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Tannins as a sustainable raw material for green chemistry: A review

Article  in  Industrial Crops and Products · October 2018

DOI: 10.1016/j.indcrop.2018.10.034

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 Industrial Crops & Products 126 (2018) 316–332

Contents lists available at ScienceDirect

Industrial Crops & Products

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

Tannins as a sustainable raw material for green chemistry: A review T

a a,⁎ b
Younes Shirmohammadli , Davood Efhamisisi , Antonio Pizzi
a
Department of Wood and Paper Science and Technology, Faculty of Natural Resources, University of Tehran, Karaj, Iran
b
ENSTIB-LERMAB, University of Lorraine, 27 Philippe Seguin, 88026, Epinal, France

A R T I C LE I N FO A B S T R A C T

Keywords: Tannins as herbal extracts are a good alternative for green chemistry. They are found aplenty in some plant
Tannins species and can be extracted by simple methods. The tannins main feature and advantage is their phenolic
Adhesive structure which is very similar to synthetic phenols. Another key feature of tannins is their actions as anti-
Bio-foam oxidants. The use of tannins is often connected to one of these features. They are now actively used in leather
Wood preservative
tanning, adhesive making (especially wood adhesives), fisheries, beverages manufacturing, animal feed and
Furfuryl alcohol
BioSource polyurethane
many others. Considerable amounts of research has also been recently conducted on the possibility of using
tannins in the manufacture of biosourced foams, wood preservatives, corrosion inhibitors, polyurethane surface
coatings, epoxy adhesives, binders for Teflon coatings and etc. This paper deals with different uses of tannins and
with the latest research which has been done on this subject.

1. Introduction as species which contain both kinds of tannins (Mueller-Harvey, 2001;

Although oil-sourced materials became widespread in the past few
decades, they are at present subject to lots of questioning due to the
fluctuating oil price, to problems of reserves depletion, to the pollution
which stems from these, etc. Nowadays, sustainable materials (e.g.
polylactic acid, chitosan, lignin, tannins etc.) are gaining an increasing
importance in order to diminish crude oil consumption and to reduce
human environmental impact (Luckeneder et al., 2016). Among them,
tannins are one of the most interesting materials that can be obtained
from plants. They are natural phenolic structures which are found
abundantly in the bark as well as wood and in a lesser amount in leaves
and fruits of a variety of plant species (Mueller-Harvey, 2001; Schofield
et al., 2001). Tannins role in plants include protection against light (UV
rays and free radicals) and defense in the case of different biological
threats (animals, insects, fungi and bacteria) (Tondi et al., 2013a). They
are also known as protecting agents of some plants from dryness,
through molecular mechanisms, as in the case of the resurrection plants
(Pizzi and Cameron, 1986). Tannins are generally classified into con-
densed and hydrolysable tannins. Hydrolysable tannins are mixtures of
simple phenols (ellagic or gallic acid; Fig. 1) (Aroso et al., 2017). As the
name indicates hydrolysable tannins can be hydrolyzed by weak acids/
bases to produce carbohydrate and phenolic acids.
Some plant species contain either gallotannins or ellagitannins and
some others contain all kinds of hydrolysable and condensed tannins.
For example Acer sp., Acacia sp., and Quercus sp. have been recognized
Ghahri and Pizzi, 2018; Salminen et al., 2004).
Commercial hydrolysable tannins due to their macromolecular
structures, sometime shortened or altered by the extraction techniques
used, their low level of phenol substitution, their low nucleophilicity,
are in limited worldwide supply and have higher price. Thus, they
appear to present a somewhat more limited chemical and economical
interest, although uses in wood adhesives have been reported (Kulvik,
1979; Spina et al., 2013) now that their macromolecular structure is
better known (Pasch and Pizzi, 2002; Giovando et al., 2013; Radebe
et al., 2013; Pizzi et al., 2009). However, hydrolysable tannins are used
extensively in leather processing since they yield leather of excellent
color, clarity and light resistance (Pizzi, 2008). Furthermore, hydro-
lysable tannins act as an antimicrobial and antiviral substance. This
ability is attracting a lot of interest to produce antimicrobial drugs
(Pizzi, 2008; Buzzini et al., 2008). Some of the species from which
hydrolysable tannins can be extracted are alder leaves (Alnus rubra)
(Hagerman and Robbins, 1987), pomegranate peel (Punica granatum L.)
(Chidambara Murthy et al., 2002), chestnut (Castanea sp.) (Hagerman,
2002), myrobolans (tree species of Terminalia phyllantus), tara (Cae-
salpina spinosa) and dividivi (Caesalpina coraria) extracts (Pizzi, 1980).
Hydrolysable tannins are combinations of simple phenols, like pyr-
ogallol and ellagic acid, and of esters of a sugar, primarily glucose along
with gallic and digallic acids (Pizzi, 1994a).
Conversely, condensed tannins constitute more than 90% of the
total world production of commercial tannins (200 000 tons per year)

⁎
Corresponding author.
E-mail address: efhami@ut.ac.ir (D. Efhamisisi).

https://doi.org/10.1016/j.indcrop.2018.10.034
Received 11 June 2018; Received in revised form 9 October 2018; Accepted 10 October 2018
0926-6690/ © 2018 Elsevier B.V. All rights reserved.
Y. Shirmohammadli et al. Industrial Crops & Products 126 (2018) 316–332

Table 1
The yield of tannin extraction from different species by various methods.
No Extraction method Plant species Yield (%) Reference

1 Hot water Pinus pinaster 6 (Vázquez et al.,

Alkaline solution (bark) 15–36 2001)
2 Water at 60 °C Silver fir (bark) 11.6 (Bianchi et al.,
European larch 20.1 2015)
(bark)
Norway spruce 18.2
(bark)
Fig. 1. Schematic representation of a hydrolysable tannins molecule.
Douglas fir 12
(bark)
(Pizzi, 2003a). The main repeating units of condensed tannins (also Scots pine 7.1
(bark)
known as proanthocyanidins or flavonoids) include: catechin and epi-
3 Acidified acetone 70% Beach pea 11.6 (Chavan et al.,
catechin (procyanidins-type tannins), prodelphinidins, profisetinidins Indian grass pea 1.54 2001)
and prorobinetidins (Fig. 2). Some other types also occur such as pro- 4 Water + salt addition Pinus oocarpa ∼39 (Vieira et al.,
pelargonidins (MW (weight average molecular weight): 578.52 g/mol), (bark) 2011)
proteracacinidins (MW: ∼730 g/mol) and proguibourtinidins which 5 Sulphite-water (12-15) or Pine (bark) 12–25 (Sealy-Fisher and
sulphite-water-urea (18- Pizzi, 1992)
are different in the number of hydroxyl groups they carry. 25)
All condensed tannins derive from polyhydroxy-flavan-3-ol oligo- 6 Hot water Pecan (nut pith) 42–43 (Pizzi, 1994a)
mers linked together mostly by CeC bonds between the A rings of the Commercial tannins
flavanol units and the pyran rings of other flavanol units. Moreover-3,4- 7 Hot water Mimosa (bark) 30–33 (Pizzi, 1994a)
Quebracho 26–29
diols, named (leucoanthocyanidin) also can form condensed tannins
(wood)
oligomers (Hemingway and Karchesy, 2012). Pine (bark) 13–15
Based on MALDI-TOF studies it was shown that mimosa tannin is
predominately a prorobinetinidin-type tannin while quebracho tannin
is mainly comprised of profisetinidins (Pasch et al., 2001). However, unprofitable. The extraction yield depends mainly on the plants species
the most potentially abundant tannin extractable throughout the world as well as the type of solvent used or of the additives added to the
are the procyanidins, found for example in pine (Pinus pinaster) trees solvent (Table 1).
bark and in grape skins (Vitis vinifera var. Merlot), which are polymers The most important species that are commercially used to extract
of 2–50 (or more) catechin units joined by CeC bonds. These linkages flavonoid tannins include: the barks of pine (Pinus radiata), oak
are not easily subject to be cleaved by hydrolysis (Schofield et al., 2001; (Quercus sp.) (partially hydrolsable too), mimosa (Acacia mearnsii) or
Shahidi and Naczk, 2003). the quebracho wood (Schinopsis balansae or lorentzii) (Pizzi, 1980;
In another more simple and practical statement, condensed tannins Arbenz and Avérous, 2015). Furthermore, tannins can be obtained as a
can be classified based on their reaction rate, for example quebracho by-product from agricultural wastes such as tea (from various species)
and mimosa tannins are considered as slow reacting tannins in com- (Chowdhury et al., 2016) and coffee (Coffea arabica) (Janissen and
parison with pine and pecan (Carya illinoensis) (faster reacting, pro- Huynh, 2018) as well as fruit residues such as persimmon (Diospyros
cyanidin/prodelphinidin-type) tannins (Pizzi and Stephanou, 1994). sp.) hulls (Sung et al., 2012), grapes (Vitis vinifera) skin (Yilmaz and
The objective of this paper is to show an overview of the current Toledo, 2004; Ricci et al., 2017) and many others (Widsten et al., 2014;
tannins applications in industry and to evaluate their useful features. Dorta et al., 2012; Saad et al., 2012). Recently the potentiality of Eur-
The potential for new applications of tannins as a sustainable raw opean medicinal herbs was also reported as possible resources for
material is also presented. tannin extraction (Maier et al., 2017).
There are various methods for the extraction of tannins, the most
2. Extraction methods important factor in their selection being the final use of extracted
tannins. Other factors which influence on both the quality and quantity
It is possible to extract tannins from different plants. But in most of the extracted tannins are the extraction method, solvent type, time
cases, the extraction efficiency and the percentage yield are low and and temperature of extraction, solvent to solid ratio and particle size of

Fig. 2. The four main structures of flavonoid tannins.

317
Y. Shirmohammadli et al.
Fig. 3. Schematic tannins extraction process to get tannin powders.
the sample (Robards, 2003).
In the first step of extraction, fresh or dried plant parts need to be
processed like grinding, milling etc (Vázquez et al., 2001; Hill et al.,
2003). Traditional methods of tannins extraction usually utilize water
as a solvent, which has lots of advantages like process simplicity, good
effectiveness and wide applicability. Industrial extraction is at present
always done by water extraction containing 1.5%–2% sodium sulphite
or bisulphite plus 0.5% sodium bicarbonate (Sealy-Fisher and Pizzi,
1992). After this, the tannin solution undergoes concentration, spray
drying or vacuum drying to get the tannins powder or solids respec-
tively, according to the drying method used (Fig. 3). Generally, tannins
extraction is performed on the most tannin-bearing plant parts which
differs from species to species (e.g. bark, wood, leaves, seeds etc.).
Choosing which solvents should be used should depend from the
phenolic material which is to be extracted and it can affect the final
quality of the extracted material. For example, acetone has proved
better than water in the extraction of higher molecular weight flavo-
noids (Xu and Chang, 2007).
Tannins are highly polymerized substances and they can be in as-
sociation with other constituents such as carbohydrates. Hence, the
extracted material contain non-phenolic materials too (Pizzi, 1980;
Bianchi et al., 2015) with the carbohydrate either being a separate
fraction (as is usual for commercial extracts) or linked to the flavonoid
chain itself (Drovou et al., 2015). This shows the necessity of having
some post-extraction phases to obtain tannins with higher purity for
certain applications. For example, commercial mimosa tannin extract is
composed of 72%–74% tannin (trimers and higher), 6%–8% flavonoid
monomers and dimers (that strictly speaking are not considered as
tannins), 13.5%–15.5% non-phenolic materials (mainly carbohydrates,
and inorganic compounds), 6.3% moisture, and 0.2% inorganic in-
soluble materials.
Extraction time and temperature are very important factors and
should be controlled precisely in order to reduce the damage to phe-
nolic compounds during the extraction (Spigno et al., 2007). High
temperature causes higher solubility by increasing both solubility and
mass transfer rate. High temperatures also decrease the viscosity and
improve the solvents movement in the matrices. High temperature for
too long a more time causes the oxidation of the phenolic compounds
and results in the yield decrease. Hence, in order to preserve the sta-
bility of the phenolic fraction of the extract, it is very important to
choose the suitable extraction time, temperature, solvent, particle size
etc. The suitable extraction plan can be vary for different plant species.
Some new methods have also been applied for the extraction of
tannins including: microwave, ultrasound-assisted extraction, and
318
Industrial Crops & Products 126 (2018) 316–332
methods based on compressed fluids as extracting agents like subcritical
water, supercritical fluids, pressurized fluids or different solvents (Dai
and Mumper, 2010).
3. Leather tanning industry
Tanning is one of the most important phases in transforming hides
to leather and as its name suggests, it is classically done using tannins.
This process gives strength, softness and resistance against chemicals,
thermal stability, and antimicrobial properties to leather (Kaygusuz
et al., 2018). Chrome tanning is one of the common industrial tanning
processes since it gives soft, light and a versatile leather with good
thermal stability and with an ease of processing which is hard to
achieve with other manufacturing methods (Sreeram and Ramasami,
2003). Conversely, chromium is recognized as being potentially carci-
nogenic and when it is discharged as waste it causes soil contamination
(Mamyrbaev et al., 2015; Tariq et al., 2009). Some of the other pro-
blems with chrome-based tanning includes limits in recovery and reuse
of wastes from leather manufacture and limited available sources, more
pollution, complications in waste treatment, increase in biological
oxygen demand (BOD) as well as chemical oxygen demand (COD) etc
(Tariq et al., 2009; Joseph and Nithya, 2009; Krishnamoorthy et al.,
2013). One of the main challenges that this industry is involved with is
the pollution which stem from chromium consumption (Kanagaraj
et al., 2008). As a result of environmental concerns and new regula-
tions, the leather industry is turning again toward using greener and
cleaner materials and processes instead of using chromium based tan-
ning processes (Onem, 2018). Vegetable tannins are good substitute for
chromium and the combination of these two systems has been con-
sidered as an acceptable cleaner solution (Krishnamoorthy et al., 2013).
Then main protein in animals is collagen, which can be found in
abundance in skin (Madhan et al., 2002). Chromium compounds are
known to react well with collagen and results in permanent changes.
These changes produce a high quality leather from biodegradable hides
(Rosu et al., 2017). Tannin polyphenols are able to create crosslinking
with collagen by numerous hydrogen bonds. Furthermore, the reaction
of tannins with collagen results in a more stable leather (Madhan et al.,
2002). Investigations have proved that a more thermal stable leather is
achievable with vegetable tannins and acrylic polymer (Madhan et al.,
2001).
4. Adhesives and coatings
4.1. Adhesive for the wood industry
Synthetic adhesives (e.g. phenolic and amino resins) which are
being used extensively in the wood industry possess some drawbacks
concerning the emission of carcinogenic formaldehyde, environmental
pollution and price fluctuations. Growing interest to use naturally de-
rived substances in the adhesive industry have emerged and they sug-
gest tannins as one of the more interesting alternatives (Faris et al.,
2016; Hubbe et al., 2017).
Tannin wood adhesives are becoming increasingly interesting be-
cause they have similar reactivity and cross linking chemistry with
formaldehyde as phenol- and resorcinol-formaldehyde systems (Van
Langenberg et al., 2010).
In wood adhesive technology, condensed tannins are now the most
extensively studied, because, besides the limitations mentioned earlier,
the reactivity of hydrolysable tannins with formaldehyde is rather
limited (Pizzi, 2006). Furthermore, the links between hydrolysable
tannin units are less resistant to moisture. Condensed tannins are in-
stead composed of units linked by bonds better resistant to moisture
(Hemmilä et al., 2013).
Many research works have been and are conducted to improve
tannin-based adhesives, like simple blend or real co-polymerization
with other resins and additives. Condensed tannins can be used in the
 Y. Shirmohammadli et al.

Table 2
Chronological order to some of the most outstanding studies on tannin adhesives.
No Resin + hardener Composite Finding Reference

1 Mimosa T + formaldehyde PW A commercial adhesive in South Africa (Pizzi and Scharfetter, 1978)
2 Mimosa T-Resorcinol-HCHO Glulam and fingerjoints A commercial adhesive in South Africa (Pizzi and Roux, 1978)
3 Treated Mimosa+ HCHO PB A commercial adhesive in South Africa, Australia, and other parts of the world. Still the (Pizzi, 1978)
most used commercially
4 Mimosa T + Methylol ureas Exterior and semi exterior PB Low cost T adhesives. Methylolureas can be successfully used as hardeners (Pizzi and Merlin, 1981)
5 Larix T (60%)-PF General and construction use PW Obtained resin had much better properties than pure PF (Yuebin et al., 1994)
6 Quebracho T-FA Hard board Results were comparable to the PF (Trosa and Pizzi, 1998)
7 PF (80%) - T (20%) PW Acceptable performance at industrial scale (Borges et al., 2006)
8 PF - Pinus oocarpa T (10%) PW Doesn't alter MOR and MOE, except parallel MOE (Ferreira et al., 2008)
9 The wattle T- Polyvinyl acetate (20%) Bonding fancy veneers to PW 20% PVAc enhanced the bonding strength of T adhesives (Kim, 2009)
10 PF (80%)-Cornstarch (15%)-quebracho T (5%) Exterior PW Better mechanical properties than PW panels made by commercial PF (Moubarik et al., 2009)
11 Cornstarch - wattle T + HCHO Interior PW Excellent mechanical properties, comparable to PF (Moubarik et al., 2010)

319
12 PF- Eucalyptus T (10-15%) Cellulose fiber composite sheets Mechanical properties comparable to that of made with pure PF (Hussein et al., 2011)
13 Mimosa tannin (50%)+lignin (50%) Interior PB While tannin alone achieved exterior grade panels (Navarrete et al., 2012)
14 Grape T (60%) - lignin (40%) Interior PB T molecules, cause a higher density, crosslinking and also higher strength (Ping et al., 2012)
15 Mimosa T/ HCHO (60%) - lignin (40%) PB Satisfied the European standard requirements for internal bonding (Bertaud et al., 2012)
16 Pine T PB and MDF Can be an industrial adhesive to manufacture PB and MDF (Valenzuela et al., 2012)
17 FA (54%)-Quebracho T (45%) –paratoluenesulfonic acid (0.9%) Composite with vegetal fibers Very short curing time and good mechanical properties (Nicollin et al., 2013)
reinforcement
18 MF/PF- T (20%) PW T and formaldehyde reaction improves the adhesive systems cross-linking and resulted in (Gangi et al., 2013)
the reinforced MF and PF
19 Mimosa/pine T-FA (50%) PB At pH = 10 it was able to satisfy European standard (Abdullah and Pizzi, 2013)
20 Pine T- PF/UF/pMDI Interior and exterior PW 20-35% synthetic adhesive addition promoted basic tannin adhesive (Zhou and Pizzi, 2014)
21 lignin polyol-T + polyethylenimine (PEI) PW PEI addition caused Higher tensile strength, heat and water resistant (Faris et al., 2016)

T: tannin, FA: furfuryl alcohol, PF: phenol formaldehyde, MOR: modulus of rupture, MOE: modulus of elasticity, HCHO: hexamine, PB: particle board, MDF: medium density fiberboard, PW: plywood- MF: melamine
formaldehyde, UF: urea formaldehyde, pMDI: polymeric isocyanate.
Industrial Crops & Products 126 (2018) 316–332
Y. Shirmohammadli et al.
manufacture of adhesives with two approaches: polycondensation re-
actions or autocondensation reactions.
Tannins can also be copolymerized with synthetic adhesive. The
purpose of this are often (1) to decrease formaldehyde emission from
synthetic resins (when a few percentages of tannin are added) or (2) to
improve water resistance of tannin-based adhesives (when a few per-
centages of synthetic resins are added). Addition of a few percentages of
polymeric isocyanate (pMDI) (from 10% up to 30%) to mimosa tannin
adhesives yielded joints with very high Young's modulus values (more
examples in Table 2) (Osman, 2012; Pizzi et al., 1993).
4.1.1. Polycondensation with aldehydes or non-aldehyde hardeners
The polycondensation reactions of tannins with aldehydes or dif-
ferent non aldehyde hardeners (glyoxal, furfuryl alcohol, hexamine
etc.) have been used extensively. In the production of wood based
composites (WBC), tannin-formaldehyde adhesives have been success-
fully commercialized for several years and are used in some countries
(Pizzi, 2016; Valenzuela et al., 2012). The exterior-grade WBC bonded
with tannin adhesives is most of the time produced by polycondensa-
tion of tannins with aldehyde hardeners. The reaction of tannins with
aldehydes has always resulted in weather- and boil-proof adhesives.
Furthermore, these adhesives possess very low formaldehyde emission
(Pizzi, 2006).
Of further interest for tannin based adhesives is their reaction with
hexamethylenetetramine (hexamine) used as a non-aldehyde-yielding
hardener under alkaline conditions (Pizzi, 1994b). Hexamine has been
proven to not decompose to formaldehyde and ammonia (Kamoun and
Pizzi, 2000; Kamoun et al., 2003) when in presence of a reactive con-
densed tannin. Thus, formaldehyde emission from these adhesives is
very low and limited exclusively to that generated by the heating of
wood itself. Panels bonded with tannin-hexamine adhesives, depending
on the conditions under which they are prepared, can meet both in-
terior- and exterior-grade standard specification requirements. Slow
reacting tannins such mimosa and quebracho can be used with hex-
amine to prepare interior grade particleboard. Exterior-grade particle-
board can be obtained with faster tannins under different pressing
conditions (Pizzi et al., 1997). The most spectacular studies about
polycondensation or copolymerization of tannins with different hard-
eners or resins are presented in Table 2.
4.1.2. Autocondensation reactions without hardeners
The term “autocondensation” refers to the opening of the pyran
rings under alkaline or acidic conditions in the absence of external
hardeners (Pizzi et al., 1995). This aspect of tannin chemistry in-
troduces self-polymerization of tannins to yield a cross-linked poly-
phenolic network.
Different tannins present different autocondensation rates. Mimosa
and quebracho tannins present a slower autocondensation than pecan
nut and pine tannins (Pizzi and Stephanou, 1994). With fast tannins just
contact with the lignocellulosic surface is enough for rapid self-poly-
merization (Pizzi, 1994a; Pizzi et al., 1995). Thus, slower tannins need
more time and results in a lower internal bond strength of the bonded
panel because of their slow hardening rate.
Meikleham et al. (1994) found that autocondensation of various
tannins is inducible by weak Lewis acids such as silica, silicates, boric
acid and aluminum chloride. Actually, Lewis acids act as a catalyst for
tannins autocondensation. The problems related to the slow reacting
tannins can be solved by Lewis acids-based autocondensation systems
(to accelerate it) which results in the need for a lower press temperature
and press time as well as in higher internal bond strengths (Pizzi et al.,
1995; Garcia and Pizzi, 1998a, 1998b). Most recently, Efhamisisi et al.
(2016) reported that poplar (Populus deltoides) plywood panels made of
quebracho tannin adhesive (50% water solution) and a small propor-
tion of boric acid (2%–4% based on the total resin) are able to meet the
bonding requirements for interior-grade panels of the relevant Eur-
opean standard (EN 314-2, 1993) Since boric acid is also an effective
320
Industrial Crops & Products 126 (2018) 316–332
biocide, panels had improved biological resistance against termites and
fungi (Efhamisisi et al., 2016).
The tannins hardened by the autocondensation approach, induced
either by the lignocellulosic substrate or by Lewis acids only resulted in
bonds of interior-grade quality (Pizzi, 2003a, 2006).
4.2. Epoxy adhesives from tannins
Recently, various plant sources such as tannins were used to make
bio-based epoxies (Mashouf Roudsari et al., 2017). It should be noted
that catechin and gallic acid are among the most studied tannin deri-
vatives and used as models of condensed and hydrolysable tannins re-
spectively. Catechin was epoxidized either by reaction with epi-
chloridrin (ECH) or by alkylation with unsaturated halogenated
compound followed by its oxidation (Boutevin et al., 2010). A full
characterization of the obtained compounds shows the presence of a by-
product with a benzodioxane group, which then decreases the average
epoxy functionality (Nouailhas et al., 2011). These by-products result
from internal cyclization reaction between phenolic alcohol in ortho-
position and ECH.
More recently two studies by Jahanshahi et al. (Jahanshahi et al.,
2016a, 2016b), one on the formation and testing of polyflavonoid
tannins epoxy resins were published, the second of which was of par-
ticular interest being an epoxidized tannin acrylic that allowed rapid
curing of the epoxy tannin without having to use a hardener.
Gallic acid epoxidation with epichlorhydrin was first reported by
Tomita and Yonezawa (1983). Aouf et al. (2013) reported conditions
allowing the synthesis of tetra epoxy gallic acid. Previous studies only
reported functionalization with two to three epoxy groups. Also it was
recently proposed another synthesis pathway leading to epoxy pre-
polymers from gallic acid allylation by reaction of gallic acid with allyl
bromide, followed by double bond oxidation using m-chloro-perbenzoic
acid (Nouailhas et al., 2011).
Benyahya et al. (2014) proposed direct use of condensed tannins
extracted from green tea which are naturally rich in polyphenols for the
synthesis of aromatic bio-based epoxy oligomers.
4.3. Tannin-based bio-adhesives for grinding wheels, angle grinder disks and
automotive brake pads matrices
A 100% biosourced thermoset material based on condensed tannin-
furanic thermoset resins has been used as the resin matrix of solid
grinding wheels (Lagel et al., 2015a). Moreover, this new thermoset
material is produced by a simple process, which can be easily in-
dustrialized. Grinding wheels based on this resin, additioned of either
tung oil or linseed oil and hardened with p-Toluensulphonic acid were
used for bonding different mineral and organic abrasive powders were
developed and characterized. These grinding wheels show excellent
abrasiveness properties when compared with a commercial grinding
wheel. More recently grinding wheel based on the lignin and furfuryl
alcohol were also developed (Liang et al., 2018). The resin developed
presented a glass transition temperature (Tg) of around 170 °C and as
for the tannin-furanic matrices presented a better performance than
grinding wheels bonded with synthetic phenol-formaldehyde adhesive
resins.
By using the same biosourced raw materials, condensed tannins and
furfuryl alcohol, a thermoset resin was developed and used and tested
for a new application: as a resin matrix of solid grinding disks for angle
grinders (Lagel et al., 2015b). The manufacturing procedure developed
is particularly easy. Cutting and grinding disks based on this green resin
were used for bonding different sizes of abrasive particles of aluminium
trioxide. The matrices used contained, on top of the basic quebracho or
mimosa tannin-furfuryl alcohol resin matrix, small proportions of
polyethylene glycol (PEG 400), tung oil, Xiameter OFX-0193 Fluid
(DC193), namely a silicone polyether copolymer emulsifier from Dow
Corning, p-Toluene sulphonic acid hardener and a majority of
Y. Shirmohammadli et al.
Fig. 4. Example of (a) fiberglass net used in grinding wheel core, (b) cured pured tannin furanic resin, and (c) the angle grinder disk obtained by the combination of
(a)+(b) (Lagel et al., 2015b).
aluminium trioxide abrasive particles. The whole was placed around to
cover a fine fiberglass net (Fig. 4). These angle grinder discs were
characterized and showed excellent abrasiveness and cutting proper-
ties. Their mechanical resistance was found to be comparable to that of
commercial grinding discs bonded with synthetic phenolic resins.
By using the same or similar biosourced raw materials as above
(condensed tannins and furfuryl alcohol) a biosourced thermoset resin
was also developed as a resin matrix of automotive brake pads (Lagel
et al., 2016; Al-Marzouki et al., 2017). The manufacturing procedure
developed again was particularly easy. Automotive brake pads based on
this green resin were characterized and showed excellent braking
properties and wear resistance when used under real car, full scale test
conditions. The basic resin and glue mix used were the same as in-
dicated above for the angle grinder disks, but contained furthermore
small amounts of graphite, neoprene, glycerol phosphate acidic ester.
Furthermore mineral (iron) wool and fiberglass cut in small pieces were
added. Not only the new resins were biosourced from renewable ma-
terials but also they did not contain any formaldehyde. Their me-
chanical resistance was found to be comparable to that of commercial
automotive brake pads bonded with synthetic phenolic resins.
4.4. Tire cord adhesives
Tire cords are the vital tire reinforcement which results in the
strength, controlled deformation and comfort of riding. Adhesion of tire
cords to the tire rubber plays a very important role in the prevention of
blowout risks (Niroomand et al., 2017). Less than 10% of the worldwide
resorcinol adhesives are consumed as the tire cord adhesives (Pizzi,
2003b). Extracts of condensed tannins have shown that they can be
used successfully as a tire cord adhesive. For this purpose, both tannin-
resorcinol-formaldehyde (Hamed et al., 1989), thermosetting tannins
formulation (Hemingway and Karchesy, 2012) and also cold setting
tannins adhesives (Gómez-Jiménez-Aberasturi, 2017) have been ex-
perimented successfully.
Investigations have shown that condensed tannins can replace a
proportion or all of the resorcinol in a standard resorcinol-for-
maldehyde-latex dip, especially in the case of using poly ester cord.
Furthermore, pecan nut pith tannin extract has shown that if used to
substitute resorcinol adhesive totally, the tire cord pull-out force can
reach twice as high as what obtainable with the standard dip (Hamed
et al., 1989).
4.5. Fortifiers of starch-based corrugated cardboard adhesive
Starch is an important biopolymer in the adhesive field which is
extensively used in the paper industry (Liu et al., 2014). Tannins are
very interesting additives used for starch-based adhesive because of
their potential effects on both adhesive properties and water-resistance.
The adhesives developed for the manufacture of damp-proofed
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corrugated cardboard are based on the addition of mimosa (wattle)
tannin, urea-formaldehyde resin, and formaldehyde to a typical Stein-
Hall starch formula of 18–22% starch content (McKenzie and Yuritta,
1972; Saayman and Brown, 1977; Clusters et al., 1979). The mimosa
tannin-urea-formaldehyde copolymer formed in situ, and any free for-
maldehyde left in the glue line is absorbed by the mimosa tannin ex-
tract. The mimosa tannin extract powder should be added at level of
4–5% of the total starch content of the mix (i.e., carrier plus slurry)
(Clusters et al., 1979). Successful results can be achieved in the range of
2%–12% of the total starch content, but 4% is the recommended
starting level. The final level is determined by the degree of water
hardness and desired bond quality. This wattle extract-UF fortifier
system is highly flexible and can be adapted to damp-proof a multitude
of basic starch formulations. Plant trials and industrial production of
this application has taken place for many years (Clusters et al., 1979).
Recently the addition of four commercial tannins on the properties
of starch-based adhesive was evaluated by using fundamental rheolo-
gical techniques (Marino et al., 2014). Experiments showed a double
effect of tannin addition on mechanical properties of the starch-tannin
adhesive. Tannin addition caused a weaker starch network, but on the
other hand the polymeric components of tannins interacted with each
other reinforcing the starch network.
4.6. Coatings
4.6.1. Tannin-based polyurethane surface coatings with or without
isocyanates
As regards the preparation of polyurethane adhesives starting from
condensed or hydrolysable tannins two approaches have been taken: (i)
modification of the flavonoid tannin in order to render easier the re-
action with isocyanates. This is due to the difficulty in reacting the
flavonoid hydroxyl groups directly with isocyanates. In this type of
application the tannins are in direct competition with more suitable
natural polyols, of which the literature abounds, to prepare semi-bio-
sourced polyurethanes; (ii) the use of a total no-isocyanate approach to
improve the environment-friendly character of such adhesives.
For the first approach, benzoylation to reduce the number of hy-
droxyl groups of the tannin before reaction with diisocyanate was tried
a long time ago (Pizzi, 1979a). A more studied approach has been to use
lignin and lignosulphonate/hydroxypropylated to prepare urethanes
(Glasser et al., 1984, 1986; Glasser and Leitheiser, 1984) although this
approach has been more directed towards coatings than adhesives. The
same and more studied approach has been to prepare novel thermo-
setting tannin-based polyurethane adhesive resins using the hydro-
xypropyl and hydroxybutyl derivatives of purified condensed tannins
from Pinus pinaster bark and other condensed tannins species by reac-
tion with diisocyanates (García et al., 2013, 2014, 2015, 2016). Hy-
droxypropylation and hydroxybutylation are one of the approaches
used to react polyphenolic materials with isocyanates to obtain
Y. Shirmohammadli et al.
Fig. 5. Formation of semi-biosourced polyurethanes adhesive resins: firstly the Reaction of P. pinaster bark tannin with propylene oxide to produce hydroxypropyl
ethers tannin derivatives (top), secondly reaction of a hydroxypropylated polyphenolic tannin with an isocyanate (bottom) (García et al., 2015).
polyurethane adhesives and resins (Fig. 5). This renders easier the re-
action of flavonoid tannins with isocyanates, due to the introduction of
much more approachable hydroxyl groups into the tannin structure,
thus increasing reaction yield.
The same approach, thus to introduce in the tannin structure more
available −OH groups but through a reaction totally different from
hydroxypropylation, consisted in reacting an aldehyde with the tannin
and then use the hydroxyl groups formed by its addition onto the fla-
vonoid structure, before their further condensation with other flavo-
noids, to react with an isocyanate (Pizzi et al., 1993; Valenzuela et al.,
2012; Pizzi and Walton, 1992). Such a system has been used and is used
industrially for wood adhesives (Valenzuela et al., 2012). More recently
the system has been adapted by eliminating formaldehyde and sub-
stituting it with glyoxal with good results (Basso et al., 2014) rendering
the approach even more environmentally interesting.
However, isocyanates are harmful to human health. Thus, the pre-
paration of polyurethane adhesives of a high level of biosourced and
environment friendly material it involves by necessity the synthesis of
non-isocyanate polyurethanes. This approach which avoids the use of
any isocyanate is attracting increasing interest. It is based on the
polycondensation of diamines with dicyclocarbonates to lead to poly-
hydroxyurethanes. This reaction has been studied by a few research
groups (Rokicki and Piotrowska, 2002; Whelan and Cotter, 1963;
Kihara and Endo, 1993; Kihara et al., 1996; Tomita et al., 2001a,
2001b, 2001c; Birukov et al., 2014; Figovsky and Shapovalov, 2002;
Camara et al., 2014; Blattmann et al., 2014; Boyer et al., 2010; Kim
et al., 2001; Ochiai et al., 2005; Ubaghs et al., 2004; Fleischer et al.,
2013) and leads to polyhydroxyurethanes of relatively low glass
Fig. 6. Non-isocyanate diurethane obtained by reacting a precarbonated flavonoid tannin with a diamine (Thébault et al., 2015).
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transition temperatures and Mn (Number average molecular weight)
lower than 30,000 g/mol−1. All the work on non-isocyanate poly-
urethanes is concentrated on synthetic materials. Thus, while iso-
cyanates are definitely not used, synthetic diamines and synthetic di-
cyclocarbonates, both of no natural origin are used, yielding
polyurethane resins that are not biosourced. While use of glycerol has
been reported (Fleischer et al., 2013) the percentage of biosourced
material is still lower than the approach of using an isocyanate reacting
with a natural polyol.
Only very recently approaches to non-isocyanate polyurethane ad-
hesives has aimed at not only eliminating the toxic isocyanate but also
at improving the percentage of biosourced material composing the
“green” polyurethane adhesive. The same reaction used for synthetic
materials has been used with both a hydrolysable tannin and condensed
flavonoid tannins, these are natural renewable materials, by reacting
them first with dimethyl carbonate, thus a non-cycqlic carbonate, fol-
lowed by reaction with hexamethylenediamine (Thébault et al., 2014,
2015) to obtain non-isocyanate urethanes of the type shown in Fig. 6.
This was the first approach to obtain a biosourced polyurethane
without using isocyanates, although, the percentage level of biosourced
material was only 45%–50%, the diamine and the carbonate being still
synthetic materials. As the amination of condensed tannins, thus the
conversion of their hydroxyl groups into amino groups, is an easy re-
action (Braghiroli et al., 2013), the aminated tannin was used to sub-
stitute the hexamethylenediamine, further improving to more than 70%
of biosourced material in the final polyurethane, and this without using
any isocyanate (Thébault et al., 2017) to obtain flavonoid oligomers
linked by urethane bridges.
Y. Shirmohammadli et al.
Fig. 7. Example of oligomers obtained by the reaction of condensed flavonoid
tannins and triethyl phosphate (Basso et al., 2017).
4.6.2. Tannin binders for Teflon coatings to metals
Recently a considerable effort has been made to develop tannin-
based adhesives capable of bonding Teflon to metal, namely steel and
aluminium, and capable of withstanding high temperatures of opera-
tion (Maris and Joutang, 2007; Basso et al., 2014, 2017). The break-
through in this bonding application, where not only tolerance to high
temperature but also total absence of formaldehyde for food application
were needed, came with the discovery of the reaction of polyphenols
such as tannin and even lignin (Basso et al., 2014) with triethyl phos-
phate (TEP).
This novel cross-linking reaction is based on the reaction, oligo-
merisation and cross-linking of tannins by TEP in presence or absence of
ammonia (this latter being preferable to the yield). Reaction of con-
densation and cross-linking of catechin monomer and of mimosa tannin
itself, as well as of resorcinol with TEP were investigated (Basso et al.,
2017). The chemical analyses revealed that reaction occurs mainly on
the C3 of the flavonoid heterocycle ring and on the aromatic C4′ and
C5′ carbons of the flavonoids B-ring (Fig. 7). The resin so obtained can
produce hard thermoset plastics and films resistant up to temperatures
in excess of 400 °C.
4.6.3. Corrosion inhibitors
In the industry, iron, steel and alloy parts exposed to acid conditions
starts to corrode by two reactions: chemical and electrochemical. This
phenomenon leads to an enormous loss due to the need to replace or fix
these metal parts (Abdullah Dar, 2011; Talib et al., 2014). One of the
practical methods to prevent metal corrosion is using anticorrosion
coats (Singh et al., 2010). The chemical and physical preparation of
metal surfaces before coating is very important. Prior to using a paint,
applying anticorrosive coating can dramatically enhance the protection
properties of the main paint. As a result of environmental concerns
which have become more severe recently and harmful effects of syn-
thetic anticorrosives, anticorrosion characteristic of tannins have been
studied by many researchers (Rahim and Kassim, 2008). Probes related
to tannins for metal surface protection and as an anticorrosion agent
started about half a century ago and some tannin-based formulations
for metal protection without need to eliminate previous corrosions
entered to the market (Peres et al., 2015; Pérez et al., 2006).
In a research work by Matamala et al. (2000), they introduced a
formulation for steel protection based on pine tannins primers which
was able to extend the duration of painting more than 50% if applied
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before the main painting. There are old reports indicating that a tannin-
based metal primer was commercially used in England since the early
1960s (Ross and Francis, 1978). Moreover, tannins anticorrosive
characteristic can be used along with dissolving tannin in other coatings
or anticorrosive substances like epoxy (Idora et al., 2017), zinc oxide
(Hadzich et al., 2018) or copper (Pérez et al., 2006) in order to improve
the anticorrosive properties of the previous traditional coatings. Then
after needed additives are added (like sulphuric acid, potassium hy-
droxide or phosphoric acid for pH adjustment) and the anticorrosive
coating is applied on the metal surfaces by different methods such as
brushing. Both types of tannins (hydrolysable and condensed) are able
to act as an anticorrosion agent for metals, because both of them have
the potential to oxidize the phenol groups (antioxidant) and to complex
the metal by ortho-diphenol complexation (Flores Merino et al., 2017).
The conventional method for coating ship hulls is to use metal-
containing antifouling paints. These provide protection by releasing a
toxic compound. Research has shown that tannins along with copper
can be used as an antifouling agent for submerged surfaces in sea water
and is able to reduce the accumulated fouling agents. Furthermore, this
formulation was able to reduce copper usage 40 times in comparison to
paints which are based on cuprous oxide (Pérez et al., 2006).
5. Tannin-impregnated paper: high pressure and low pressure
lamination
Tannin-furanic high pressure laminates are the tannin-furanic resin
as the bonding agent, were prepared by acid catalysis. The mixture of
mimosa tannin, furfuryl alcohol and pTSA (para-toluene-4-sulphonic
acid) were prepolymerized in a rotary at 60 °C for 30 min. The resin so
prepared was used to impregnate alpha cellulose paper and the papers
so prepared were pressed together to bond in a solid reinforced sheet
forming high pressure laminates (Fig. 8) (Abdullah et al., 2014). The
high pressure laminates prepared were tested for abrasion resistance,
cross-cut adhesion test, water vapor resistance and staining test and
compared with phenol-formaldehyde high pressure laminates from.
Color and gloss measurement were also done.
Equally, paper sheets impregnated with a tannin-furanic resin were
applied in a hot press onto a wood particleboard substrate; the resin in
the impregnated paper functioning also as the adhesive of the im-
pregnated paper sheet onto the board (Pizzi, 1979b; Abdullah et al.,
2013a, 2013b). The surface quality of these low pressure paper surface
laminates with a mimosa tannin resin was comparable to the com-
mercial synthetic melamine-urea-formaldehyde (MUF) resin. The
tannin-bonded low pressure laminates performed better than the MUF
ones for application on wood panel surfaces. The main disadvantage of
the tannin resins for this type of application is their dark brown, almost
black color that render them suitable only for application in cement
building shutter boards. The moisture content of the impregnated pa-
pers were varied between 23% and 10%. Impregnated papers with
mimosa tannin adhesive resin gave excellent results for water vapor
resistance and the cross-cut test according to relevant standards.
Moisture content of the impregnated papers were found to influence the
Fig. 8. Example of a high pressure laminate. Mechanical gear composed of 30
tannin-furanic impregnated papers pressed together (Abdullah et al., 2014).
Y. Shirmohammadli et al.
abrasion resistance for both the mimosa tannin resin and the MUF resin
impregnated papers. Color measurements were carried out to relate the
different paper colors to the two different moisture contents used. Im-
pregnated papers with mimosa tannin resins at 23% moisture content
have a lighter shade compared with impregnated papers with mimosa
tannin resins at 10% moisture content.
6. Wood protection
Wood and items made from wood are organic and lignocellulosic
materials, which are prone to be attacked by biological deterioration
agents, creating a need for preservative-treated wood. Concerns about
the durability of solid timbers have resulted in the use of chemical
treatments by a variety of application methods including pressure im-
pregnation, immersion, diffusion, and vacuum-assisted treatments
(Reinprecht, 2016; Cooper, 2007). Nowadays, because of public
awareness about heath and dangers of toxic substances, environmental
performance and sensitivity of wood preservatives are playing an in-
creasing role in their development and use (Shmulsky and Jones, 2011).
Researchers are looking for natural materials with herbal or animal
origins to replace old toxic wood preservatives (Singh and Singh, 2012).
A lot of attempts carried out to improve the bio-durability or other
properties of wood as well as wooden composites with tannin-based
preservatives.
Laks et al. (1988) reported that tannins extracted from the bark of
Pinus taeda have some limited effectiveness against fungal attack, but
that they are more effective in the complexed form with copper (II)
ions. The association between tannins and boric acid could also be
another remedy. Pizzi and Baecker (1996) used preservative solutions
based on tannins and boron in which boric acid was used to induce
hardening reactions of polyflavonoid tannins, promoting the formation
of a cross-linked flavonoid oligomer network in the xylem structure.
Equally, boric acid can be partially fixed into the wood by the trapping-
in the tannin polymer.
The modification of mimosa tannin with a copper-ammonia com-
plex also appeared to promote the antidecay properties of treated wood,
while unmodified tannin had no preventive effect on the fungal attack
(Yamaguchi and Okuda, 1998; Yamaguchi and Yoshino, 2001). In a
new study it was, however, reported that impregnation of wood with
the 5% or 10% aqueous solution of mimosa tannin can increase re-
sistance of wood against white rotting fungus (Silveira et al., 2017).
Termiticidal properties of tannins were also studied (Tascioglu et al.,
2012); the woods treated with mimosa and quebracho tannins showing
good resistance against the attack of subterranean termites at the high
level of tannin loading inside the wood (∼80–100 kg of tannins in each
cubic meter of wood). However, the tannin of the pine bark appeared to
have no effectiveness against termite damage.
The wood preservative based on the interaction of tannin and boron
was promoted by the addition of hexamine (Thevenon et al., 2009,
2010). The tannin preservative can be rendered more waterproof by
adding hexamine and consequently co-added boric acid can be fixed
well inside the wood. Treated samples with this innovative preservative
were resistant against the attack of fungi, termites and boring beetle
even after aging periods (Tondi et al., 2012a, 2012b). On the other
hand the formation of harden preservative of tannin/hexamine + boric
acid inside the wood yields improved mechanical and fire resistance
(Tondi et al., 2012c, 2014). The weathering resistance of treated wood
with tannin-based co-polymers was also studied (Tondi et al., 2013b). It
was concluded that since tannin is an aromatic compound, it suffers a
similar degradation as lignin during exposure to the exterior climatic
factors. In another study, greater color changes than the controls as a
result of weathering processes were detected in beech wood samples
impregnated with mimosa tannins (Yalcin et al., 2017). Addition of
polyethylene glycol and caprolactam to the tannin-based preservative
was also tried to increase the elasticity of the polymer formed within
the wood (Tondi et al., 2015, 2017; Hu et al., 2017). The wood
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protection of tannin/hexamine + boric acid showed also high potential
to produce durable plywood panels designed for both interior and
humid conditions (Efhamisisi et al., 2016, 2017). As shown here, a large
amount of research has been carried out on tannin based preservatives
possibly promising a new generation of future wood protectants.
More recently the hardening of tannins with furan components such
as furfural and furfuryl alcohol has been evaluated as a completely
biosourced polymer (Abdullah and Pizzi, 2013; Tondi, 2017). Although
the modification of wood properties with furfuryl alcohol is well
documented and commercialized, it seems that the reaction of furfural
(as aldehyde) with tannins can be another modifying approach to in-
troduce biosourced wood preservatives.
7. New materials
7.1. Foams
Studies considering the tannins and furfuryl alcohol combination as
an adhesive have resulted in the creation of almost totally biosourced
foams. The first report of feasible tannin-furfuryl alcohol foams ap-
peared in 1994 (Meikleham and Pizzi, 1994). This was followed by
numerous different studies implemented in order to eliminate these
foams shortcomings and to better understand their characteristics to
make them more efficient (Li et al., 2012a; Lacoste et al., 2013; Zhao
et al., 2010).
Tannin foams are made in three stages: mixing, expansion and
curing, respectively. In first stage, all ingredients including: tannin
extract, furfuryl alcohol, formaldehyde, blowing agent, additives and
water are added and mechanically stirred until achieving a homo-
geneous and notable viscous blend. In the second stage a potent acid as
a catalyst is added to the blend. Furfuryl alcohol acts as an agent for
heat generation for its reaction with other ingredients and also for its
self-polymerization reaction. By evaporating the solvent (physical
blowing agent) as a result of rising temperature, tannin and furfuryl
alcohol starts to cure at the same time. Finally in the last step the
network of tannin, furfuryl alcohol and formaldehyde starts to harden
and stabilizing (Tondi and Pizzi, 2009).
Manufacturing companies of polyurethane and carbon foams have
some growing interest toward using tannin-furfuryl alcohol in their
products, because with this new combination they can possibly solve
their products drawbacks like low fire resistance and the lack of en-
vironment presents friendliness (Basso et al., 2014). Because for-
maldehyde presents numerous shortcomings and threats, recent re-
searches have succeeded to produce tannin-based foams without any
formaldehyde and/or blowing agent addition (Basso et al., 2013).
Since polyflavonoid tannins are phenolic materials, foams which are
made of these materials are fire resistant as much as synthetic phenolic
foams. These flavonoid-furanic foams are comprised of about 95% of
natural materials (Tondi et al., 2008). Some of the applications of these
foams include acoustic absorbers (Lacoste et al., 2015), metal ion ad-
sorption (Tondi et al., 2009), floral foams (Basso et al., 2016), sandwich
panels (Zhou et al., 2013), crash protection, packaging etc. Many in-
vestigations have also been carried out to improve tannin foams char-
acteristics like hydrophobisation (Delgado-Sánchez et al., 2016), com-
pressive strength and impact (Li et al., 2013), flexibility (Li et al.,
2012a) and mechanical integrity (Li et al., 2012b). For example, Li et al.
(2012b) mentioned that the low mechanical strength of tannin foams is
one of the barriers to their applications. Thus, they improved tannin
foams compressive strength as much as 37% in comparison to con-
ventional formulation. They added new substances including oligo-
meric precursors (hydroxyl terminated) and glutaraldehyde as a cross
linker.
More recently, promising results for the manufacture of foams have
been shown in the case of mixing hydrolysable and condensed tannins
with pulping by-products including lignosulfonate and Kraft black li-
quor for insulation of buildings (Merle et al., 2016a, 2016b).
Y. Shirmohammadli et al.
7.2. Wood-plastic composites
Wood plastic composite (WPC) are created as a result of wood
supply shortages in order to use recycled wood and plastics in a more
useful way. They consist of a thermoplastic matrix and lignocellulosic
component for reinforcement. Furthermore, additional elements to
improve physico-mechanical characteristics of the composite can be
added (Ashori, 2008). As far as lignocellulosic components have hy-
droxyl groups, they cannot react with thermoplastics matrixes. For
creating interfacial interactions between lignocellulosic components
and the plastic matrices it is necessary to use coupling agents. Coupling
agents like maleic anhydride are able to form chemical bonds between
dissimilar compounds of WPC (organic wood and inorganic polymer)
(Zhou et al., 2016a).
Lignin has been used with plastics (e.g. polypropylene) in the
manufacture of WPC with good final products characteristics when
using proper coupling agent like reactive flexible segment (Xu et al.,
2014). Also, Lee et al. (2015) manufactured a composite comprised of
polylactic acid, coffee, lignin and polypropylene. Their results showed
that lignin can act successfully as a coupling agent and led to an im-
provement in physical, mechanical and thermal properties.
Pine cones which contain high amount of phenolic substances have
been shown to be usable with polypropylene and showed that pine
cones are capable to be used as a reinforcing filler in the manufacture of
WPC (Ayrilmis et al., 2010). Therefore, since contraindications of use
do not exist between tannin and plastics, also lignin showed good
properties with plastics in the WPC production. Due to the tannins and
lignin similarity of chemical structure, it is suggested that the potential
exist for tannins too to be used in WPC production as coupling agents.
8. Food industry
8.1. Beverage
Tannins are added several times during winemaking to give color
stability, protections against oxidation, odor and mouth-feel, proteic
material precipitation and flavor improvement (Parker et al., 2007).
Phenols main addition in winemaking is by grapes skin and seeds which
aid to make wine. More tannin addition to wine can be in the form of
direct addition, storing in oak barrels or addition of oak flakes
(Harbertson et al., 2012). Extraction of condensed tannins from the
seed and skin of grapes has showed that, skin tannin extraction yields
more than seeds, thus the skin condensed tannins have a more im-
portant effect in winemaking (Cerpa-Calderón and Kennedy, 2008).
Wine phenols oxidation reactions affect the wine taste, odor, and color
changes. The polyphenols present are the one that most of the time are
capable to prevent oxidation reactions and acts as natural wine pre-
servatives.
Astringency means the puckering and drying of the mouth as a re-
sult of the saliva protein precipitation by phenolic compounds (García-
Estévez et al., 2018). Since tannins precipitate proteins, they cause
astringency in food, this being one of the main characteristics of red
wines (Picariello et al., 2018). This feeling can be more intense when
drinking wine without eating. White wines have less phenols in their
composition (about 500 mg/l) in comparison to red wine (about
1500 mg/l), thus astringency is much more marked in red wines, being
one of their characteristics. During the past decades peoples have
tended to consume less astringent wines and consequently phenolics
proportions in wines have also decreased.
Tannins which are used in winemaking are named "enological tan-
nins" or " oenatannins" and can be obtained from different botanical
resources like oak wood, grape seed and skin, plant gall, chestnut,
quebracho etc (Sanz et al., 2008). Anthocyanidins are considered as the
main kind of condensed tannin which influence the color of the grapes
and consequently of wine. Wine antioxidant properties are known to be
beneficial for human health like being anti-cancer and lowering the
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level of diabetic and cardiovascular illnesses (Yang et al., 2018). Tan-
nins can be added to compensate for some wines low tannin levels
because now wines might not be kept anymore for aging for too long in
oak barrels (García-Estévez et al., 2017).
8.2. Fisheries
The outer layer of some fish eggs have glycoprotein as a constituent
and at spawning time, when the eggs contact the water, they hydrates
and becomes sticky. This phenomenon (sticky surface) is very im-
portant in a natural environment, because it allows the eggs to stick to
the plants underwater and achieves an increase in the survival rate of
the species (Kynard et al., 2011). In order to incubate fish eggs artifi-
cially, a vertical water flow hatching machine (Weiss jars) is used. In
this type of equipment the eggs need to circulate. To ensure a suitable
level of circulation, the eggs stickiness of should be eliminated. If the
eggs stickiness is not eliminated, they will stick together and forms
clumps (mass adhesion) or stick to the equipment parts resulting in the
destruction of the eggs (Siddique et al., 2016). The de-sticking process
improves embryonic development, eases the conditions of control, and
improves the hatching percentage in the incubator (Al Hazzaa and
Hussein, 2003). The eggs de-sticking process is an essential stage in the
reproduction of some fish species such as white bass (Morone chrysops),
lake sturgeon (Acipenser fulvescens), etc. since they produce very good
meat while their eggs are very sticky. Thus, their breeding and re-
production can be of great economic importance.
There are several chemical treatments to remove the jelly layer of
fish eggs (such as carbamide in saline solution, powdered milk dis-
solved in saline solution, sodium sulfite etc.) (Al Hazzaa and Hussein,
2003) and/or other methods like mechanical separation, scouring eggs
with clean water or abrasives (starch, clay, charcoal or bentonite)
(Demska‐Zakęś et al., 2005). One of the very frequent used methods in
de-sticking eggs is flushing the eggs in a urea-salt solution, and after-
ward to float them in a low concentration tannin solution for a very
short time (Kujawa et al., 2010). In a study by Hosseini and Khara
(2015) they compared the impact of clay suspension and tannic acid for
egg de-sticking of Beluga (Huso huso). The de-sticking process took
45 min and 1.5 min for a clay suspension and a tannic acid treatment,
respectively. Furthermore, the hatching and survival percentage for
tannic acid-treated eggs was much higher than for the clay suspension
treatment, while tannic acid showed even lower fungal contamination.
In the de-sticking process the optimum concentration and exposure
time should be investigated for each fish species, since each fish species
egg presents different sticking characteristics. High concentration and
exposure time can result in egg hardening and consequently high
mortality of the embryos.
8.3. Packaging
In the past decades, oil derived polymers have been used extensively
in the packaging industry (Shchipunov, 2012) and nowadays many
studies have been carried out to use natural materials in the packaging
of different goods still presenting the needed characteristics (Weber
et al., 2002; Ghaderi et al., 2014). Some of the natural polymers-based
films which are used in the packaging industry include chitosan, chitin,
starch and cellulose (Tang et al., 2012; Rhim and Ng, 2007). Particu-
larly, nano-sized cellulose has attracted lots of interest and has been
extensively studied (Charreau et al., 2013).
Oxidation is a chemical reaction which results in the production of
free radicals, leading to a chain reaction which can cause cells damage.
A molecule which is able to prevent the chain oxidation reaction of
other molecules is called antioxidant (it is a free radical scavenger).
Foods degradation results in the creation of free radicals, while poly-
phenols act as antioxidants preventing this phenomenon (Fang and
Bhandari, 2010). In different studies, it has been demonstrated that
tannins have antioxidant properties (Missio et al., 2017; Beninger and
Y. Shirmohammadli et al.
Hosfield, 2003; Noferi et al., 1997). Using tannins in packaging to-
gether with other natural polymers like nanocellulose has been in-
vestigated to prepare a natural polymer with antioxidant properties
which can be used for different applications like food/pharmaceutical
packing, tissue engineering, wound dressing, etc (Zhou et al., 2016b).
Missio et al. (2018) have prepared a completely natural and biode-
gradable nano-cellulose film which had a very hydrophobic structure
(excellent air impediment), was very heat resistant and showed gradual
and proper antioxidant releasing property. Such findings show a very
promising future for tannin in the packaging industry. To expand its
application some more studies are needed to better understand the
nanocellulose-tannin interaction, to optimize the combination percen-
tages of tannin and nano-cellulose for different purposes etc.
9. Animal food and feeds
Different kinds of drugs and methods are used for ruminants in
order to control parasites. Among these, feeding the animals with plants
which are high in tannins has been investigated as a step toward or-
ganic farming systems (Athanasiadou et al., 2000; Hoskin et al., 2000).
These tannins can be used along with other substances in animal's food
or can be fed to animals in the form of some tannin-rich plant species.
Investigations have proven that another benefit of condensed tan-
nins are their ability to diminish cattle’s rumen deterioration of dietary
protein and also enhance the amino acid absorption in the small in-
testine. Thus, it is suggested to use tannins (about 2%–4.5% dry mass of
food) to improve digestion of dietary protein by protecting proteins
against bacterial elimination of amino acids and inhibiting bloats in
animals. Conversely, tannins shortcomings when using excessive tan-
nins (> 5.5% dry mass of food), include: fiber digestion impairing and
tannins ability to bind proteins and carbohydrates, hence to decrease
nutrient availability for grazing animals. This should not be ignored
(Hervás et al., 2003; Goel et al., 2005). However, the mechanism by
which tannins decrease the digestion of ruminal protein and promote its
utilization is not precisely understood. Condensed tannins have shown
that they possess a more marked influence on animal's digestion, and
hydrolysable tannins can cause toxin manifestations as a result of hy-
drolysis in cattle’s rumen (Goel et al., 2005).
Generally, condensed tannins are able to enhance digestibility of
nitrogen in grazing ruminants. Furthermore, they increase growth of
wool, production of milk, and amount of lambing in sheep and cattle,
reducing worm burdens and improve animal welfare (Mueller‐Harvey,
2006). Condensed tannins to feed animals can be obtained from farm
legumes such as white and white and red clover (Min et al., 2003). In
very high quantity, nutrients can act as a toxic and detrimental sub-
stance, but in required quantity they are very beneficial for health
(Lyman et al., 2008). Thus, these findings infer that more research is
needed to optimize the dosage of different kinds of tannins for different
kinds of animals.
10. Environmental applications
10.1. Adsorbents for proteins and antibiotics
Protein-precipitation and formation of insoluble complexes with
tannins has been known since ancient times for leather tanning and in
the food industry. Phenolic hydroxyl and hydrophobic areas in the
proanthocyanidins react with the carbonyl groups and complex with
the amino and amido groups of amino acids of proteins, respectively, to
insolubilize them (Girard et al., 2018). Studying the complex of tannins
and protein can be beneficial for altering food structure. Some research
investigated this potential to exploit this characteristic to include de-
livery of micronutrients (Links et al., 2016), to increase wheat gluten
strength (Girard et al., 2016) and to decrease glucose metabolism
(Amoako and Awika, 2016). Proteins in beverages such as wine, beer
and juice affect using the taste and color negatively by creating small
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Industrial Crops & Products 126 (2018) 316–332
lumps during storage and their elimination by using tannin is ad-
vantageous (Chibata et al., 1986). Furthermore, complexes of tannins
and protein in animal feed are of critical importance since they affect
the forage protein, diminish emissions of greenhouse gas from rumi-
nants, decrease ammonia and urea excretion and inhibit bloat (Zeller
et al., 2015). The influencing factors on the protein-tannin interaction
include pH, temperature, tannin : protein ratio, their structural chem-
istry, etc. (Naczk et al., 1996).
Accumulated antibiotics are one of the substances which should be
eliminated during water/wastewater treatment in order to prevent fu-
ture antibiotic resistance (Dodd, 2012). This goal can be reached by
electrochemical treatments (Dirany et al., 2012), membrane bioreactor
(Kovalova et al., 2012) and activated carbons (Acosta et al., 2016).
Activated carbons are used in different fields such as air purification
(Choi et al., 2016), water/wastewater treatment (Zietzschmann et al.,
2016) and purification of pharmaceutical products (Li et al., 2015). In a
recent research work Selmi et al. (2018) reported that in terms of an-
tibiotic adsorption, mimosa tannin and agave americana fibers as pre-
cursors of activated carbons resulted in a better performances than
commercial activated carbons.
10.2. Metal ions recovery
Access to clean water for everyone is one of the main necessities and
rights in every society. In order to satisfy this need, water treatment has
been one of the essential stages to provide clean water without con-
taminants (Ali and Gupta, 2006). Toxic metals contaminations, such as
by lead, mercury, cadmium, and copper is lethal and should be elimi-
nated from the water matrix since if they are consumed, they will ac-
cumulate in the body and cause serious diseases. Current means of
wastewater treatment (such as chemical precipitation, ion exchange,
and electrochemical methods) are expensive and usually do not provide
a treatment sufficient enough to satisfy the relevant regulations
(Luzardo et al., 2017). Amid various means of water treatment, ad-
sorption has been known to be the most effective and economical one,
especially for the treatment of contamination at low concentration
(< 100 mg L−1) in a large volume (Xu et al., 2017). The type of ad-
sorbent is of basic importance in the wastewater treatment process.
Since tannins possess adjacent phenolic hydroxyls, they display specific
affinity to metal ions and the ability to chelate them (Slabbert, 1992; Oo
et al., 2009; Tondi et al., 2009). One of the problems with tannin in
watery matrices is their water solubility and in order to use tannins in
water treatment industry, tannins should be insolubilized/immobilized.
For this purpose some matrices such as nanocellulose, collagen, meso-
porous silica, activated carbon, etc. have been used (Xu et al., 2017).
Moreover, condensed tannin gel adsorbent has been investigated suc-
cessfully in order to gold (Ogata and Nakano, 2005), palladium (Kim
and Nakano, 2005) (which is known as valuable metals), and lead
(Zhan and Zhao, 2003) (which is a very toxic and accumulate in food
chain) recovery from aqueous solutions. Much recently the potentiality
of tannin extracted from pine tree bark was evaluated for antimony (Sb)
uptake from water solutions (Bacelo et al., 2018). The tannin was firstly
polymerized by the sodium hydroxide and formaldehyde. Then, the
produced adsorbent was assessed on the sequestration of different
species of Sb (III and V). The result showed that it was effective for both
species, in diluted and heavily-contaminated waters.
Bacelo et al. (2016) suggested that there is still room for innovation
about tannin-based biosorbents such as use of alternative tannin
sources, optimization of chemical modifications, study the effect of
competing ions or substances in solution, and etc.
11. Medicinal applications
Since centuries ago, different kinds of plants which are reach in
tannins have been used in traditional medicines all around the world
(Scartezzini and Speroni, 2000; De las Heras et al., 1998). An old
Y. Shirmohammadli et al.
example of tannin use is green tea with antioxidant and antitumor ef-
fects (Yoshizawa et al., 1987; Perchellet et al., 1992). Tannins are
considered as astringent substances which means that they bond pro-
teins in order to form a protective layer (which happens in leather
tanning). In the terms of topical application, this protective layer can
improve curing speed of ulcers, wounds and burnings. This protective
layer stops bleeding, prevent infection, shields against mechanical and
chemical irritation, bacterial, and micro-organisms (de Jesus et al.,
2012). Naturally hydrolysable tannins have been known to have more
astringent characteristics than condensed tannins and show more of this
ulcer curative feature.
Tannins are known to have anti-inflammatory effects which help to
minimize symptoms of alimentary diseases such as esophagitis, gas-
tritis, enteritis, and inflaming bowel sickness (Ashok and Upadhyaya,
2012). Hydrolysable tannins also have shown therapeutic effects
against Acyclovir-resistant herpes viruses when it is applied on the
mucous membrane of the mouth (Quideau et al., 2004). Moreover,
tannins have shown antibacterial (Akiyama et al., 2001), antiviral (Lu
et al., 2004) and antiparasitic (Kolodziej and Kiderlen, 2005) char-
acteristics.
Recent study have indicated that extracts of Kakadu plum
(Terminalia ferdinandiana) leaf which are high in tannins have shown
inhibitory influence against microbial triggers of autoimmune in-
flammatory disorder (Courtney et al., 2015). This effect is because of
tannins action against bacteria which is one of causes of this kind of
autoimmune disease. Reach tannin plants also have shown curative
effects against pathogens causing diarrhea both in animals and humans
and used instead of antibiotics to cure this disease (Würger et al., 2014;
Siqueira et al., 2012).
As far as tannins can interfere with digestion and nutrient absorp-
tion, long term use of strongly astringent herbs is not recommended and
should be cautiously used in the patients with inflamed or ulcerated
gastrointestinal tract (Bone and Mills, 2013). Tannins also can result in
nausea which is probably as a result of protein binding in the stomach.
High levels of absorbed tannin in the blood can cause constipation,
hepatotoxicity or damages to other organs. Ruminants that are fed with
highly tannin containing plants are particularly susceptible to these
effects. Furthermore several studies on the use of tannins as anticancer
and antiviral agents have been reported a summary of which has been
reported (Pizzi, 2008).
12. Status of the technologies, industrial scale applications,
limitations
Some of the technologies described are already applied industrially,
some to a limited scale, while others are still emerging technologies.
Thus leather-making using vegetable tannin extracts is in operation
already from 1870, although the use of vegetable tannins is decreasing
for this application due to two factors: (i) the substitution of leather
shoe soles by synthetic materials and (ii) the use of chrome salts tanning
for soft leathers such as shoe uppers and other applications. It is this
decrease that has prompted interest in other possible applications of
tannins. The second technology that is already applied industrially is for
wood adhesives for panel products. This application started to grow
industrially from the early 1970′s and there are now factories in South
Africa, Australia, two South American countries (Valenzuela et al.,
2012) and even in a couple of factories in Europe and Japan where
tannin adhesives for wood panels are now used. The limitation in their
use in this field is the enormous volume of oil derived adhesives used in
this field. Literally, there is not enough extraction factories around to
satisfy possible demand to substitute synthetic oil derived adhesives. In
the last few years some new tannin extraction factories have indeed
been built or are under construction, namely in Sumatra and in Chile,
but while the potential for tannin extraction is huge the growth of
additional factories is slow. An area where limited industrial utilization
is occurring, now for several years is as fortifiers and waterproofer of
327
Industrial Crops & Products 126 (2018) 316–332
corrugated cardboard starch adhesives. The percentages of tannin ex-
tracts used are relatively small and their use is focused, in some
countries, on corrugated cardboards for boxes for boat transport of
fruits through the moist air of the tropics, to avoid the boxes to fall
apart. This application has been running for a few decades now.
Medicinal applications are also known for a number of years such as
the use of monoflavonoids in pharmacopea. These are specialized,
highly purified tannins, for pharmaceutical use. This is a field of
growing interest for a number of novel applications.
Equally, metal ions recovery is now in industrial practice for many
years. The most interesting example of this is the separation of the rare
metal Germanium from Copper ore. The tannins complexes pre-
ferentially Germanium and thus this valuable resource can be isolated
from Copper, after which the tannins are burned to recover the metal.
Tannins are also extensively used for many years in the beverage
field. Thus, they are used to precipitate proteins in wine-making.
Equally, many people do not realize that highly purified tannin extracts
are added to beer and fruit juices to give them the taste that otherwise
they would not have. The percentages are small, between 1% and 3%
but thir utilization is extensive in the beverage field.
One of the older uses of tannin extracts is as corrosion inhibiting
primers for metal coatings. This used started commercially in the UK in
the 1960’s. It was then discontinued and it is now coming to the fore
again in a number of countries.
All the other applications described in this review are emerging
technology, some of them, such as fireproof foams, nearer than others
to a possible industrial exploitation, but emerging technologies none-
theless. Other technologies in this field are also under consideration,
but they are far less developed as yet than the ones described in this
review.
13. Conclusions
Tannin is a bio-phenol with excellent antioxidant properties that
can be widely used in industry as a green and sustainable raw material.
In this review, the current industrial uses of tannins and also the po-
tential applications of them are thoroughly investigated. The use of
biosourced alternatives such as tannins using them instead of toxic
synthetic substances (such as phenol, diisocyanate, chromium, etc.) can
ultimately lead to a healthier environment. Tannins extraction can be
economically affordable in the case of extracting them from plant parts
of high tannin contents and using proper extraction methods (time,
temperature, solvent, particle size etc.). It should also be noted that
tannin is a renewable resource and there also are many sources for its
production.
Tannins have a wide range of applications due to their chemical
characteristics and structure differences. In some applications, the
phenolic structure of tannin and in others its antioxidant properties,
sometimes both, are important. Some tannin applications (such as
leather tanning) have a historical background, but research still con-
tinues to optimize and increase their efficiency.
Tannin copolymers with other natural materials, such as lignin and
furan derivatives, have introduced new applications for tannins with a
higher percentage of bio materials. As tannins play a prominent role in
general defense strategies of plants, extensive research has been re-
cently done to use them in protecting of perishable wood species
against biological threats (against insects and fungi). Wood protection
with tannins can be carried out either alone or in combination with eco-
friendly pesticides. The co-polymerization of tannins with other poly-
mers (like furan components, caprolactam, etc.) not only can be con-
sidered as yielding a simple preservative, but also can act as a mod-
ifying polymer to improve physico-mechanical properties of wood.
Acknowledgments
The authors would like to gratefully acknowledge the financial
Y. Shirmohammadli et al.
contribution of Iran national science foundation.
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