J.

of Supercritical Fluids 66 (2012) 291–296

Contents lists available at SciVerse ScienceDirect

The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Free of water tanning using CO2 as process additive—An overview on the process
development
Renner Manfred ∗ , Weidner Eckhard, Jochems Björn, Geihsler Helmut
Fraunhofer Institute UMSICHT, Osterfelder Str. 3, 46047 Oberhausen, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Leather is a product traded worldwide. The majority of leathers are cattle skins tanned by using
Received 2 November 2011 chromium-III salt, which are in the focus of this work. The article describes the shortening of tanning
Received in revised form 16 January 2012 time by using compressed carbon dioxide as process additive from 30 to 5 h in lab-scale (63 mL auto-
Accepted 16 January 2012
clave). In pilot-scale (20 L autoclave) a tanning process practically free of wastewater is demonstrated.
Compared to conventional processes less chromium-III salt is used and the process time can be reduced to
Keywords:
2.5 h. Some underlying principles for the process intensification caused by carbon dioxide are described.
Free of water
The article concludes with first results from a demonstration plant of technical size with a volume of
Tanning
Animal skin
1700 L, which is able to tan a mass of up to 700 kg (>100 m2 ) per batch in a rotating drum.
Carbon dioxide © 2012 Elsevier B.V. All rights reserved.
Process intensification

1. Introduction energy for 3%. An overall amount of about 14 million m3 of wastew-

Tanning of leather is one of the oldest human technologies. In
100,000 B.C. the utilization of leather and fur allowed the Nean-
derthals to survive in climatically not acceptable regions [1,2]. At
that time the animal hides were conserved by using smoke. Later,
humans chewed fats into the skin. In 2010 a 5500-year-old lace-
up shoe tanned by vegetable tanning agents was found [3]. In 3000
B.C. the Egyptians imported aluminum salts over thousands of kilo-
meters for tanning for example loincloths of priests [4]. In 1858
tanning with chromium salts was developed by Knapp [5]. This
method revolutionized the tanning industry due to the high quality
of chromium tanned leather [6].
Nowadays over 2000 km2 of leather are produced every year. To
produce this amount, about 7 million tons of skin, 500,000 tons of
salt, 500,000 tons of chromium-III salt are needed. The turnover
of leather as an intermediate product is approx. US $45 billion.
Approximately 90% of all leather is tanned by using chromium-
III salt. After China the EU is the second largest producer in the
world. Chinas production capacity has doubled since 1998 and was
613 million m2 in 2006. In 2007 the European tanneries produced
approx. 325 million m2 in 1650 tanneries with 26,000 employees
[7–9].
Leather manufacturing is extremely intensive with respect to
raw materials and work. The raw materials account for 50–70%
of the production costs, wages for 7–15%, chemicals for 10% and
∗ Corresponding author. Tel.: +49 208 8598 1411; fax: +49 208 8598 1424.
E-mail address: manfred.renner@umsicht.fraunhofer.de (R. Manfred).
ater is generated worldwide. According to estimations the costs of
environmental protection measures in European tanneries account
for approx. 5% of their turnover [10].
The high amount of consumables and chemicals used illustrates
the enormous demand for an intensified and environmentally
friendly process. The high consumption of fresh water, mostly
drinking water, and the strong contamination of water strongly
influence on the perception of leather as a “natural product”. The
new process principle described in the following combines advan-
tages of the conventional method, mainly high quality, with the
possibility of considerable savings in process time, chemicals and
water.
The following section provides a brief overview on the most rel-
evant process steps of the conventional tanning process. Tanning
methods can be categorized into three groups regarding the tan-
ning agents. It is possible to tan with metal salts like chromium
and aluminum, vegetable tanning agents like quebracho and tara
and synthetic tanning agents like syntane. During the process the
skin has to be prepared for an optimal absorption of the tanning
agent into the skin prior to cross-bonding between skin collagen
and tanning agent [11–14].
1.1. Conventional tanning process
For conservation purposes, skins are usually salted and dried
for the transport to tanneries or they are transported in chilled
or frozen form. In a tannery, the skins are washed and softened
at the beginning of the production cycle by washing out salt
and adjusting moisture. This so-called softening is carried out at

0896-8446/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2012.01.007
292 R. Manfred et al. / J. of Supercritical Fluids 66 (2012) 291–296
Fig. 1. Chromium complex bound to skin collagen [25].
pH-values of 7–9. In the next step, the liming – i.e. the fatty top
skin – is destroyed and the hair is removed from the skin by adding
lime and sulfur compounds. Proteins are washed out and breaking
of polypeptide groups leads to higher fibre mobility. During lim-
ing collagen is “exposed” and the penetration of tanning agents
into the skin is facilitated. The high alkalinity of the lime (pH > 10)
is strongly reduced for the next working step, the pickling pro-
cess. This is essential because the skin swells at high pH values and
swelling can lead to the destruction of collagen chains. During the
pickle, the skin is prepared for the tanning process at a pH value
of 2.5 (8–20 h). Lime residues are thus neutralized and removed
and the diffusion capability for the tanning agents is increased fur-
ther [15]. The next step is tanning, taking place in rotating tanning
drums over a period of 12–20 h. The skins are brought into intensive
contact with liquid containing a tanning agent, usually a solution
of water and chromium-III salts. During this stage, the pH value is
adjusted from 2.5 at the beginning of the process to 3.8 at the end of
the process [16–18]. This permits optimum penetration of the tan-
ning agent at a low pH value and by steadily raising the pH value the
tanning agent bonds with the reactive groups of the skin collagen,
the carboxyl groups [19,20]. This complexation is shown in Fig. 1.
If chromium interlinks collagen molecules via chemical bonds this
results in a high mechanical strength and cooking stability of the
leather [23]. The tanning can be called successful if 3.8 to 5% of
Cr2 O3 by weight are absorbed in the leather [21]. This concentra-
tion is used as a first criterion, comparatively easy to monitor, to
define high leather quality for trials on laboratory scale [22]. Due to
its color, the intermediate product generated in this step is called
“wet-blue”. Subsequently finishing wet blue with colors, oils and
specific chemicals brings about different forms of appearance like
smooth leather for clothes, stiff leather for shoes or soft leathers for
furniture [17,24].
1.2. CO2 -intensified tanning process
The basic idea of the new process is to carry out the tanning step
under the pressure of CO2 . Limed and pickled skins were provided
by a tannery as a whole or in parts as described in Section 2.2. The
skins were put into contact with either of two tanning solutions
(Section 2.1). For comparison the tanning was performed at ambi-
ent pressure and at elevated pressures in a CO2 -atmosphere in the
equipment described in Section 2.4. In initial experiments, a surplus
of tanning solution was applied, similar to conventional tanning.
The dependency of chromium content and shrinkage temperature
from the time of tanning and pressure was investigated.
In the course of the development an optimized method was
found, where the amount of water was minimized, resulting in a
process practically free of wastewater. For that purpose a part of
the water present in the skin after the pickling step was removed.
This water was replaced by tanning solution 2. The skin thus pre-
treated was introduced into high pressure equipment and treated
under different pressures at varying contact times. The quality was
assessed either by measuring the chromium content and/or shrink-
age temperature.
For both procedures it was found that leather of very high quality
can be obtained at a drastically reduced time of contact by carrying
out the tanning step above a certain pressure of CO2 . Additionally,
wastewater, containing chromium can be reduced to almost zero.
2. Materials and methods
2.1. Tanning solution
Similar to conventional tanning, chromium-III salt was used as
tanning agent for all experiments. The tanning solution consisted
of water, chromium-III salt, salt, formic and sulfuric acid. In the
tanning industry all weights are related to the weight of the wet
skin before the tanning step (example: 150 g water on 100 g wet
skin means 1:1.5).
2.1.1. Tanning solution 1
Tanning solution 1 consisted of 1:10 water, 1:0.09 chromium-
III salt (Baychrom F), 1:0.005 formic acid, 1:0.008 sulfuric acid and
1:0.12 sodium chloride. That means that a mass of wet skin of 1 kg
is contacted with 10 kg of water, 0.09 kg of Baychrom F, 0.005 kg of
formic acid, 0.008 kg of sulfuric acid and 0.12 kg of salt.
2.1.2. Tanning solution 2
Tanning solution 2 consisted of 1:0.3 water (previously removed
from the wet skin), 1:0.05 chromium-III salt (Baychrom F), 1:0.0003
formic acid and 1:0.0003 sulfuric acid. That means that from 1 kg
mass of wet skin a mass of 0.3 kg of water is removed and replaced
by 0.3 kg of water, 0.09 kg of Baychrom F, 0.0003 kg of formic acid
and 0.0003 kg of sulfuric acid.
2.2. Skin
An average cattle skin has a surface area of 7–9 m2 . It is divided
into several parts. The part with the highest quality and the most
regular structure is the so-called “croupon”. The neck (described
in Sections 3.1 and 3.2) and the croupon (described in Section 3.3)
were taken for this work. The neck had a thickness of 2–2.4 mm and
the croupon one of 2.6–3 mm. Both were obtained by splitting the
whole skin with a band knife. The neck was taken as one part per
trial (area of about 0.25 m2 ). The croupon was divided into 5 parts
(with an area of about 0.2 m2 per part). For the experiments shown
in Section 3.3 the parts 1–5 (see Fig. 2) were divided further into 4
equally sized parts.
2.3. Quality assessment
Chromium tanned leather has to be resistant against boil-
ing water without degeneration of the collagenous structure. As
cooking stability is most commonly used in industry, the quality
assessment of wet-blue in this work was carried out by measuring
the shrinkage temperature. This criterion was assessed by using the
equipment shown in Fig. 3. After the tanning process a defined part
 R. Manfred et al. / J. of Supercritical Fluids 66 (2012) 291–296
Fig. 2. Parts of cattle skin.
Fig. 3. Measurement of shrinkage temperature.
of the leather was punched out. This sample was placed firmly with
an interlock on one side of the apparatus. The other side was con-
nected by a yarn using a hook. A weight tightened the system. The
sample was subsequently submerged into water. The water was
heated up until it boiled. When the leather sample shrinked at a
temperature below 100 ◦ C the quality was not sufficient.
2.4. High pressure equipment
2.4.1. 63 mL high pressure view cell
A conventional high pressure cell was used for carrying out the
experiments presented in Fig. 4. The autoclave has a volume of
63 mL and a maximum of 250 ◦ C and 35 MPa could be reached. A
height adjustable magnetic stirrer mounted in the middle of the
Fig. 4. Left: lab-scale equipment; middle: 20 L pilot-scale plant; right: 1700 L demonstration plant.
293
Fig. 5. Reduction of process time using CO2 as process intensifier in lab-scale [26].
horizontal autoclave was used for stirring the tanning solution at a
speed of 40 rpm.
2.4.2. 20 L high pressure tanning bin
The PLC-controlled “pilot-scale plant” was especially build for
high pressure tanning. Inside the horizontal autoclave a rotatable
cage can be used for tanning comparable to industrial procedures.
In order to ensure that the skin moves around continuously inside
the cage some metal pins were screwed in vertically. The motion is
relevant for mass transport and regularity of the chromium distri-
bution. The maximum working parameters were 32 MPa, 80 ◦ C and
20 rpm.
2.4.3. 1700 L high pressure tanning bin
To carry out test series in preindustrial scale a “demonstration
plant” with a volume of 1700 L was build. The autoclave is also
positioned horizontally. A mass of up to 700 kg (>100 m2 leather)
can be tanned per batch in a rotating drum. The design of the drum
is comparable to conventional pressure-less tanning bins. The use
of pins, mounted to the inner side of the rotating drum, intensifies
the motion of the skins and thus a good contact of gas and tanning
agent. The equipment allows the feeding of tanning liquids against
pressures of up to 26 MPa.
3. Results
3.1. Chromium tanning under CO2 -pressure as function of
pressure and contact time
The results demonstrated in Fig. 5 (63 mL autoclave) and Fig. 6
(pilot-scale plant) were carried out comparable to conventional
294 R. Manfred et al. / J. of Supercritical Fluids 66 (2012) 291–296

Fig. 6. Process time using CO2 as process intensifier in pilot-scale. Fig. 7. Process time using CO2 at different pressures in pilot-scale.

Tanning those skins in our equipment without applying gas

processing using an aqueous phase as reservoir for the mass trans-
pressure, results in bad quality (not shown in Fig. 7).
port of chromium ions (tanning solution 1).
For carrying out experiments under pressure, the soaked skin
A detailed description of the processing is given by Renner et al.
was introduced into the pressure vessel and CO2 -pressure was
[26]. Fig. 5 shows the comparison of conventional processing and
built up in some minutes. During the high-pressure process the
processing under the influence of compressed carbon dioxide at
chromium ions diffuse to the reactive sites (carboxyl groups) of
10 MPa. The skin samples had a diameter of 2 cm. Mass ratios
the skin collagen. Fig. 7 shows the influence of pressure and time.
between skin and solution 1 were identical in all experiments. Dur-
The values for 10 MPa were taken from Fig. 6 and are used to com-
ing tanning each skin sample was tanned individually. The samples
pare the results obtained with solution 1 and solution 2. It can be
were wetted by the tanning solution, not submerged.
seen that the tanning time can be further reduced, even at lower
The quality of the leathers produced was assessed using emis-
pressures.
sion spectrometry, by measuring the reduction of the chromium
The trials carried out at 2 MPa of carbon dioxide pressure failed
content of the tanning solution during tanning. With 3 wt% of
to produce high leather quality. A threshold pressure could be iden-
chromium in skin (equal to 4 wt% of Cr2 O3 ) a high quality is reached.
tified at 3 MPa. At a time of 2 h at 3 MPa and at 5 MPa positive and
A shortening of process time from 30 to 5 h using carbon diox-
negative results were achieved, indicated by overlapping of plus
ide at 10 MPa could be proved. Chromium content and maximum
and minus in Fig. 7. As mentioned in Section 2.2 different parts of
uptake of 3.6 wt% chromium are comparable to industrial values
the skin have been tanned. Some parts were of high quality even
[27,28]. Similar observations in lab-scale have been published by
after 2 h, while others did not reach sufficient cooking stability.
other workgroups [29–31].
At such low times, variations in skin properties (pore distribution,
The results were transferred into pilot-scale. The skin samples
fiber compactness) are of relevance for the tanning results. At con-
weighted about 700–900 g. The tanning sessions were carried out
tact times of 2.5 h and beyond, all parts (either from croupon or
at the same tanning solution to hide mass ratios as in laboratory
neck) were of high quality.
scale. The basket rotation was set to 10 rpm and the hide was pulled
A wastewater reduction of more than 90% was achieved with
continuously through the tanning solution as is done in the conven-
this approach. With a conventional tanning process, approx.
tional process.
1–2 tons of chromium loaded water is generated during the pro-
Tanning sessions that produced high leather quality are shown
duction of one ton of leather. The new method produces less than
in the form of plus signs, and those that produced lower quality
10 kg of wastewater per ton of leather. The amount of chromium-III
in the form of minus signs. Fig. 6 shows that tanning time can be
salt used can be reduced by about 45%, the amount of sulfuric and
shortened to 2.5 h using 20 and 30 MPa and to 3 h using 10 MPa.
formic acid by about 95%.
The main focus of the investigation was on whether the shrinkage
The further reduced process time can be attributed to the greater
criterion of cooking stability was reached or not. It became apparent
surface area available for the diffusion of carbon dioxide. In the
that at 30 MPa, no significant reduction of the tanning time versus
approach applied in lab-scale experiments, lower parts of the hide
10 MPa can be achieved.
were immersed in the tanning solution, while the upper side was in
direct contact with CO2 . The gas could predominantly diffuse into
3.2. Tanning free of chromium contaminated wastewater the skin via the upper side. In pilot-scale, experiments (Fig. 6) with
“free-flowing tanning” solution 1 were performed. In difference to
One of the most important problems of the tanning industry is lab-scale, the skins were moved by means of the rotating drum, thus
the wastewater after the tanning step, which is highly charged with repeatedly exposing both upper and lower side of the skin surface
chromium and salt. The objective of the investigation presented in to CO2 . By this effect, the required contact time for a good quality
this section was the reduction of chemicals and chromium contam- was reduced from 5 h in lab-scale to 3 h in pilot scale. In a second
inated wastewater. The results shown in Fig. 7 were obtained in a approach, no free flowing liquid (tanning solution 2) was present in
modified process. the autoclave. The samples were moved mechanically. Due to the
The skins were partly dewetted mechanically before tanning. lack of free liquid, they have been in continuous contact with the
This removed mass was substituted by tanning solution 2, which gas phase. This method resulted in a further (slight) reduction of
was soaked up into the skin in 30 min. tanning time (3 h to 2.5 h). Even more important than time saving
 R. Manfred et al. / J. of Supercritical Fluids 66 (2012) 291–296
Fig. 8. Leather shrinkage by variation of pressure and time.
is the avoidance of waste water and the reduction of the required
amount of chromium and salt by applying this modified tanning
process.
3.3. Influence of pressure using a minimum of chemicals for
different parts of skin
The aim of this investigation was to identify conditions for the
tanning of all parts of skin with varying cross sections and fiber
compactness. The ratio of masses was calculated as shown in Sec-
tion 2.1.2. For each point in Fig. 8 four samples were produced and
assessed. The average weight of the samples was around 600 g.
A process time of 2 h results in leathers with a shrinkage tem-
perature (TS ) between 86 and 92 ◦ C. For 30 and 4 MPa TS does not
increase above 93 ◦ C at a tanning of 4 h. Using 5 MPa TS can be
increased from 95 to 97 ◦ C at a tanning time between 3 and 6 h.
A shrinkage temperature of 100 ◦ C can be obtained after 2.5 h and
6 MPa for all investigated parts of the skin. All 20 samples showed
cooking stability.
4. Discussion and conclusions
The results demonstrate the effectiveness of tanning, which is
considerably intensified by application of pressurized CO2 . In lab-
scale and pilot-scale tanning time could be shortened by factors
of 3–6 using CO2 as process intensifier at 10 MPa. Trials in pilot-
scale showed that increasing pressure from 10 to 30 MPa has no
significant influence. Regarding the tanning time the mass of the
liquid phase in the autoclave looms large. The larger the area for
the diffusion of compressed carbon dioxide into the skin the shorter
the time needed for tanning is.
In a new approach it was found that a surplus of (free) tan-
ning liquid in the autoclave could be avoided if tanning is carried
out under CO2 -pressure. In that case the tanning time could be
shortened to 2.5–3 h. Furthermore it was found that the pressure
required for obtaining a good quality can be as low as 3 MPa.
Reducing the overall mass of water in the tanning bins requires
an increase of the concentration of chromium salts in the tanning
solution, to achieve a sufficient quality of the leather. Absorbing
water with high chromium content into partly dewetted skins is
resulting in a higher concentration gradient of chromium. Thus
diffusion is accelerated.
Additionally the skin matrix is most likely widened by CO2 .
This behavior was investigated for several complex solids, includ-
ing certain biopolymers [32–37]. Regarding the sizes of chromium
295
polynucleate complexes diffusing into the skin, even a slight widen-
ing has a great influence on penetration. According to Nishad [39],
Covington [40] and Braeumer [41], penetration is not the time lim-
iting step, but most of the process time is taken by the diffusion
inside the collagen microfibrils [41]. The chromium complexes have
a size of about 0.75 nm and 1.29 nm [38]. The polynucleate com-
plexes have to diffuse between the fibrils for reaching reactive
binding sites [42]. The gap between the microfibrils is estimated
to be 1.4 nm [43]. The “diffusion tunnels” in the fibrils can take up a
length of several centimeters [44–47]. Having no (free) liquid phase
outside the leather CO2 can penetrate directly over the surface into
the skin. This way the mass transport is influenced positively.
First trials carried out at Fraunhofer UMSICHT using a demon-
stration plant (1700 L autoclave volume) with a rotating drum
showed very promising results. An area of over 100 m2 per batch
can be treated now. It was found that lower pressure than in pilot
scale resulted in very high leather quality, probably because of an
intensified flexing of the material. Flexing is improved from smaller
to bigger skins which, due to their size and shape, are able to twist.
Torsion seems to improve the mass transport of tanning agents
and CO2 . This assumption is confirmed by know-how from con-
ventional tanning [48].
To sum up it can be noted that the newly introduced tanning
process bears a great potential for environmental protection. The
process time for tanning can be considerably reduced. Chromium
contaminated wastewater can be reduced by over 95%. Theoret-
ically, this could result in savings of 14 billion liters per year.
160,000 tons of chromium can be saved per year because now it
is only necessary to use just as much chromium as is needed for
producing high leather quality. Overdosing can be reduced con-
siderably. This reduction of the tanning agent may lead to saving
another 6 billion liters of water which would be necessary for the
production of the chromium.
Acknowledgments
The authors would like to thank the German Ministry of Edu-
cation and Research for the financial support. Furthermore, the
authors would like to thank Helmut Geihsler and the students Jan
Rech, Björn Jochems and Anna Oelbermann for their assistance with
the investigations.
References
[1] E. Delson, K. Harvati, Return of the last Neanderthal, Nature 443 (2006)
762–763.
[2] M. Bolus, R.W. Schmitz, Der Neandertaler, Thorbecke Verlag, Ostfildern, 2006.
[3] Wissensmagazin Scinexx, Springer-Verlags. <http://www.g-o.de/wissen-
aktuell-11777-2010-06-10.html> (accessed 21.03.11).
[4] W. Groenman-van Waateringe, M. Kilian, H. van Londen, The curing of hides
and skins in European prehistory, Antiquity 73 (1999) 884–890.
[5] F. Knapp, Natur und Wesen der Gerberei und des Leders, reprint of the paper
published by Verlag der Cottaschen Buchhandlung, Collegium 1919 (1858)
131–166.
[6] G. Reich, Herstellung und Struktur–Eigenschaftsbeziehungen von Leder, Leder
und Häutemarkt 10 (2002) 31–39.
[7] World Statistical Compendium for Raw Hides and Skins, Food and Agriculture
Organization of the UN, ISBN 978-92-5-005972-3, 2008.
[8] M.L.M. Stoop, Water management of production systems optimised by envi-
ronmentally oriented integral chain management: case study of leather
manufacturing in developing countries, Technovation 23 (2003) 265–278.
[9] A. Shiklomanov, J.C. Rodde, Summary of the monograph world water
resources at the beginning of the 21st century prepared in the framework
of the IHP UNESCO. <http://webworld.unesco.org/water/ihp/db/shiklomanov/
summary/html/summary.html> (accessed 21.04.11).
[10] E. Yigit, B.O. Bitlisli, Study in cost accounting in garment leather, Journal of the
Society of Leather Technologists and Chemists 90 (2006) 68–72.
[11] A.D. Covington, B. Shi, High stability organic tanning using plant polyphenols,
Journal of the Society of Leather Technologists and Chemists 82 (1998) 64–71.
[12] H.R. Tang, R.A. Hancock, A.D. Covington, Complexation between Polyphenols
and Aluminium Salts, Plenum Press, New York, 1992, pp. 437–445.
296 R. Manfred et al. / J. of Supercritical Fluids 66 (2012) 291–296
[13] A.D. Covington, R.L. Sykes, The use of aluminium salts in tanning, The Journal
of the American Leather Chemists Association 79 (1984) 72–93.
[14] E. Heidemann, Fundamentals of Leather Manufacturing, Eduard Roether Verlag,
Darmstadt, 1993, pp. 372–411.
[15] H. Herfeld, A. Zissel, Bibliothek des Leders Band 2: Arbeiten der Wasserwerk-
statt bei der Lederherstellung, Umschau Verlag, Frankfurt, 1990.
[16] K. Faber, Bibliothek des Leders, Band 3: Gerbmittel, Gerbung, Nachgerbung,
Umschau Verlag, Frankfurt, 1990.
[17] G.E. Moog, Der Gerber Handbuch für die Lederherstellung, Ulmer Verlag,
Stuttgart, 2005.
[18] F. Silvestre, C. Rocrelle, L. Rigal, A. Gaset, Optimum conditions for the reactivity
of chromium (III) salts on collagen in the solvent tanning process, J. of Chemical
Technology and Biotechnology 60 (1994) 1–6.
[19] K. Kühn, Struktur und Biochemie des Kollagens, Chemie in unserer Zeit 4 (1974)
97–103.
[20] M.H. Cuq, C. Palevody, M. Delmas, Fundamental study of cross-linking of col-
lagen with chrome tanning agents in traditional and Cr.A.B. processes, J. of the
Society of Leather Technologists and Chemists 83 (1999) 233–238.
[21] B. Brodsky, J.A.M. Ramshaw, The Collagen Triple-Helix Structure, Matrix Biology
15 (1997) 545–554.
[22] A.D. Covington, Chrome tanning: exploding the perceived myths, precon-
ceptions and received wisdoms, The Journal of American Leather Chemists
Association 96 (2001) 467–480.
[23] K.H. Gustavson, The effect of esterification of the carboxyl groups of collagen
upon its combination with chromium compounds, Journal of the American
Chemical Society 74 (1952) 4608–4611.
[24] A.D. Covington, Modern tanning chemistry, Chemical Society Reviews 26
(1997) 111–126.
[25] A.D. Covington, Tanning Chemistry—The Science of Leather, 1st ed., RSC Pub-
lishing, Cambridge, 2009, pp. 212–215.
[26] M. Renner, E. Weidner, G. Brandin, Sustainable and environmentally friendly
production of leather, Chemical Engineering and Transactions 13 (2008)
311–318.
[27] M. Renner, E. Weidner, Prozessintensivierung der Ledergerbung durch
verdichtetes Kohlendioxid, Chemie Ingenieur Technik 9 (2008) 1394–1395.
[28] M. Renner, E. Weidner, G. Brandin, High-pressure carbon dioxide tanning,
Chemical Engineering Research and Design 87 (7) (2009) 987–996.
[29] W. Zhang, Y. Feng, L. Liao, M. Chen, W. Dan, H. Cheng, K. Wang, Z. Li, Chrome
tanning under the condition of supercritical carbon dioxide, Leather Science
and Engineering 13 (2003) 10–13.
[30] W. Zhang, Y. Feng, H. Cheng, L. Liao, M. Chen, W. Dan, K. Wang, Z. Li, Chrome
tanning under the condition of supercritical CO2 Fluid (3): the optimal initial
pH and temperature for SCF-CO2 tanning, Leather Science and Engineering 14
(2004) 8–10.
[31] C. Perre, A.L. Hans, M. Dedieu, O. Gand, L. Saldinari, L. Dutel, From skin to leather
in dense pressurized CO2 , Proceedings International Symposium of Supercrit-
ical Fluids (2003).
[32] R.G. Wissinger, M.E. Paulaitis, Swelling and sorption in polymer–CO2 mixtures
at high pressures, J. Polymer Science and Polymer Physics 25 (1987) 2497.
[33] T.L. Sproule, J.A. Lee, H. Li, J.J. Lannutti, D.L. Tomasko, Bioactive polymer surfaces
via supercritical fluids, J. of Supercritical Fluids 28 (2004) 241–248.
[34] A.R. Berens, G.S. Huvard, Interaction of polymers with near-critical carbon diox-
ide, in: K.P. Johnston, J.M.L. Penninger (Eds.), Supercritical Fluid Science and
Technology, ACS, Washington, DC, 1989, pp. 207–223 (ACS Symposium Series,
406).
[35] O. Muth, Th. Hirth, H. Vogel, Polymer modification by supercritical impregna-
tion, J. Supercritical Fluids 17 (2000) 65–72.
[36] J. Pantoula, J. von Schnitzler, R. Eggers, C. Panayioutou, Sorption and swelling in
glassy polymer/carbon dioxide systems. Part II. Swelling, J. Supercritical Fluids
39 (2007) 426–434.
[37] Y. Zhang, K.K. Gangwani, R.M. Lambert, Sorption and swelling of block copoly-
mers in the presence of supercritical carbon dioxide, J. Supercritical Fluids 11
(1997) 115–134.
[38] T. Ramasami, Approach towards a unified theory for tanning, The Journal of
American Leather Chemists Association 96 (2001) 290.
[39] N.F. Nishad, A. Dhathathreyan, T. Ramasami, Influence of crosslinking agents
on the pore structure of skin colloids and surfaces, Biointerfaces 57 (2007)
118–123.
[40] A.D. Covington, Theory and mechanism of tanning: present thinking and future
implications for industry, Journal of the Society of Leather Technologists and
Chemists 85 (2000) 24–34.
[41] K. Bräumer, Das Faserprotein Kollagen, Die angewandte makromolekulare
Chemie 40/41 (1974) 485–492.
[42] J.W. Smith, Molecular pattern in native collagen, Nature 219 (1968) 157.
[43] A.J. Bailey, N.D. Light, E.D.T. Atkins, Chemical cross-linking restrictions on mod-
els for the molecular organization of the collagen fiber, Nature 288 (1980)
408.
[44] P. Fratzl, Biologische Materialien–dem Bauplan natürlicher Hochleis-
tungswerkstoffe auf der Spur, Physik in unserer Zeit 5 (1999) 196–200.
[45] K. Kühn, Untersuchungen zur Struktur des Kollagens, Die Naturwissenschaften
5 (1967) 101–109.
[46] M.E. Brown, R.L. Dudley, A conformational study of collagen as affected by
tanning procedures, The Journal of American Leather Chemists Association 92
(1997) 225–233.
[47] M. Van der Rest, R. Garrone, Collagen family of proteins, Federation of American
Societies for Experimental Biology (1991) 2814–2823.
[48] G. Reich, From Collagen to Leather—The Theoretical Background, BASF Service
Center, Ludwigshafen, 2007, p. 45.