Accepted Manuscript

Ultrasound assisted chrome tanning: towards a clean leather production tech-

nology

Embialle Mengistie, Ilse Smets, Tom Van Gerven

PII: S1350-4177(16)30068-2
DOI: http://dx.doi.org/10.1016/j.ultsonch.2016.03.002
Reference: ULTSON 3144

To appear in: Ultrasonics Sonochemistry

Received Date: 7 September 2015

Revised Date: 20 February 2016
Accepted Date: 1 March 2016

Please cite this article as: E. Mengistie, I. Smets, T. Van Gerven, Ultrasound assisted chrome tanning: towards a
clean leather production technology, Ultrasonics Sonochemistry (2016), doi: http://dx.doi.org/10.1016/j.ultsonch.
2016.03.002

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Ultrasound assisted chrome tanning: towards a clean leather production technology

Embialle Mengistie, Ilse Smets, Tom Van Gerven

Embialle Mengistie, Ilse Smets, Tom Van Gerven ()

KU Leuven, Department of Chemical Engineering,
Celestijnenlaan 200F,
3001 Leuven, Belgium
Email: [embiallemengistie.beyene; thomas.vangerven; ilse.smets]@cit.kuleuven.be]

Abstract
Nowadays, there is a growing demand for a cleaner, but still effective alternative for production
processes like in the leather industry. Ultrasound (US) assisted processing of leather might be
promising in this sense. In the present paper, the use of US in the conventional chrome tanning
process has been studied at different pH, temperature, tanning time, chrome dose and US
exposure time by exposing the skin before tanning and during tanning operation. Both prior
exposure of the skin to US and US during tanning improves the chrome uptake and reduces the
shrinkage significantly. Prior exposure of the skin to US increase the chrome uptake by 13.8% or
reduces the chrome dose from 8% to 5% (% based on skin weight) and shorten the process time
by half while US during tanning increases the chrome uptake by 28.5% or reduces the chrome
dose from 8% to 4% (half) and the tanning time to one third compared to the control without US.
Concomitantly, the resulting leather quality (measured as skin shrinkage) improved from 5.2% to
3.2% shrinkage in the skin exposed to US prior tanning and to 1.3% in the skin exposed to US
during the tanning experiment. This study confirms that US chrome tanning is an effective and
eco-friendly tanning process which can produce a better quality leather product in a shorter
process time with a lower chromium dose.
Keywords: ultrasound, leather processing, chrome tanning, chrome uptake, shrinkage

1
1. Introduction

Tanning is the process of converting the putrescible skin and hides from different animals into a
durable and manageable material called leather. Leather making is a very long process and
consists of many different chemical and mechanical process steps [1]. The most important step
of the whole leather making process is the tanning step, which is performed commonly either by
vegetable or mineral tanning. More than 85-90% of the leather making is performed by chrome
tanning, which is the most common type of mineral tanning currently applied [2,3]. Chrome
tanning is preferred by most tanners because chrome tanned leathers are characterized by top
handling quality, high hydrothermal stability and excellent user properties in addition to the
shorter time required to produce finished leather [4].

Conventional chrome tanning is a two-step process. In the first phase, the tanning agent
(chromium sulfate) will diffuse through the pores of the skin to reach the reaction site, i.e., the
carboxyl groups of the collagen. Then, the chromium will react with the carboxyl group of the
collagen to form inter- and intra-molecular crosslinks which increase the resistance against
physical, chemical and biological agents [5, 6].

Due to diffusion limitations of the chrome tanning agents (as well as the other chemicals used in
the rest of the tanning unit operations), in conventional tanning, only 60% to 70% of the total
chromium applied in the tanning process is consumed in the skin matrix while the other 30% to
40% remains in the spent liquor [1, 7]. The low diffusibility of the chrome tanning agents results
in different problems in the leather industry. The first problem relates to the quality of the leather
produced. One of the methods to measure the quality of leather is the hydrothermal stability,
which is dictated by the amount of chrome that has reacted with the carboxyl groups of the
collagen and has, thereby, been fixed in the leather matrix. The more chromium can be fixed, the
higher the hydrothermal stability [5]. Hydrothermal stability of leather products is commonly
measured by shrinkage and boiling tests. The target is to produce leather that has the lowest
percentage of shrinking possible (target is to reach 0% shrinkage) when the skin is boiled at 100
o
C for 1-5 min or having a higher shrinkage temperature (possibly higher than 100 oC) during the
shrinkage test when the skin is tested to determine the temperature at which the skin starts to
shrink [8]. If more than the currently maximum chromium uptake of 70% could be achieved, the

2
hydrothermal stability would increase [9, 5]. The second problem is a high manufacturing cost
due to the loss of chrome tanning agent into the liquor instead of diffusing into the skin and the
subsequent intensive technologies involved in the treatment and recovery process [10]. The last
but not the least problem is the one caused by the discharge of chrome containing wastes into the
environment which creates health problems for human, animal and other life forms [11].

To achieve a higher diffusion rate, in conventional tanning, a higher concentration of chemicals

in the liquid is applied, which, however, only results in marginally better uptake efficiencies
while causing even higher cost and environmental problems [12, 13]. In addition to the dose of
the tanning agent, many factors like temperature, pH and tanning time affect the rate of diffusion
[14]. It is clear that an eco-friendly and effective alternative has to be explored so as to alleviate
these problems. Applying ultrasound during the production process presents a potential answer.

A sound wave with a frequency above the human audible range (16 Hz16 kHz) is called
ultrasound (US). Power US is a sound with a frequency of 20-100 kHz, which is commonly used
for enhancing physical processes such as cleaning, emulsificaion, crystallization, extraction in
addition to accelerating chemical reactions [15, 13].

The sonochemical activity arises mainly from acoustic cavitation in liquid media [16, 17]. The
effects of cavitation can either be chemical or physical. Strong acoustic streaming, high shear
stress near the bubbles, micro-jets near solid surfaces because of turbulences and collapse of
cavitation bubbles, increase in local temperature and pressure and generation of free radicals
from the use of power ultrasound are some of the effects which have been used for different
applications [18-20]. Detailed studies of power ultrasound have been conducted on the
application of the effects of cavitation in environmental sciences, biotechnology, polymer
chemistry, electrochemistry, nanotechnology, chemical synthesis, green chemistry, food
processing, and other manufacturing processes [19, 21-23]

In solid-liquid systems, the implosion of cavitation bubbles accelerates the liquid to move with a
velocity of up to 104 cm/s and generates micro-jets directed towards the solid surface [24-26].
These micro-jets cause an increase of the pore diameters at the surface of the solids and create

3
micro-mixing in the liquid near the surface. This results in an increased diffusion of solutes
inside the pores of the solid surface and thus facilitates mass transfer. In materials like leather,
the localized temperature increase and the swelling effect due to US may also improve the
diffusion [13, 20].

US technology has already been well exploited in the dyeing step of leather processing and was
found to be very efficient in increasing the dyeing quality of the finished leather, reducing the
environmental risk and costs for dyeing. In an experiment carried out for dyeing wet-blue bovine
hides and sheep skins using an ultrasonic bath with a frequency of 38 kHz and intensity of 1.36
W/cm2 at different temperatures, the process time was shortened by up to 70% and the dye
uptake was increased by up to 50% [27]. A dyeing experiment using cow crust leather was also
carried out using US (33 kHz and 150 W) at a varying dye amount, temperature, dye type and
time. The dye uptake (dye administered minus dye in the spent liquor divided by the dye
administered) increased by 30-45% and 15-35 % when compared to the control process in
stationary and conventional drumming, respectively. The study also indicated that it is possible
to achieve 97.5%, 85%, 91.6% dye uptake in 3 h dyeing time using US compared to only 56.3%,
38.9%, 28.9% without US in a stationary condition for acid black, metal-complex black and
direct black dyes, respectively [26]. Sivakumar et al. (2010) also studied the effect of US on
chrome tanning by using a pickled cow pelt at pH 2.8 and 32 oC with an 8% basic chromium
sulfate dosage. As a result, they found a 2-3 fold increase of the chrome uptake by using 80-
100W ultrasound at the indicated parameters [12].

In addition, improvement has been achieved by using US in the pre-tanning operations such as
soaking, liming and degreasing during which hair and grease are removed from the hides. US (33
kHz and 150 W) helps to improve the fat removal in the degreasing process (duration of 2 h) of
sheep skin with kerosene as a solvent from 2.2% in the control (conventional tanning) to 54.6%
with the aid of US [28-30].

4
It is clear that technologies which can increase the diffusion and uptake of chrome into the
leather, thereby decreasing the tanning cost, producing quality leather with high hydrothermal
stability, and alleviating environmental problems have to be explored. There have been studies
before on the effect of ultrasound in leather manufacturing, but these had different processing
steps in scope, such as dyeing, unhairing, etc. To the best of our knowledge, there are no
detailed investigations performed on the effect of ultrasound exposure prior and during chrome
tanning. Moreover, the knowledge gap on the effect of ultrasound on the quality of the leather
produced by ultrasound assisted-chrome tanning needs to be filled. In addition, the optimum
operational parameters for US assisted chrome tanning have to be determined. Therefore, the aim
of this study is to investigate whether US application before or during the chrome tanning
process improves the chrome uptake by the skins, thereby improving the leather quality and
alleviating environmental burdens that are currently prevailing. Furthermore, if it is
demonstrated that US assisted chrome tanning is beneficial, the optimum operational parameters
are determined.

2. Material and Methods

2.1 Experimental setup
From a wet salted sheep skin a pickle was prepared (by lowering of the pH value to the acidic
region in the presence of salts to help with the penetration of tanning agents) following the
conventional procedure at Modjo tannery, Ethiopia during which hair and grease are removed
from the skins. Then, the skin was cut into 5 x 5 cm samples taken from the same lateral
positions of the skin following the line of the backbone of the animal to achieve samples with a
relatively similar thickness and grain surface [12, 29-30].

The skin was exposed to US, either before chrome tanning or during chrome tanning. An US
power generator UP200S from Hielscher Ultrasonics GmbH (Germany) with working frequency
of 24 kHz was used, coupled to an S14 (14 mm diameter) sonotrode (an acoustic power density
of 105 W/cm2) at full pulse. For all US experiments, these frequency and power density settings
were kept constant. Figure 1 summarizes the experimental flow diagram. In the first series of
experiments the pickled skin pieces were exposed to US prior to chrome tanning for 10 up to 60
min. Then, the exposed skins were chrome tanned with between 4% and 8% by weight basis

5
chromium sulfate for 2 up to 6 hours [12, 29]. An industrial grade basic chromium sulfate
(25.48% Cr2O3, 33% basicity) from Soda Sanayii A. (Turkey) was used for all the tanning
experiments.

The chrome tanning process was conducted in a 2000 mL glass beaker filled with water, of
which the weight was equal to 170 times the weight of the skin and it was kept in a water bath to
maintain the temperature at the specified value (within a range of 2 oC).
The beaker was stirred with a magnetic stirrer adjusted to 30 rpm. At the start of the tanning
procedure half of the basic chromium sulfate was added, whereas the remaining half was added
after one hour. An analytical grade sodium formate (3% by weight of the skin) was used as a
masking agent shortly after the tanning agent is added. One hour after the tanning process
started, the tanning bath was basified using 6% (by weight of the skin) sodium bicarbonate (in
three equal aliquots administered in one hour) while strictly monitoring the pH each time the
sodium bicarbonate is added [5]. A control experiment was performed by tanning the skin
without exposure to US. During the chrome tanning procedure, the starting pH of the tanning
bath was maintained at a pH of 2.5 to 4 (which later was basified by the addition of sodium
bicarbonate) and a temperature of 30 up to 50 oC.

In the second series of experiments, the skins were exposed to US during the chrome tanning
process. The dose of chemicals and the length of the tanning time were varied in a similar
fashion as in the first experiment while exposure time was set between 20 and 120 min. The
starting pH was fixed at a value of 3 and the temperature at a value of 40 oC, as this appeared to
be the optimal value of the first series results.

Figure 1. US tanning experimental flow diagram.

2.2 Analysis methods

UV Spectrophotometry. The spent chrome liquor samples were collected at regular time
intervals and analyzed for the chromium concentration using a spectrophotometric method [31].
A Shimadzu UV-visible spectrophotometer UV-1601PC at 540 nm wavelength was used for the
analysis. The % chromium uptake at time t was calculated using the formula below.

6
    
%Cr
= x 100 [eq.1]
 

Where Cri is initial chrome concentration in the liquor and Crf is the chrome concentration at
time t

Boiling test. The percent shrinkage of the skin was measured by boiling the tanned piece of skin
at 100 oC for 5 min and calculating the difference between the original surface area and the
surface area of the skin after boiling using the formula below. The area of the skin was measured
using the graduation on a ruler by drawing the size of each piece of the skin on a white plastic
[5].
 
%shrinkage = x 100 [eq.2]


Where Ai is initial area of the skin and Af is final area of the skin after boiling for 5 min

Scanning Electron Microscopic (SEM) Analysis. The morphology of the raw and tanned skin
with and without US exposure has been studied with SEM analysis. The above obtained leather
samples were without any additional pretreatment cut into uniform sizes and then gold-coated
using an Edwards sputtering device. The analysis was performed using a Philips XL40 Scanning
Electron Microscope.

Mercury Intrusion Porosimetry (MIP) analysis. The pore area, pore diameter and pore
volume of skin subjected to tanning with and without US have been measured by Mercury
Intrusion Porosimetry (MIP). In the MIP technique, mercury is injected at high pressure through
the pores of the material. The pressure required to force mercury into the pores of the sample is
inversely proportional to the pore sizes in the material (skin) [32]. The leather samples were air
dried at room temperature for 24 h to make them ready for the MIP analysis. Then, the samples
were analyzed using an Autopore IV 9500, Micrometrics, Norcross, GA, MIP instrument. Since
high pressure might damage the skin and might give false results, preliminary MIP analyses were
performed in a range of pressures from 0.54-30, 000 psia (low to high). Throughout these
experiments the maximum pressure before the skin starts to crack was determined to be 3.38
psia. This pressure has then been used for all subsequent experiments.

7
Tensile strength analysis. The quality of the leather to withstand external forces and its
elasticity has been also tested both for the raw pickle with (denoted by raw with US) and without
US (denoted by raw) exposure and for tanned leather with (denoted by US prior or during
tanning) and without US. As a pretreatment, the leather samples were dried at room temperature
for 24 h. Then the samples were tested for their strength by an Instron 4505 (100kN) static
testing machine.

Statistical analysis. The strength and direction of association between US exposure time with
the chrome uptake and shrinkage was tested using Kendalls tau-b test (r) while the significance
of differences in chrome uptake and shrinkage between different US exposure times was
analyzed by Friedman rank tests (X2 and p value) using SPPS 20. The Kendalls tau-b test values
vary from -1 to 1. In the Kendalls tau-b test, an increase from zero in both direction shows
significance difference between data points while the negative or positive sign shows the
direction of increase or decrease along the data points. A Friedman test is significant when the X2
values is greater than 3.418 (at 95% confidence and 0.5 degree of freedom) and p value is less
than 0.05.

3. Results and discussion

The first experiment which was conducted to choose the optimum value of the tanning
parameters was performed by applying US on the skin for 10-60 minutes before tanning after
which the treated skin was used for the chrome tanning process. The rationale behind is the ease
of manageability and control of parameters of the process when the skin is exposed to US prior
to tanning besides the hypothesis that the US might help opening the pores thus increasing the
diffusion of chromium into the skin afterwards. In a subsequent second experimental series, US
was applied during the tanning process.

3.1 US before tanning

3.1.1 Tanning results
The effects of pH, temperature and exposure time on chrome uptake and shrinkage are shown in
Table 1. The results indicate that the chrome uptake was higher and the shrinkage was lower at
lower pH values than at higher values both for the control and the skin exposed to US before

8
 tanning. The optimal pH appears to be at the value of 3. The chrome uptake was higher and the
shrinkage was lower at lower temperatures compared to higher temperatures, with an optimal
performance at 40 oC. Normally, increasing temperature is known to increase the reaction
between the chrome and the collagen [5]. The relatively lower chrome uptake at 50 oC compared
to the results at 40 oC might be due to the effect of the higher temperature on the nature of the
collagen at an early stage of the process. Before the skin is fully tanned this higher temperature
might shrink the skin due to protein denaturation, such that the pores might be less open for the
chrome to enter the reaction site. The results also indicate that, as the duration of US exposure
increases, the chrome uptake also increases while the shrinkage decreases (X2=12.7, r=0.9,
p<0.05).

The maximum chrome uptake and the lowest percentage of shrinkage were achieved at a pH of
3, a temperature of 40 oC and an US exposure time of 60 min for the skin exposed to US prior to
tanning (Table 1). For the US untreated skin (control), the optimal conditions were also pH 3 and
temperature of 40 oC in which the resulting chromium uptake of 61.4% falls within the common
range (conventional drum tanning) of 60 to 70% [7]. The chrome uptake has increased
significantly by the use of US for 60 min: from 61.4% uptake in the control to 75.2% in the US
treated sample while the leather quality has improved from 5.2% shrinkage in the control to
3.2% in the US treated sample.
Table 1. Effect of US exposure before tanning at different pH, time and temperature (chrome
dose: 8 %; tanning time: 6 h). The optimal values at each US exposure time are in bold.

US exposure pH Temperature (C)

time (min) 30 40 50
% Cr %Shrinkage % Cr %Shrinkage % Cr %Shrinkage
uptake (SD) uptake (SD) uptake (SD)
(SD*) (SD) (SD)
0 2.5 53.4(.14) 9.1(.22) 58.5(.42) 7.3(1.4) 55.4(.84) 8.9(.32)
3.0 54.2(.84) 9.0(1.7) 61.4(.72) 5.2(.62) 60.5(.62) 6.1(1.2)
3.5 50.9(.42) 9.3(1.2) 59.9(.96) 7.2(.42) 58.5(.32) 7.4(.72)
4.0 48.6(1.4) 10.3(.9) 56.9(.44) 10.1(1.2) 55.8(.72) 10.8(.62)
10 2.5 62.2(.14) 6.4(.42) 63.3(1.7) 6.7(.42) 61.2(.72) 6.3(.32)
3.0 62.3(.14) 6.3(.51) 64.0(.52) 6.3(.52) 62.3(.21) 6.2(.14)
3.5 58.2(.17) 7.3(.64) 58.2(.31) 7.2(.86) 58.3(.14) 7.7(.17)
4.0 57.8(1.0) 7.4(1.2) 55.7(.54) 8.2(1.2) 51.3(.62) 8.8(1.0)

9
20 2.5 64.3(1.7) 5.2(.46) 65.3(.84) 5.7(.62) 56.4(1.4) 6.0(1.4)
3.0 66.7(1.3) 5.2(1.4) 67.5(.46) 4.2(.74) 61.5(.42) 6.5(.24)
3.5 63.2(.42) 6.3(.84) 63.8(.12) 6.2(.96) 56.9(.21) 6.2(.72)
4.0 51.4(.28) 7.2(.42) 54.2(.62) 7.3(1.7) 56.8(.96) 8.9(.24)
30 2.5 68.3(.70) 5.7(1.7) 71.1(.24) 5.7(1.4) 56.2(.42) 6.1(.96)
3.0 71.1(.84) 4.7(.84) 73.3(.82) 3.5(1.4) 68.4(1.4) 5.2(.62)
3.5 66.2(1.7) 5.3(.64) 71.8(.1.2) 5.4(.64) 60.4(.32) 6.4(.42)
4.0 60.7(1.4) 6.5(.72) 60.3(.17) 6.3(.24) 58.0(1.7) 6.3(.84)
60 2.5 72.2(.70) 4.6(.48) 73.2(.42) 4.2(.42) 64.9(.64) 5.8(.68)
3.0 74.1(.84) 4.5(1.7) 75.2(.34) 3.2(1.4) 68.5(.96) 5.2(.24)
3.5 71.7(.78) 4.5(.72) 72.1(.52) 4.2(.88) 65.2(.46) 5.8(1.7)
4.0 68.9(.14) 5.5(.48) 66.3(.42) 5.2(.62) 63.1(.42) 6.3(.94)
* Values in parenthesis are the standard deviation (SD) on the basis of three
measurements

Chromium sulfate dose. The effect of prior exposure of the skin to US on chromium sulfate
dose (at a pH of 3, a temperature of 40 C and tanning length of 6h) on chrome uptake is shown
in Figure 2. The skin exposed for 20 min to US before tanning achieves a 60.4% chrome uptake
with only 7% chrome dose (% based on skin weight) which the control reaches at an 8% chrome
dose. Similarly, the skin treated with US for 30 and 60 minutes reaches the normal 60-61%
chrome uptake with 3% less chrome dose compared to the control (without US).

By exposing the skin to US before tanning for 30 and 60 minutes it is possible to produce the
same quality leather with only 5% (3% less) dose of chromium (60.3-61.5% chromium uptake
and 4.9-5% shrinkage ) compared to the conventional tanning (61.4% chromium uptake and
5.2% shrinkage at 8% dose and 6 h of tanning).

Figure 2. Effect of prior exposure of the skin to US on chrome dose (pH 3; 40 oC; 6 h tanning
time). [solid lines: %chrome uptake, dotted lines: %shrinkage]

Tanning time. The effect of exposure of the skin to US before tanning on the required tanning
duration (at a pH of 3, a tanning temperature of 40 C and a chrome dose of 8%) is shown in
Figure 3. Measurements were done on the skin exposed to US prior to tanning for 20 to 60 min

10
and skin without US (control). The results indicate that it is possible to achieve a relatively better
chrome uptake than the control (61.4% uptake at 6 h tanning time) by exposing the skin to US
for 20 min, 30 min and 60 min with only 5 h, 4 h and 3 h of tanning time length, respectively
(X2=15, r=1, p<0.02).

Similarly, the percent shrinkage of the skin shows an improvement when the skin was treated
with US. Prior US treatment of the skin helps to produce a leather which has approximately the
same shrinkage (5.2%) as the control (without US treatment) with 1 h less tanning time for the
skin exposed for 20 min, with 2 h less tanning time for the skin exposed to US for 30 min and
with 3 h less tanning time for the skin exposed for 60 min (X2=13.75, r=-0.9, p<0.03). In the
same line, it is possible to achieve a much better quality leather product compared to the
conventional tanning by increasing the tanning time within 3-6 h and by exposing the skin for 60
minutes to US prior to tanning.

Figure 3. Effect of prior exposure of skin to US on the length of tanning time (pH 3; 40 oC;
chromium sulfate 8%). [solid lines: %chrome uptake, dotted lines: %shrinkage]

3.1.2 Discussion

SEM analysis. A morphological study on the effect of US exposure on the surface of the skin
ready for tanning has been performed using SEM analysis. Photographs of the surface of US
treated (60 minutes) and untreated skins are shown in Figure 4. The photographs show that the
surface of the skin has become smoother due to US treatment. In addition to the SEM analysis,
visual observation also revealed distinct differences between dried US treated and untreated
skins. The skin that was not treated with US is whitish opaque and flexible while the skin treated
with US (without chrome tanning) became translucent, hard and very brittle when fully dried.

Figure 4. SEM analysis of skin surface (a) without or (b) with US treatment.
Diffusion parameter analysis. The pore size and pore area of the air dried skin with and
without US have been analyzed with MIP. The results from the MIP analysis are given in Table
2. US appears to increase the total pore area of the skin by 66%. Likewise, the median pore

11
diameter increased more than 7 fold by application of US. As indicated by many studies, one of
the effects of US on skin is the expansion of pores in the skin which enhances diffusion
compared to skin that is not exposed to US [1, 28]. However, other studies, especially those
reporting US assisted leather dyeing, indicated that prior exposure of the skin to US causes only
a temporary expansion of the pores [12, 33]. It was, therefore, concluded in these earlier studies
that prior exposure of the skin to US does not improve dye diffusion into the skin matrix.
However, the current study shows that there is a permanent change in the pore size of the skin
which allows better diffusion of chemicals into the skin matrix. This difference in the results
might be due to the fact that the US could have a different effect on the untanned skin ready for
chrome tanning (i.e., this study) and tanned (hydrothermally stable) skin ready for dyeing (i.e.,
previous studies).
Table 2. MIP diffusion parameters for skin with and without US.

Parameters (unit)
Without US With US
Total pore area (m2/g) 1.71 2.84
Median pore diameter (m) 1.51 10.77

3.2 US during tanning

3.2.1 Tanning results
Chromium sulfate dose. The effect of variation in amount of chromium sulfate applied (%
based on skin weight) has been studied by applying US for different time lengths during the
tanning process [Figure 5]. The results indicate a significant increase in chromium uptake both as
the dose of the chromium sulfate increases from 4% to 8% and the length of US exposure time
increases from 20 to 60 minutes in comparison to the control without US (X2=12.8, r=0.9,
p<0.05). The chromium uptake for 4% chromium sulfate dose (minimum administration in the
experiment) is 61-67%, for the US exposure time of 20-60 min. In the same manner, the
chromium uptake for the 8% chromium sulfate dose (the maximum administration in the
experiment) for the US exposure time of 20-60 min lie between 83 and 90%. Therefore, the
difference or increase in chromium uptake from the control for the 4 % chromium sulfate is 17-
24% at US time of 20-60 min, while the difference in chromium uptake from the control for the
8% chromium sulfate addition is 21-29% at the US time of 20-60 min.

12
The results also indicate that, in a similar fashion as the chromium uptake, the shrinkage of the
skin decreases both as the chromium sulfate addition and the US exposure time increase. It is
clear that the same quality leather as in the control (8% chrome dose) can be produced by
exposing the skin for 20 minutes with only 4% chrome dose or better quality leather is obtained
by exposing the skin to US during tanning for 30 and 60 min with 4% chrome. Tanning exposed
to US for 30 and 60 min using a chrome dose from 4-8% can result in a better quality leather
with 1.3-4.4% shrinkage (X2=14.25 r= -1, p<0.05).

Figure 5. Effect of skin exposure to US during tanning on different doses of chromium sulfate
(pH 3; 40 oC; 6h tanning time). [solid lines: %chrome uptake, dotted lines: %shrinkage]

Tanning time. The effect of US during tanning at a varying length of tanning time was
measured by applying US during tanning for 20, 30 and 60 min [Figure 6.]. The overall results
show that as the length of exposure to US during tanning increases, the chromium uptake
increases (X2=12.75 r= 0.75, p<0.05) and the shrinkage decreases (X2=14.25 r= -0.85, p<0.05).
For each length of US exposure time the chromium uptake significantly increases compared to
the control (without US) for all the lengths of tanning times. Almost the same chrome uptake (as
compared to the control) can be reached only at one third of the tanning time taken by the control
(6 h) while producing the same quality leather by using US during tanning for 60 min. It is also
possible to achieve a higher chromium uptake (89.8%) and higher quality leather (1.3%
shrinkage) by increasing the time from 2 h while exposing the tanning process to US for 30 and
60 min.

By using only half of the chromium dose that the conventional tanning process consumes (4%
instead of 8%), it is possible to produce a better quality leather product by exposing the skin for
60 min US during the 6 h of tanning process. Alternatively, by applying US for 60 min, it is
possible to complete the tanning process in one third of the conventional tanning time, keeping
the 8% chromium sulfate dosage.

Figure 6. Effect of skin exposure to US during tanning on lengths of tanning time (pH 3; 40 oC; 8
% chromium sulfate). [solid lines: %chrome uptake, dotted lines: %shrinkage]

13
Extended US exposure. For validation of the results obtained, the tanning process was also
exposed to US for longer durations during tanning. When the skin was exposed to US during the
tanning process for 90 and 120 minutes, compared to the tanning exposed for 60 minutes, there is
no significant improvement both in the chrome uptake and the shrinkage. Only a 0.3% chrome
uptake improvement was achieved by increasing the US exposure time from 60 to 90 minutes
while there was no further improvement measured above 90 minutes. The same way, the
shrinkage did not change significantly between 60, 90 and 120 minutes of US exposure during
tanning.

Table 3. Effect of extended US exposure at Table 4. Effect of extended US exposure at

different chrome doses. different tanning time.

Chrome US exposure time Tanning US exposure time

dose (%) 90 minutes 120 minutes time (h) 90 minutes 120 minutes
4 68.9 5.5 69.1 5.3 2 69.1 5.3 70.2 5.2
5 79.4 4.3 80.2 4 3 79.2 4.1 79.8 4.3
6 87.4 3.5 87.8 3.5 4 86.2 3.8 86.4 3.8
7 88.8 3.2 89 3.1 5 89.9 3.1 90.1 3.1
8 90.2 2.9 90.2 2.9 6 90.2 2.9 90.2 2.9

3.2.2 Discussion
From the results above it is clear that application of US during tanning shows much better results
compared to the skin tanned with US treatment prior to tanning. For the skin treated with US for
60 minutes the percentage chromium uptake increased from 57.2% for the prior exposure to
66.7% in the sonicated tanning experiment for the lowest chromium sulfate dose (4% by weight)
while it increases from 75.2 to 89.8 % for the highest chromium sulfate dose (8% by weight),
respectively.

Difference in results of US before and during tanning. The difference in efficiencies of the
prior exposure and exposure during tanning can be explained as follows. When a liquid is
irradiated by US, micro-bubbles (so called cavitations) can appear, grow and collapse violently.
Near a solid surface, these cavitations will implode asymmetrically, which generates micro-jets
towards the solid surface. These micro-jets enlarge the pores in the skin and, thereby, facilitate
the diffusion process. The pore size increase is corroborated by the MIP measurements on the
14
skin, which is sonicated before tanning. When US is applied during the tanning process, the local
temperature increase together with the low pH (3) of the tanning bath causes swelling of the skin.
As the swelling of the skin increases, the pore sizes also increase. Moreover, the bubbles created
in the liquid (tanning bath) collapsing near the surface of the skin generate shockwaves and
micro-jets. Then the micro-jets and shockwaves drive the chrome through the wider pores and
facilitate the mass transfer of chrome from the liquid to the skin [34]. When US is applied prior
to the tanning, the facilitated mass transfer cannot be exploited.

Resulting leather quality assessment. Finally, for a tanning process to be efficient, the quality
of the leather product has to be examined. The results above confirm that use of US during
tanning extremely improved the quality which is proved by the hydrothermal stability (through
the boiling test results). In addition to this, the elasticity of the resulting leathers is another
common quality indicator. To this end, the elongation at break of the different samples is
compared. As can be inferred from Table 5, the leather tanned with US during tanning can be
elongated the furthest, confirming its highest elasticity which might be due to the higher number
of carboxylic groups of the collagen that have formed complexes with the chrome species. As
expected, the percentage of elongation increases with decreasing tensile strength.

Table 5. Tensile strength measurements.

Sample Ultimate tensile Elongation at break (%)

strength [Mpa]
Raw 27.07 35.64
Tanned without US 10.20 82.72
Raw with US 48.23 16.05
Tanned with prior US 7.47 111.55
Tanned with US 2.24 122.41

Finally, the pictures of the SEM analysis in Figure 7 show that the folded pattern and the upper
grain surface of the leather are similar for all tested skins samples. This shows that, there is no
significant change in the outer morphology and fiber structure of the leather due to the use of
ultrasound. However, the pore spaces appear to be more filled in the skin which was sonicated
during tanning, which might be due to the fact that more chromium has reacted with the carboxyl
groups of the skin.
15
Figure 7. SEM analysis of grain surface of tanned leather (a) without US, (b) with US prior to
tanning and (c) with US during tanning.

Economic view. Some studies have been conducted indicating the potential of ultrasound to be
scaled up to industrial implementation [19, 35-37]. With a proper choice of operation and design
parameters it could be an economic and environmentally friendly alternative for the conventional
leather tanning process. Although detailed studies still have to be done, a preliminary
investigation shows that the amount of money saved by using less chrome and shortening the
process time, can compensate the electrical energy and the ultrasound equipment cost. Moreover,
additional benefit can be gained from the reduction of the cost of wastewater treatment because
less chromium is passed through the liquor after tanning. Therefore, the cost of the reduced
environmental pollution and associated risks is expected to make the entire ultrasound assisted
chrome tanning more cost effective [34]. A detailed cost-benefit analysis is currently being
performed and will be reported in due course.

4 Conclusion
In chrome tanning, application of US on the skin before tanning as well as during tanning have
significant positive effects on the chromium uptake and the shrinkage of the skin. However, it is
clear that application of US during tanning gives the best result. With application of US to the
skin during tanning for 60 minute at a pH of 3 and temperature of 40 oC, it is possible to achieve
the same chromium uptake and skin shrinkage only with 4 % chromium sulfate dose compared
to 8 % when using no US. One can also choose to decrease the required time of tanning by
applying 60 min of US during tanning: compared to no US treatment the tanning time can be
decreased from 6 h to 2 h.

Acknowledgements

The authors would like to acknowledge VLIR-UOS (IUC-JU), which is a partnership program
between Belgian Universities and Jimma University in Ethiopia, for the financial support of the
project. The authors would also like to thank Christine Wouters, Rafael Santos, Patricia Elsen
and Bart Pelgrims (KU Leuven, Belgium) for their help in the FTIR, SEM, MIP and tensile

16
strength measurements, respectively. Finally, the authors also acknowledge Soda Sanayii A.
(Turkey) and BUCKMAN (Belgium) companies for offering chemicals for the experiments and
Modjo tannery (Ethiopia) for the permission to work on their process and for providing pre-
tanned skins to perform experiments on.

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Ultrasound assisted chrome tanning: towards a clean leather production technology

Highlights

Lower chrome requirement, shorter tanning time needed or better quality obtained by the
use of ultrasound

By using ultrasound a lower environmental impact is achieved in terms of chromium
dissipation and subsequent required waste(water) treatment

Optimum process parameters for efficient leather production using ultrasound are
determined

27