Volume 101 Page 260

An Eco-Benign Semi-Metal Tanning System for

Cleaner Leather Production
Department of Applied Ecology, Technologies of Polymers and Chemical Fibers, Kiev National University of
V. PLAVAN1*, M. KOLIADA1 and V. VALEIKA2
1

Technologies and Design, 2, Nemirovich-Danchenko str., Kiev 01011, Ukraine

2
Department of Organic Technology, Kaunas University of Technology,
73, K. Donelaicio str., Kaunas LT-44029, Lithuania

Abstract
In this study we developed a semi-industrial-scale tanning process to replace chrome tanning in
the production of high quality prosthetic leathers, based on a multi-step vegetable-aluminium tannage.
Tara and mimosa tannins were used as vegetable tanning agents in order to obtain a wet-white tanned
leather; a pretannage with glutaraldehyde or a preparation based on masked multi-functional
phosphonium compound (THPS) were introduced to improve penetration of tannins. The treatment of
pelt with THPS instead of chromium before vegetable-aluminium tanning allows it to reach a shrinkage
temperature of up to 106°C by using half as much tannin. The liquid wastes of the phosphonium
compounds and the tanning vegetable-aluminium solution are capable of biodegradation to the level
of some proteins, which is evidenced by the ratio BOD:COD. Besides, the absence of chromium
compounds in the liquid waste improves the biodegradation of the other substances. It was determined
that leather treatment with glutaraldehyde or phosphonium compounds positively influences the
leatherʼs ageing resistance. The leather tanned with tara tannins has more stable properties than the
others assessed. The extra stability is likely to be due to mechanism of tanning process. Peculiarities
of interaction between vegetable tannins and collagen were studied by IR-spectroscopy. The influence
of pretreatment by different compounds before tanning on the thermal properties of derma collagen
was studied by DTA and DSC.

INTRODUCTION case. The use of glutaraldehyde and its derivatives

combining with vegetable tannins could be seen as an
During the last 20 years new tanning methods,
alternative to chromium tanning.3 Also it is known that
which avoid the application of possibly toxic chromium
glutaraldehyde has high antimicrobial properties.12 It
compounds, were developed.1 Researchers
has been reported that THPS could be used as a
throughout the world are looking for alternative tanning
chrome free tanning agent13,14 and improved
systems to overcome the problems of chromium
hydrothermal stability was observed when THPS was
tanning. Well-documented mineral tannages, like
used in combination with other tanning agents.15 This
aluminium,2 silicon,3 titanium,4 iron5,6 or zirconium
preparation has such advantages as fine tanning
salts.7 The hydrothermal stability of the leather-tanned
properties, low toxicity, high biodegradability and
using these tanning materials is lower than that of
absence of metals.16 A further environmental benefit is
chrome-tanned leather. Pure vegetable tannages are
that THPS is rapidly oxidised, in the environment, to
thus not suitable as chrome replacements, whilst
trihydroxymethylphosphine oxide which has a very low
combination tannages employing vegetable tannins
aquatic toxicity.17
and metal salts are potential alternatives to chrome
The aim of the research is development of
tanning, capable of producing hydrothermally stable
chromium-free tanning technology providing produce
leathers.8-10 Despite the fact that such a tanning
of leather with high hydrothermal stability and with
method enables chromium compounds to be avoided,
more stable physical-mechanical properties during
it does not mean that the leather obtained would be
long time.
inorganic salt-free. Due to the requirements, which
continually become stricter for leather, especially
MATERIALS AND METHODS
medical leathers, and for recycling of leather wastes,
the manufacture of inorganic salt free leather becomes
Materials
very important. The method of organic tanning using
aldehydes or phosphonium compounds (THPS) either The laboratory scale investigations were conducted
separately or together11 with synthetic and vegetable on skin pieces (12 x 15cm), which were taken from
tannins, should be the most suitable alternative in such wet-salted sheepskins prepared under conventional

* Corresponding authors: E-mail: plavan.vp@knutg.com.ua

260
technology. The samples for the experiments from the
back and butt sections of sheepskins were used.
Chemical materials used for leather processing were
of commercial grade: chromium compounds
(Chromotel XGS, Russia) having basicity 33% and
26% Cr2O3; tara tannins (Chemitan TA, PP Chemipol
Sp. Z.O.O., Poland); mimosa Acasia Molisima
(commercial name Weibull, Tanac S. A., Brasil); THPS
(commercial name Granofin FCC, Clariant,
Switzerland). Other materials, which are conventionally
used in leather industry, were provided from a tannery
Joint-Stock Company Chinbar (Ukraine). The chemical
materials used for the analysis were of analytical grade.
Physical and chemical testing of leather
The shrinkage temperature (Ts) was measured with
a special instrument. Strength indexes of leather
(tensile strength, relative elongation), and chemical
indexes: pH, matter soluble in dichloromethane and
amount of Cr2O3 in the leather were determined using
conventional methods (A2. Standard ISO 3376:2002.
Leather – Physical and mechanical tests –
Determination of tensile strength and percentage
extension. A3. Standard ISO 4045:2008. Leather –
Chemical tests – Determination of pH. A4. Standard
ISO 4048:1977. Leather – Determination of matter
soluble in dichloromethane. A5. Standard ISO 5398-
1:2007. Leather – Chemical determination of chromic
oxide content – Part 1: Quantification by titration.) The
total content of matter extractable by water was
determined according to described method.18
The method of determination of hydrothermal
stability is based on comparison of tensile strength
properties of leather that was kept long time in water
at various conditions.
The procedure of sample preparation for the test is
as follows: samples -as for tensile strength test are cut
from leather. Part of samples is kept for 18 hours in
distilled water at 20 ± 3°C. After that, the samples after
removal of excess water are tested. Other samples are
kept 1 hour in distilled water at 20 ± 3°C, 6 hours at
60°C and 0.5 hour again at 20 ± 3°C. After water
excess removal the tensile strength test is carried out
on the samples. The hygrothermal stability is
expressed in percents as ratio of tensile strength
values of leather kept in hot water and of leather kept
in cold water.
IR-spectroscopy. IR-spectroscopy was employed to
investigate the nature of interaction between the
tannins and collagen. As a model of collagen, gelatin
films with a thickness of 20µm were used. To produce
the films, tannin solutions with a concentration of 50g/l
were introduced into a 4% acetic acid solution of gelatin
at 35°C. The tannin consumption was 10% of the
collagen mass. The obtained solution was poured onto
a polytetrafluoroethylene tray and dried until a film is
formed at 20-22°C. IR absorption spectra were
recorded using FT-IR spectrometer Tensor-37 (Bruker,
Germany).
Thermogravimetric and differential thermal analysis.
Thermogravimetric (TG) and differential thermal
analysis (DTA) and were carried out by using the
Paulig-Erdei derivatograph over the 22-760°C
temperature range in the air with simultaneous removal
of destruction products. Temperature intervals of the
destruction of the samples under study were evaluated
in terms of differentiation curves of mass loss. The
initial (Tstart) and final (Tfin) temperatures for the
destruction were found as well as the maximum
destruction rate temperature (DTGmaxima) and the
change in the mass of samples at this rate.
Processing procedure
The pieces of wet-salted sheepskins in either the
delimed or pickled stage were processed by
conventional technology.
Subsequent processes for the experimental samples
were carried out varying methods of treatment before
tanning and tanning. Amounts of materials used are
presented in % based on limed pelt weight.
Treatment before tanning of delimed samples
according to variants 1 and 2: H2O 100%, temperature
18-22°C, NaCl 5-6%, run 15 minutes, formic acid 0.8-
1.2%, run 2-2.5 hours, glutaraldehyde 4%, run 2 hours,
neutralized by H2SO4 down to pH7-8 sodium metasilicate
1% (calculated as SiO2), run 2 hours, draining.
Treatment before tanning of pickled samples
according to variants 3 and 4: H2O 100%, temperature
18-22°C, THPS 2.5%, run 2 hours, NaHCO3 1-1.5%,
run 1.5 hours.The final pH of solution is 5.2-5.5.
Vegetable tanning stage was executed preparing a
fresh bath (variants 1 and 2), or in the bath of the
treatment before tanning (variants 3 and 4): H2O up to
200% (including volume of 100g/l tannins solution),
temperature 18-22°C, mimosa (1 and 3 variant) or tara
(2 and 4 variant) tannins 10%, run 17-18 hours, formic
acid 0.2%, run 2 hours (the final pH of solution is 3.5-
3.7), draining.
Aluminium tanning stage was carried out in the same
way for all experimental samples: 100% H2O,
temperature 18-22°C, KAl(SO4)2 2% (calculated as
Al2O3), run 2 hours, NaHCO3-1.5-2.0, run 1.5 hours.
The final pH of solution is 3.8-4. After that, washing, fat-
liquoring and drying were carried out for the
experimental samples.
Control samples were processed up to tanning in the
same way as the experimental samples. Further, they
were tanned according to the conventional technology
of leather for prosthetic use. This technology provides
chroming with chromium compounds (0.5% Cr2O3),
treatment with an emulsion of fatliquoring materials and
vegetable tanning (10% tannins).
Biodegradation capability. To determine the capacity
of the substances for biodegradation a ratio BOD :
COD was evaluated.
Ageing resistance. The ageing resistance of leather
was determined using an oxidation in the copper ion –
hydrogen peroxide system.19 The leather specimens
were treated with 3% hydrogen peroxide solution
containing 5-10-4 copper sulfate for 10 days. After each
treatment the shrinkage temperature of the leather was
determined.
261
 Resistance to perspiration. The method involves a 24-
hour treatment of leather at 40°C with artificial sweat
solution of the following composition (g/l): sodium
chloride 20; ammonium carbonate 0.8; disodium
phosphate 0.2; urea 24. Two parallel samples are used
for analysis. One of them is treated with artificial sweat
for 24 hours, of which 8 hours are at 40°C and then 16
h is under normal conditions. Then the sample is taken
from the solution and dried for 24 hours, of which 8 hours
are in a drying apparatus at 40°C and 16 hours under
normal conditions. The control sample is treated in the
same way but using distilled water. Such treatment is
repeated 6 times. After that the shrinkage temperatures
of the samples are determined and compared.
RESULTS AND DISCUSSION
The assessment of chrome-free tanning methods
were conducted estimating qualitative indexes of
processed leather (Table I). The organoleptic analysis
showed that the leather treated before tanning with
both THPS and glutaraldehyde had a fine grain without
cracks.
The treatment of pelt with THPS (3 and 4 variants)
instead of chromium before vegetable-aluminium
tanning allows it to reach a shrinkage temperature of
up to 106°C and leads to practically complete
exhaustion of tannins. It is evident that the tanning
enhances leatherís structure, but, on the other hand, it
can influence the calculated value of strength limit of
leather because the calculation result depends on
thickness of the specimen. In the case of tanning after
treatment with THPS, the thickness of leather
increased due to full exhaustion of tannins and filling
of dermis. So, it can be the reason why the tensile
strength values of the leather treated with THPS were
lower in comparison with the leather produced using
glutaraldehyde (1 and 2 variants). On the other hand,
tensile strength of the leather treated with THPS was
not less than that of the control one.
The pH of the experimental leather was higher
(pH5.5-6.1) compared with the control specimen
(pH4.2), which points to less acid in the dermis. Further,
this property would have an influence on the durability
of such leather in store or in wear.
The treatment of leather with phosphonium
compounds (3 and 4 variants) promotes high
resistance to ageing and perspiration. An analysis of
TABLE I
Physical tests results of prosthetic leather
Variants Vegetable Tensile Relative
tannin strength elongation at
(N/mm2) break (%)
1 Mimosa 16.1 80
2 Tara 14.7 100
3 Mimosa 13.2 75
4 Tara 12.7 86
Control Mimosa 12.8 65
262
the results shows that during oxidation the shrinkage
temperature of leather decreases, and it points to
partial detanning of leather. The shrinkage temperature
of leather treated with phosphonium compounds
decreased on the average by 43.5%, which is lower
than that for control sample (47.7%), in contrast to
leather treated with glutaraldehyde, where the
decrease in shrinkage temperature was 51.2%.
The comparison of the effect of tannin choice shows
that, when treated with phosphonium compounds or
glutaraldehyde and tanned with tara tannins (2 and 4
variants) leather has more stable properties over time.
The authors think that the mechanism of tanning is
accounted for by these properties. The vegetable tannins
mimosa and tara are different in their chemical structure.
Unlike mimosa tannins, tara tannins have carboxyl
groups in their structure.20-22 As is seen in the Figure 2,
the differences in the spectra of the two films are
observed in the low-frequency region (1500-600 cm-1).
In the spectrum of the gelatin film treated with tara
tannins there appear two pronounced bands: 1) with a
frequency of 1360cm-1 (overtone at 1700cm-1), which
is likely to correspond to the hydrogen bond between
in-plane deformation vibrations of the -OH group and
valence vibrations of the CO group (1300-1200cm-1),
where the shift to the low-frequency region may be due
to stronger hydrogen bonds, and 2) with a frequency
of 1230-1200cm-1, which may correspond to
asymmetric valence vibrations of =C-O- in aromatic
compounds or to valence vibrations of the C-O(H)
bond. In the absorption spectrum of the gelatin film
treated with tara tannin there appears a band at 770cm-1,
which is characteristic of ring-puckering deformation
vibrations of the C-H group of aromatic ring having 4
to 5 adjacent hydrogen atoms, and there disappears
the band at 970cm-1, which can be found in the
spectrum of the gelatin film treated with mimosa
tannins and is likely to correspond to in-plane
deformation vibrations of the C-H bond of aromatic ring.
Besides, in the spectrum of the gelatin film treated with
tara tannins there is no absorption band at 1160cm-1, in
contrast to the spectrum of the gelatin film treated with
mimosa tannins. Thus, interaction of mimosa as such
pyrocatechin vegetable tannin takes place in formation
of hydrogen bonds between phenolic hydroxyl groups
of tannins and amine groups of derma collagen.
Interaction of tara tannins, which belong to the
pyrogallol class, proceeds through both forming
pH of Ts Decrease Ts of leather (%)
leather (°С) After treatment by After oxidation
artificial sweat during 10 days
100 5.8 19.6 54.2
96 5.5 16.6 47.1
105 6.1 7.4 46.2
106 5.8 5.5 39.3
94 4.2 10.1 47.7
hydrogen bonds between phenolic hydroxyl groups of TABLE III
tannins and amine groups of derma collagen and Thermodynamic features for melting process of collagen
forming co-ordination, ionic bonds between carboxyl by DSC methods
groups of tannins and functional groups of derma
collagen. Variants Тmax °K Cpmax, ∆Н, kJ/kg
Thermo-oxidative destruction of leather after tanning kJ × K-1 × kg-1
has been studied for evaluation of structural
transformation of dermis collagen. Results of the study 1 393…403 7.14…7.28 352.8
affirm that organic-mineral tanning provides the 2 393…398 10.83…1.75 508.8
formation of a thermostable system of tanning agents 3 403 8.27 469.8
in the structure of dermal collagen as evidenced by a 4 398 11.26 583.1
high temperature of maximum decomposition rate Control 403 6.77 281.3
(Table II).
The relation between thermal characteristics of has been found which allows one to determine the
samples both in quantity and composition of tannages degree of structuring for the tanning of dermal collagen
with the various tanning materials and to evaluate the
TABLE II efficiency of the tanning process. The use of
The results of thermooxidation destruction for samples glutaraldehyde or phosphonium compounds instead of
of leather chromium compounds for the preparation of hide to
vegetable-aluminium tanning gives a more ordered
Variants Tstart°С Tfin, °С DTGmaxima °С ∆m Tmax %
structure of dermal collagen due to formation of cross-
1 58 680 313 38.1 linking and, foremost covalent bonds in the interstitial
2 55 719 306 34.4 space. A less heterogeneous, i.e. more homogeneous
3 70 730 316 34.8 structure of dermal collagen forms during tanning with
4 55 655 321 38.7 mimosa tannins after pretreatment of hide with
Control 62 680 317 32.3 glutaraldehyde owing to spatial dimer, trimer and
polymer structures produced due to interaction

Figure 2. Microstructure of leather after tanning by different methods: 1) glutaraldehyde –mimosa; 2) THPS–mimosa;
3) conventional method of vegetable tanning.

Figure 1. IR spectrum of collagen films before and after treatment with tannins.

263
between glutaraldehyde and dermal collagen. A lower
melting temperature and, at the same time, higher
melting enthalpy ∆H of dermal collagen (Table III)
points to the presence of flexible mobile bonds
produced due to the modification of collagen with
organic compounds in tanning with tara tannins.
The pretanning of leather with glutaraldehyde or
phosphonium compounds before vegetable tanning
helps towards their steady diffusion into the dermis
which gives a microstructure with uniform, moderately
dense arrangement of quite full bundles of collagen
fibres with a densely ʻsewedʼ papillary layer and grain
(Fig. 2). Due to this, the leather gains improved quality.
The microstructure of dermis in the control sample
reveals a very dense arrangement of collagen fibre
bundles, the bundles being thin and without distinct
contours. There is also observed a distinct boundary
between the layers of dermis which is characteristic for
many types of sheepskin and can lead to exfoliation of
leather when exploited. Such peculiarities of the dermal
microstructure in the experimental and control samples
absolutely correspond to their elastic properties and
organoleptic estimation.
TABLE IV
Physical-chemical properties for leather of non-chromium
method of tanning on pilot-scale
Qualitative indexes Developed Conventional
of leather technology technology
Shrinkage temperature °С 98 98
Tensile strength, N/mm2 18.2 20
Relative elongation 42 25
at break,%
рН of tanned leather 5.0 4.5
Content in the leather %
– matter soluble in 8.5 9.8
dichloromethane
– washable by water substances 3.4 4.0
– chromium compounds – 0.9
Hydrothermal stability % 70.8 75.0
The recipes developed were examined on a semi-
industrial scale aiming to confirm the high hydrothermal
stability obtained in the laboratory scale tests. The
semi-industrial scale trials were conducted using wet-
salted cow hides (thickness 2.8-3.0mm). The samples
for the experiments were taken from the back and butt
sections of skin. Processes after pickling: treatment
before tanning and vegetable-aluminium tanning were
carried out according to the method described in
variant 4. Afterward, a conventional fatliquoring and
dyeing were applied in order to obtain the final product
(crust leather) and to evaluate its main physical and
performance properties (Table IV). The obtained values
of the qualitative indexes show that direct application of
the developed method for the processing of heavy hide
was not satisfactory. Independently of the fact that
some indexes of the experimental leather were not
worse or only somewhat less than those of the control
leather, it allows conclusion that this method cannot be
264
directly applied for manufacture of all sorts of skins or
hides.
The wastes of the phosphonium compounds and of
the vegetable-aluminium tanning are capable of
biodegradation, and this is evidenced by the BOD:
COD ratio, which are 0.49 and 0.58 mgO2/l
correspondingly. The ratio BOD:COD is 0.4-0.5 when
conventional technologies are used. The BOD:COD
ratio ≤0.6 evidences that the wastewater can be
purified in the natural way, i.e. by self-purification. This
index is higher when the fraction of organic compounds
in the total content of the used substances is more
abundant. It leads to conclusion that absence of
chromium compounds in the liquid waste improves the
biodegradation of the other materials. Currently the
investigation is being continued developing THPS-
vegetable-aluminium tanning method for other sorts of
skins and hides.
CONCLUSIONS
The treatment of pelt with THPS instead of
chromium before vegetable-aluminium tanning allows
reaching a shrinkage temperature up to 106°C by using
half as much tannin. Leather treatment with both
glutaraldehyde and phosphonium compounds
positively influences the leatherʼs ageing resistance.
The leather tanned with tara tannins has more stable
properties. The wastes of the phosphonium
compounds and of the vegetable-aluminium tanning
are naturally capable of biodegradation. The absence
of chromium compounds in the liquid waste improves
the biodegradation of the other substances. The
technology developed can be used for producing of
prosthetic leather, which requires high exercise stability
as well as sweat resistance.
(Received 2 May 2017)
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