickle-
based)
Chrome tanned
leather (Pickle-
less)
Comparable to
No color issues, slightly
conventional pickle-less Bluish green color, coarse
Visual coarse grain, slight
processed wet blue grain, swelling effect,
Assessment swelling, reasonable
color, no swelling, good reasonable penetration.
penetration.
penetration.
Cr2O3 % (dry
6.450.21 4.350.16 4.760.14
weight basis)
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Table 2
Exhaustion, chromium distribution and shrinkage temperature data of pickle-based and pickle-
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Table 3
Analytical data on leaching studies in control (C) and experimental (E) chrome tanned leathers
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Table 4
Organoleptic assessment data of the control (C) and experimental (E) chrome tanned leathers
On a scale of 0 to 10, the qualitative descriptors such as excellent, good, average and poor are
weighed as 9, 7 good 8, 4 average 6 and 3, respectively. While the terms such as fuller,
more and less are weighed as 9, 7 more 8 and 4 less 6, respectively. Higher numbers
indicate better properties except wrinkles.
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Table 5
Composite liquor analysis for control (C) and experimental (E) chrome tanning
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Table 6
Physical properties of crust leathers
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Table 7
Data on recycling of the spent ethanol liquor in the pickle-based chrome tanning process
64.7 60 63.2
liquor
Fresh ethanol
added (%) 100 35.3 40
Photographic
images of
chrome tanned
leathers
Shrinkage
temperature 106 108 109
(oC)
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Figure Captions
Fig. 1. Digital images of control and experimental chrome tanned leathers and their respective
process liquors from (a) pickle-less chrome tanning in ethanol medium (b) pickle-less chrome
tanning in water medium (c) pickle-based chrome tanning in ethanol medium and (d) pickle-
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chrome tanned leathers from (a) pickle-based (b) pickle-less chrome tanning in ethanol medium
Fig. 3. Scanning electron microscopic images showing he cross section of control and
experimental chrome tanned leathers from (a) pickle-based and (b) pickle-less chrome tanning in
Fig. 4. Organoleptic properties of control and experimental crust leathers processed through (a)
26
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Fig. 1.
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Fig. 2.
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Fig. 3.
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Fig. 4.
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