NANOTECHNOLOGY IN LEATHER INDUSTRY REVIEW:

A NOVEL NANO-SIO2 TANNAGE FOR MAKING CHROME - FREE LEATHER

ASUGUI, Wynna Mae R.(1) CONTRERAS, Veronica Mae T. (2) MANRIQUE, Francois Claire M.(3)

ABSTRACT
Leather industry is an old manufacturing industry that produces a broad range of different goods made of
leather such as bag, shoes, belts, footwear, garments, etc. The common raw materials for leather are
animal skins that will undergo certain chemical treatments. There are several methods that can be used
to transform animal skin into leather, i.e. Chrome tanning which is the most popular, easiest and low-cost
method used worldwide that has become a problem in these days due to its effect to the environment as
well as to humans. In the process of making chromed tanned leather, harmful chemicals are used such
as chromium salts (harmful to humans) and the large amount of waste produced such as the water and
solid waste that contains toxins (harmful to the environment). Due to this problem, nanotechnology takes
place providing a substitute to the chrome tanned leather using a novel pickle less combination tannage
based on nano – SIO2 and oxazolidine producing a chrome – free leather. By the use of Scanning
Electron Microscope, the size and distribution of SIO2 in protein were investigated. The hydrothermal
stability, mechanical properties and the antifungal fungal effect of the final leather as well as eco – friendly
characteristics of the combination tannage were examined. The result shows that the leather tanned
using the oxazolidine – SIO2 shows a higher resistance to mould, a better biodegradability of organic
compound in the effluent and the process flaunt significant reduction to total solid waste compared to the
chrome tanned leather.(1)
Keywords: chrome tanned leather, oxazolidine, nano – SIO2, pickle less combination tannage
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INTRODUCTION understanding, manipulating, and controlling
Chrome tanned leather in the 21st matter at the above-mentioned length, so that
century is ubiquitous worldwide. In every the physical, chemical, and biological
household, it can be easily seen due to its properties of the materials (individual atoms,
usefulness to humans but due to its harmful molecules, and bulk matter) can be
effects and with the enhancement of engineered, synthesized, and altered to
environmental consciousness, researchers develop the next generation of improved
drive to explore and discover products as well materials, devices, structures, and systems. It
as processes to provide the world an is used to produce intended textile
alternative to the popular chrome tanning characteristics such as elevated tensile
system. resistance, distinctive surface structure soft
Nanotechnology is an increasing hand durability, water repellent, flame
interdisciplinary technique that is often seen retardant, antimicrobial properties, and the
as a fresh industrial revolution. It deals with like. With the help of nanotechnology, the
material from 1 to 100 nm in size. We can world can have eco-friendly leather that is
define nanotechnology in textiles as chromium free. Nanoparticles can be a useful
tool in tanning system due to its size and its MATERIALS AND METHODS
ability to combine with polymer substrate. Materials
Introducing nano – SIO2 to a collagen As mentioned earlier, leather is made
fiber being the organic phase and nano – from animal skin. Processed goat skin was
SIO2 as the inorganic phase can produce used in the study. The chemicals all in
better quality of leather due to the strong commercial grade: formic acid, sodium
bonding of organic and inorganic phase. At bicarbonate, sulfuric acid, sodium formate,
the same time, through the use of oxazolidine sodium bicarbonate, Relugan D (BASF),
as the pre – tanning agent increases the Relugan DLE (BASF), Lipoderm liqor
leather shrinkage temperature as well as SLW(BASF), Lipoderm liqor SAF(BASF),
providing greater resistance to chemical CORIPOL MK (TFL) and water. Nano - SIO2
attack of leather.(1) and oxazolidine was prepared.(1)

STATEMENT OF THE PROBLEM Methods

The study aims to develop a novel 1. Optimization of oxazolidine for pre-
combination tannage based on a nano-SiO2 tanning.

and oxazolidine as an alternative for chrome- The goat skin undergone bating

free tanning by answering the following process using 2% of sodium bicarbonate at

questions: (2) pH 4. Meanwhile. oxazolidine, with varying

1. What is the effect of the size and %wt (1wt%, 1.5 wt%, 2 wt%, 2.5 wt%) was

distribution of nano-SiO2 in the leather introduced together with the bated pelt to a

produced? drum for 2 hrs. Then, to adjust the pH from 4

2. What are the characteristics of the to 3.5, 2 wt% of formic acid was added to the

leather produced using nano-SiO2 and drum and it has been kept for an hour.

oxazolidine in terms of:

2.1. Protein content 2. Oxazolidine – nano - SiO2

2.2. Hydrothermal stability combination tanning.

2.3. Mechanical properties The pre - tanned goatskin was first

2.4. Antifungal effect squeezed and shaved. For the nano - SIO2

2.5. Environment Benefit tanning, varying %wt of SIO2 ( 3wt%, 5wt%

and 7wt%) was introduced and drummed for
about 3 -4 hrs. Upon complete penetration of
nano - tanning agent the mixture of 1 wt%
sulfuric acid and 1 wt% formic acid diluted
with 150 wt% water were added to decrease Differential Scanning Calorimeter
the pH from 2.5 to 1.5 hrs. The pre-tanned (DSC) will be used to test the hydrothermal
goatskin is then to be leave overnight in the denature temperature of combination tanning
mixture. Next day, a basification was carried leather.
out by adding 2wt% sodium formate and The leather will be air-dried to an
2wt% sodium bicarbonate (1:10 dilution) in ambient temperature, and is moistened using
four instalments at an interval of 15 min. water for 24 hrs. Then, the excess water is to
Finally, the drum was run for another 2 hrs be removed by pressing the sample lightly
and the pH was checked to be 5.0 - 5.5. using laboratory tissue. Moisture content was
between 60% - 70%. Lastly, seal the sample
3. Conventional chrome tanning and in in a DSC cell and heated at a constant rate
post tanning process. of 5/min. The peak temperatures on DSC
The tanned leather is to be shaved to curve were defined as shrinkage
a uniform thickness of 0.8mm. temperature(℃).
For the post tanning process, the
following is to be done: 5. Mechanical properties test of
● Neutralization using 100 wt% water; 1 leather samples.
wt% sodium formate; 1.25 wt% Test the mechanical properties using
sodium bicarbonate for 1 hr. the standard procedures. Each value
● Washing using 100 wt% of water for reported was an average of four (2 along the
10 mins. backbone, 2 across the backbone)
● Retanning using 100 wt% water; 3 measurements.
wt% Relugan D (BASF) for 30 mins; 2
wt% Relugan DLE (BASF) for another 6. Color measurement.
30 mins. Reflectance measurements were
● Fatliquoring using 4 wt% Lipoderm made for oxazolidine-nano-SiO2 combination
liqor SLW(BASF); 3 wt% Lipoderm tanned leathers by using X-RiteColor 8200
liqor SAF(BASF); 3 wt% CORIPOL Series spectrophotometer,. The L (lightness),
MK (TFL) for 45 mins a (red and green axis where ‘a’ ＞0 means
● Fixing using 2 wt% formic acid for 75
mins. Lastly, pile it overnight. red and ‘a’＜0 means green), b (yellow and

blue axis, where ‘b’ ＞0 means yellow and ‘b’

4. Differential scanning calorimetry
studies.
＜0 means blue) and c (chromaticity) values oxygen demand (COD) with German
Lovibond instrument. Total solids (TS, dried
were calculated.
at 103-105 ℃ for 1 hr) according to the
standard procedures. (1)
7. Scanning Electron Microscopic
analysis
RESULTS AND DISCUSSION
To observe the size and distribution of
1. Optimization of oxazolidine offer
nano-SiO2 , SEM will be used. The
Oxazolidine which was used as the
micrographs of nano-SiO2 on the grain
pre-tanning agent in the study was used to
surface and in the cross -section were
improve the mechanical properties of the
obtained by operating the SEM at low
bated skin of the goat for the squeezing and
vacuum with an accelerating voltage of 20KV
shaving process and more so to change the
in different lower and higher magnification
surface charge for the penetration of nano-
levels.
precursors (tetraethoxy silane, TEOS) before
hydrolysis.
8. The antifungal effect of leather
The result shows that increasing the
tanned with oxazolidine –nano -SiO2
amount of oxazolidine increases the Ts and
To test the antifungal effect of the
the penetration time of nano-SiO2 tanning
samples, the bacterial stains Aspergillusniger,
agent. 2.0% oxazolidine was chosen for
Aspergillus flavus and Paecilomyces Bainier
further experiments.
were selected. The cell density of the culture
was determined by a standard plate count
2. The hydrothermal stability of nano-
method. The cultures were diluted with
SiO2 and oxazolidine combination tanned
sterilized water to give cell density of 100-200
leather
cfu/mL. The samples were placed on the
DSC analysis was used to determine
plates with appropriate Czapek medium
the hydrothermal denature temperatures of
firstly, then 0.1mL cultures was patched on
collagen with and without the presence of
each sample. Finally, the samples were
nano-SiO2.
incubated at 28 for 6 days.
The thermal denature of the collagen
can be explained by the position, width,
9. Analysis of spent tan liquor
height and symmetry of the thermogram
Spent tan liquor from experimental
peak. On the other hand, measuring the
processing was collected and analyzed for
hydrothermal stability of collagens can be
biological oxygen demand (BOD), chemical
done by knowing the shrinkage temperature
of the collagen which is normally related to
the onset temperature of its peak in a DSC 4. Color measurement results
pattern. An increase in the shrinkage The result shows that the color
temperature is usually an indication of an measurement of the combination tanned
increase in the stability of wet collagen. leather is suitable for making pastel shades.
Comparing the known shrinkage
temperature of chrome tanned skin to the 5. The influence of nano-SiO2 content
skin treated with oxazolidine and oxazolidane on the size and distribution of SiO2 in protein
and nano-SiO2 combination, it can be SEM (Scanning Electron Microscopy)
concluded that the hide treated with only was used to study the fiber structure and the
oxazolidine has no obvious endothermic peak size and distribution of SiO2 in protein. The
and the hide’s that treated with the fiber structures obtained from SEM for
combination of oxazolidine and nano-SiO2 chrome tanned leather (more opened
shows endothermic peaks that are similar to structure) and the new combination tanned

chrome tanned leather. 99.6 °C，103.4 °C leather (tight structure) was similar. The
results obtained shows that the size scale of
and 107.1 °C are the shrinkage temperatures
SiO2 particles in final leather is closely
of the final leather reach.
dependent on the content of SiO2.
It is indeed obvious that combination
tannage can efficiently improve the
6. The antifungal effect of the
hydrothermal stability of leathers. The hide
oxazolidine and nano-SiO2 combination
that has a combination tanned of oxazolidine
tanned leather
(2 wt%) and nano-SiO2 (5 wt%) was
In determining the antifungal ability of
assessed further.
the combination tanned leather (subjected to
various fungal) dual plate assay was used.
3. Mechanical properties of leather
The experiment shows that the
tanned with oxazolidine- nano-SiO2
combination tanned leathers which were
The physical strength values of
incubated for 6 days has no mildew, while the
combination tanning are all superior to the
chrome tanned leather which was incubated
stipulated standards of chrome-free leather
for 3 days began to grow mildew and became
and close to the chrome tanned leather.
degraded in 6 days of incubation.
This shows that the hides that treated
with nano-SiO2 demonstrate a higher
resistance to mold than the usual chrome
tanned leather and significantly reduced the the new combination tanned leather
pollution of neutral alt. produced have greatly enhanced and can be
compared to the existing chrome tanned
7. Environment benefit leather properties.
Spent tan liquor analysis was used to
assessed the impact of the combination REFERENCE
tanning system on the environment for TS, Yan Lu, et al. A Novel Nano-SiO2 Tannage for
BOD5 (BOD 5 days later) and COD. Making Chrome-Free Leather.
Result shows that the COD value in
combination tannage is higher than in chrome
tanning while the TS load value for
combination tanning process is lower than
that of the chrome tanning process. This
means that the environmental pollution by
tanning process is avoided by the new
combination tanning system.
On the other hand, the
biodegradability of the organic compound is
commonly evaluated by dividing the value of
BOD5 to the value of COD. If the value
obtained is higher, then it is easier to
biodegrade the organic compound. (2)

CONCLUSION
The researchers were able to develop
a new pickle less combination tannage that is
based on oxazolidine (act as a cross-linking
agent) and nano-SiO2 (acts as a precursor).
The size and distribution of the nano-SiO2
has a great significance for the improvement
of the hydrothermal stability of leathers.
Moreover, characteristics (protein content,
hydrothermal stability, mechanical properties,
anti-fungal effect and environment benefit) of