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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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Younes Shirmohammadli Davood Efhamisisi

University of Tehran University of Tehran


A.Pizzi Pizzi
University of Lorraine


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Industrial Crops & Products 126 (2018) 316–332

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Industrial Crops & Products

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

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


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;

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

Corresponding author.
E-mail address: (D. Efhamisisi).
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)
Norway spruce 18.2
Fig. 1. Schematic representation of a hydrolysable tannins molecule.
Douglas fir 12
(Pizzi, 2003a). The main repeating units of condensed tannins (also Scots pine 7.1
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
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.

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

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)
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. Industrial Crops & Products 126 (2018) 316–332

manufacture of adhesives with two approaches: polycondensation re- biocide, panels had improved biological resistance against termites and
actions or autocondensation reactions. fungi (Efhamisisi et al., 2016).
Tannins can also be copolymerized with synthetic adhesive. The The tannins hardened by the autocondensation approach, induced
purpose of this are often (1) to decrease formaldehyde emission from either by the lignocellulosic substrate or by Lewis acids only resulted in
synthetic resins (when a few percentages of tannin are added) or (2) to bonds of interior-grade quality (Pizzi, 2003a, 2006).
improve water resistance of tannin-based adhesives (when a few per-
centages of synthetic resins are added). Addition of a few percentages of 4.2. Epoxy adhesives from tannins
polymeric isocyanate (pMDI) (from 10% up to 30%) to mimosa tannin
adhesives yielded joints with very high Young's modulus values (more Recently, various plant sources such as tannins were used to make
examples in Table 2) (Osman, 2012; Pizzi et al., 1993). bio-based epoxies (Mashouf Roudsari et al., 2017). It should be noted
that catechin and gallic acid are among the most studied tannin deri-
4.1.1. Polycondensation with aldehydes or non-aldehyde hardeners vatives and used as models of condensed and hydrolysable tannins re-
The polycondensation reactions of tannins with aldehydes or dif- spectively. Catechin was epoxidized either by reaction with epi-
ferent non aldehyde hardeners (glyoxal, furfuryl alcohol, hexamine chloridrin (ECH) or by alkylation with unsaturated halogenated
etc.) have been used extensively. In the production of wood based compound followed by its oxidation (Boutevin et al., 2010). A full
composites (WBC), tannin-formaldehyde adhesives have been success- characterization of the obtained compounds shows the presence of a by-
fully commercialized for several years and are used in some countries product with a benzodioxane group, which then decreases the average
(Pizzi, 2016; Valenzuela et al., 2012). The exterior-grade WBC bonded epoxy functionality (Nouailhas et al., 2011). These by-products result
with tannin adhesives is most of the time produced by polycondensa- from internal cyclization reaction between phenolic alcohol in ortho-
tion of tannins with aldehyde hardeners. The reaction of tannins with position and ECH.
aldehydes has always resulted in weather- and boil-proof adhesives. More recently two studies by Jahanshahi et al. (Jahanshahi et al.,
Furthermore, these adhesives possess very low formaldehyde emission 2016a, 2016b), one on the formation and testing of polyflavonoid
(Pizzi, 2006). tannins epoxy resins were published, the second of which was of par-
Of further interest for tannin based adhesives is their reaction with ticular interest being an epoxidized tannin acrylic that allowed rapid
hexamethylenetetramine (hexamine) used as a non-aldehyde-yielding curing of the epoxy tannin without having to use a hardener.
hardener under alkaline conditions (Pizzi, 1994b). Hexamine has been Gallic acid epoxidation with epichlorhydrin was first reported by
proven to not decompose to formaldehyde and ammonia (Kamoun and Tomita and Yonezawa (1983). Aouf et al. (2013) reported conditions
Pizzi, 2000; Kamoun et al., 2003) when in presence of a reactive con- allowing the synthesis of tetra epoxy gallic acid. Previous studies only
densed tannin. Thus, formaldehyde emission from these adhesives is reported functionalization with two to three epoxy groups. Also it was
very low and limited exclusively to that generated by the heating of recently proposed another synthesis pathway leading to epoxy pre-
wood itself. Panels bonded with tannin-hexamine adhesives, depending polymers from gallic acid allylation by reaction of gallic acid with allyl
on the conditions under which they are prepared, can meet both in- bromide, followed by double bond oxidation using m-chloro-perbenzoic
terior- and exterior-grade standard specification requirements. Slow acid (Nouailhas et al., 2011).
reacting tannins such mimosa and quebracho can be used with hex- Benyahya et al. (2014) proposed direct use of condensed tannins
amine to prepare interior grade particleboard. Exterior-grade particle- extracted from green tea which are naturally rich in polyphenols for the
board can be obtained with faster tannins under different pressing synthesis of aromatic bio-based epoxy oligomers.
conditions (Pizzi et al., 1997). The most spectacular studies about
polycondensation or copolymerization of tannins with different hard- 4.3. Tannin-based bio-adhesives for grinding wheels, angle grinder disks and
eners or resins are presented in Table 2. automotive brake pads matrices

4.1.2. Autocondensation reactions without hardeners A 100% biosourced thermoset material based on condensed tannin-
The term “autocondensation” refers to the opening of the pyran furanic thermoset resins has been used as the resin matrix of solid
rings under alkaline or acidic conditions in the absence of external grinding wheels (Lagel et al., 2015a). Moreover, this new thermoset
hardeners (Pizzi et al., 1995). This aspect of tannin chemistry in- material is produced by a simple process, which can be easily in-
troduces self-polymerization of tannins to yield a cross-linked poly- dustrialized. Grinding wheels based on this resin, additioned of either
phenolic network. tung oil or linseed oil and hardened with p-Toluensulphonic acid were
Different tannins present different autocondensation rates. Mimosa used for bonding different mineral and organic abrasive powders were
and quebracho tannins present a slower autocondensation than pecan developed and characterized. These grinding wheels show excellent
nut and pine tannins (Pizzi and Stephanou, 1994). With fast tannins just abrasiveness properties when compared with a commercial grinding
contact with the lignocellulosic surface is enough for rapid self-poly- wheel. More recently grinding wheel based on the lignin and furfuryl
merization (Pizzi, 1994a; Pizzi et al., 1995). Thus, slower tannins need alcohol were also developed (Liang et al., 2018). The resin developed
more time and results in a lower internal bond strength of the bonded presented a glass transition temperature (Tg) of around 170 °C and as
panel because of their slow hardening rate. for the tannin-furanic matrices presented a better performance than
Meikleham et al. (1994) found that autocondensation of various grinding wheels bonded with synthetic phenol-formaldehyde adhesive
tannins is inducible by weak Lewis acids such as silica, silicates, boric resins.
acid and aluminum chloride. Actually, Lewis acids act as a catalyst for By using the same biosourced raw materials, condensed tannins and
tannins autocondensation. The problems related to the slow reacting furfuryl alcohol, a thermoset resin was developed and used and tested
tannins can be solved by Lewis acids-based autocondensation systems for a new application: as a resin matrix of solid grinding disks for angle
(to accelerate it) which results in the need for a lower press temperature grinders (Lagel et al., 2015b). The manufacturing procedure developed
and press time as well as in higher internal bond strengths (Pizzi et al., is particularly easy. Cutting and grinding disks based on this green resin
1995; Garcia and Pizzi, 1998a, 1998b). Most recently, Efhamisisi et al. were used for bonding different sizes of abrasive particles of aluminium
(2016) reported that poplar (Populus deltoides) plywood panels made of trioxide. The matrices used contained, on top of the basic quebracho or
quebracho tannin adhesive (50% water solution) and a small propor- mimosa tannin-furfuryl alcohol resin matrix, small proportions of
tion of boric acid (2%–4% based on the total resin) are able to meet the polyethylene glycol (PEG 400), tung oil, Xiameter OFX-0193 Fluid
bonding requirements for interior-grade panels of the relevant Eur- (DC193), namely a silicone polyether copolymer emulsifier from Dow
opean standard (EN 314-2, 1993) Since boric acid is also an effective Corning, p-Toluene sulphonic acid hardener and a majority of

Y. Shirmohammadli et al. Industrial Crops & Products 126 (2018) 316–332

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 corrugated cardboard are based on the addition of mimosa (wattle)
cover a fine fiberglass net (Fig. 4). These angle grinder discs were tannin, urea-formaldehyde resin, and formaldehyde to a typical Stein-
characterized and showed excellent abrasiveness and cutting proper- Hall starch formula of 18–22% starch content (McKenzie and Yuritta,
ties. Their mechanical resistance was found to be comparable to that of 1972; Saayman and Brown, 1977; Clusters et al., 1979). The mimosa
commercial grinding discs bonded with synthetic phenolic resins. tannin-urea-formaldehyde copolymer formed in situ, and any free for-
By using the same or similar biosourced raw materials as above maldehyde left in the glue line is absorbed by the mimosa tannin ex-
(condensed tannins and furfuryl alcohol) a biosourced thermoset resin tract. The mimosa tannin extract powder should be added at level of
was also developed as a resin matrix of automotive brake pads (Lagel 4–5% of the total starch content of the mix (i.e., carrier plus slurry)
et al., 2016; Al-Marzouki et al., 2017). The manufacturing procedure (Clusters et al., 1979). Successful results can be achieved in the range of
developed again was particularly easy. Automotive brake pads based on 2%–12% of the total starch content, but 4% is the recommended
this green resin were characterized and showed excellent braking starting level. The final level is determined by the degree of water
properties and wear resistance when used under real car, full scale test hardness and desired bond quality. This wattle extract-UF fortifier
conditions. The basic resin and glue mix used were the same as in- system is highly flexible and can be adapted to damp-proof a multitude
dicated above for the angle grinder disks, but contained furthermore of basic starch formulations. Plant trials and industrial production of
small amounts of graphite, neoprene, glycerol phosphate acidic ester. this application has taken place for many years (Clusters et al., 1979).
Furthermore mineral (iron) wool and fiberglass cut in small pieces were Recently the addition of four commercial tannins on the properties
added. Not only the new resins were biosourced from renewable ma- of starch-based adhesive was evaluated by using fundamental rheolo-
terials but also they did not contain any formaldehyde. Their me- gical techniques (Marino et al., 2014). Experiments showed a double
chanical resistance was found to be comparable to that of commercial effect of tannin addition on mechanical properties of the starch-tannin
automotive brake pads bonded with synthetic phenolic resins. adhesive. Tannin addition caused a weaker starch network, but on the
other hand the polymeric components of tannins interacted with each
4.4. Tire cord adhesives other reinforcing the starch network.

Tire cords are the vital tire reinforcement which results in the 4.6. Coatings
strength, controlled deformation and comfort of riding. Adhesion of tire
cords to the tire rubber plays a very important role in the prevention of 4.6.1. Tannin-based polyurethane surface coatings with or without
blowout risks (Niroomand et al., 2017). Less than 10% of the worldwide isocyanates
resorcinol adhesives are consumed as the tire cord adhesives (Pizzi, As regards the preparation of polyurethane adhesives starting from
2003b). Extracts of condensed tannins have shown that they can be condensed or hydrolysable tannins two approaches have been taken: (i)
used successfully as a tire cord adhesive. For this purpose, both tannin- modification of the flavonoid tannin in order to render easier the re-
resorcinol-formaldehyde (Hamed et al., 1989), thermosetting tannins action with isocyanates. This is due to the difficulty in reacting the
formulation (Hemingway and Karchesy, 2012) and also cold setting flavonoid hydroxyl groups directly with isocyanates. In this type of
tannins adhesives (Gómez-Jiménez-Aberasturi, 2017) have been ex- application the tannins are in direct competition with more suitable
perimented successfully. natural polyols, of which the literature abounds, to prepare semi-bio-
Investigations have shown that condensed tannins can replace a sourced polyurethanes; (ii) the use of a total no-isocyanate approach to
proportion or all of the resorcinol in a standard resorcinol-for- improve the environment-friendly character of such adhesives.
maldehyde-latex dip, especially in the case of using poly ester cord. For the first approach, benzoylation to reduce the number of hy-
Furthermore, pecan nut pith tannin extract has shown that if used to droxyl groups of the tannin before reaction with diisocyanate was tried
substitute resorcinol adhesive totally, the tire cord pull-out force can a long time ago (Pizzi, 1979a). A more studied approach has been to use
reach twice as high as what obtainable with the standard dip (Hamed lignin and lignosulphonate/hydroxypropylated to prepare urethanes
et al., 1989). (Glasser et al., 1984, 1986; Glasser and Leitheiser, 1984) although this
approach has been more directed towards coatings than adhesives. The
4.5. Fortifiers of starch-based corrugated cardboard adhesive same and more studied approach has been to prepare novel thermo-
setting tannin-based polyurethane adhesive resins using the hydro-
Starch is an important biopolymer in the adhesive field which is xypropyl and hydroxybutyl derivatives of purified condensed tannins
extensively used in the paper industry (Liu et al., 2014). Tannins are from Pinus pinaster bark and other condensed tannins species by reac-
very interesting additives used for starch-based adhesive because of tion with diisocyanates (García et al., 2013, 2014, 2015, 2016). Hy-
their potential effects on both adhesive properties and water-resistance. droxypropylation and hydroxybutylation are one of the approaches
The adhesives developed for the manufacture of damp-proofed used to react polyphenolic materials with isocyanates to obtain

Y. Shirmohammadli et al. Industrial Crops & Products 126 (2018) 316–332

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- transition temperatures and Mn (Number average molecular weight)
action of flavonoid tannins with isocyanates, due to the introduction of lower than 30,000 g/mol−1. All the work on non-isocyanate poly-
much more approachable hydroxyl groups into the tannin structure, urethanes is concentrated on synthetic materials. Thus, while iso-
thus increasing reaction yield. cyanates are definitely not used, synthetic diamines and synthetic di-
The same approach, thus to introduce in the tannin structure more cyclocarbonates, both of no natural origin are used, yielding
available −OH groups but through a reaction totally different from polyurethane resins that are not biosourced. While use of glycerol has
hydroxypropylation, consisted in reacting an aldehyde with the tannin been reported (Fleischer et al., 2013) the percentage of biosourced
and then use the hydroxyl groups formed by its addition onto the fla- material is still lower than the approach of using an isocyanate reacting
vonoid structure, before their further condensation with other flavo- with a natural polyol.
noids, to react with an isocyanate (Pizzi et al., 1993; Valenzuela et al., Only very recently approaches to non-isocyanate polyurethane ad-
2012; Pizzi and Walton, 1992). Such a system has been used and is used hesives has aimed at not only eliminating the toxic isocyanate but also
industrially for wood adhesives (Valenzuela et al., 2012). More recently at improving the percentage of biosourced material composing the
the system has been adapted by eliminating formaldehyde and sub- “green” polyurethane adhesive. The same reaction used for synthetic
stituting it with glyoxal with good results (Basso et al., 2014) rendering materials has been used with both a hydrolysable tannin and condensed
the approach even more environmentally interesting. flavonoid tannins, these are natural renewable materials, by reacting
However, isocyanates are harmful to human health. Thus, the pre- them first with dimethyl carbonate, thus a non-cycqlic carbonate, fol-
paration of polyurethane adhesives of a high level of biosourced and lowed by reaction with hexamethylenediamine (Thébault et al., 2014,
environment friendly material it involves by necessity the synthesis of 2015) to obtain non-isocyanate urethanes of the type shown in Fig. 6.
non-isocyanate polyurethanes. This approach which avoids the use of This was the first approach to obtain a biosourced polyurethane
any isocyanate is attracting increasing interest. It is based on the without using isocyanates, although, the percentage level of biosourced
polycondensation of diamines with dicyclocarbonates to lead to poly- material was only 45%–50%, the diamine and the carbonate being still
hydroxyurethanes. This reaction has been studied by a few research synthetic materials. As the amination of condensed tannins, thus the
groups (Rokicki and Piotrowska, 2002; Whelan and Cotter, 1963; conversion of their hydroxyl groups into amino groups, is an easy re-
Kihara and Endo, 1993; Kihara et al., 1996; Tomita et al., 2001a, action (Braghiroli et al., 2013), the aminated tannin was used to sub-
2001b, 2001c; Birukov et al., 2014; Figovsky and Shapovalov, 2002; stitute the hexamethylenediamine, further improving to more than 70%
Camara et al., 2014; Blattmann et al., 2014; Boyer et al., 2010; Kim of biosourced material in the final polyurethane, and this without using
et al., 2001; Ochiai et al., 2005; Ubaghs et al., 2004; Fleischer et al., any isocyanate (Thébault et al., 2017) to obtain flavonoid oligomers
2013) and leads to polyhydroxyurethanes of relatively low glass linked by urethane bridges.

Fig. 6. Non-isocyanate diurethane obtained by reacting a precarbonated flavonoid tannin with a diamine (Thébault et al., 2015).

Y. Shirmohammadli et al. Industrial Crops & Products 126 (2018) 316–332

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).
Fig. 7. Example of oligomers obtained by the reaction of condensed flavonoid
tannins and triethyl phosphate (Basso et al., 2017).
5. Tannin-impregnated paper: high pressure and low pressure
4.6.2. Tannin binders for Teflon coatings to metals
Recently a considerable effort has been made to develop tannin- Tannin-furanic high pressure laminates are the tannin-furanic resin
based adhesives capable of bonding Teflon to metal, namely steel and as the bonding agent, were prepared by acid catalysis. The mixture of
aluminium, and capable of withstanding high temperatures of opera- mimosa tannin, furfuryl alcohol and pTSA (para-toluene-4-sulphonic
tion (Maris and Joutang, 2007; Basso et al., 2014, 2017). The break- acid) were prepolymerized in a rotary at 60 °C for 30 min. The resin so
through in this bonding application, where not only tolerance to high prepared was used to impregnate alpha cellulose paper and the papers
temperature but also total absence of formaldehyde for food application so prepared were pressed together to bond in a solid reinforced sheet
were needed, came with the discovery of the reaction of polyphenols forming high pressure laminates (Fig. 8) (Abdullah et al., 2014). The
such as tannin and even lignin (Basso et al., 2014) with triethyl phos- high pressure laminates prepared were tested for abrasion resistance,
phate (TEP). cross-cut adhesion test, water vapor resistance and staining test and
This novel cross-linking reaction is based on the reaction, oligo- compared with phenol-formaldehyde high pressure laminates from.
merisation and cross-linking of tannins by TEP in presence or absence of Color and gloss measurement were also done.
ammonia (this latter being preferable to the yield). Reaction of con- Equally, paper sheets impregnated with a tannin-furanic resin were
densation and cross-linking of catechin monomer and of mimosa tannin applied in a hot press onto a wood particleboard substrate; the resin in
itself, as well as of resorcinol with TEP were investigated (Basso et al., the impregnated paper functioning also as the adhesive of the im-
2017). The chemical analyses revealed that reaction occurs mainly on pregnated paper sheet onto the board (Pizzi, 1979b; Abdullah et al.,
the C3 of the flavonoid heterocycle ring and on the aromatic C4′ and 2013a, 2013b). The surface quality of these low pressure paper surface
C5′ carbons of the flavonoids B-ring (Fig. 7). The resin so obtained can laminates with a mimosa tannin resin was comparable to the com-
produce hard thermoset plastics and films resistant up to temperatures mercial synthetic melamine-urea-formaldehyde (MUF) resin. The
in excess of 400 °C. 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
4.6.3. Corrosion inhibitors
black color that render them suitable only for application in cement
In the industry, iron, steel and alloy parts exposed to acid conditions
building shutter boards. The moisture content of the impregnated pa-
starts to corrode by two reactions: chemical and electrochemical. This
pers were varied between 23% and 10%. Impregnated papers with
phenomenon leads to an enormous loss due to the need to replace or fix
mimosa tannin adhesive resin gave excellent results for water vapor
these metal parts (Abdullah Dar, 2011; Talib et al., 2014). One of the
resistance and the cross-cut test according to relevant standards.
practical methods to prevent metal corrosion is using anticorrosion
Moisture content of the impregnated papers were found to influence the
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 Fig. 8. Example of a high pressure laminate. Mechanical gear composed of 30
was able to extend the duration of painting more than 50% if applied tannin-furanic impregnated papers pressed together (Abdullah et al., 2014).

Y. Shirmohammadli et al. Industrial Crops & Products 126 (2018) 316–332

abrasion resistance for both the mimosa tannin resin and the MUF resin protection of tannin/hexamine + boric acid showed also high potential
impregnated papers. Color measurements were carried out to relate the to produce durable plywood panels designed for both interior and
different paper colors to the two different moisture contents used. Im- humid conditions (Efhamisisi et al., 2016, 2017). As shown here, a large
pregnated papers with mimosa tannin resins at 23% moisture content amount of research has been carried out on tannin based preservatives
have a lighter shade compared with impregnated papers with mimosa possibly promising a new generation of future wood protectants.
tannin resins at 10% moisture content. More recently the hardening of tannins with furan components such
as furfural and furfuryl alcohol has been evaluated as a completely
6. Wood protection biosourced polymer (Abdullah and Pizzi, 2013; Tondi, 2017). Although
the modification of wood properties with furfuryl alcohol is well
Wood and items made from wood are organic and lignocellulosic documented and commercialized, it seems that the reaction of furfural
materials, which are prone to be attacked by biological deterioration (as aldehyde) with tannins can be another modifying approach to in-
agents, creating a need for preservative-treated wood. Concerns about troduce biosourced wood preservatives.
the durability of solid timbers have resulted in the use of chemical
treatments by a variety of application methods including pressure im- 7. New materials
pregnation, immersion, diffusion, and vacuum-assisted treatments
(Reinprecht, 2016; Cooper, 2007). Nowadays, because of public 7.1. Foams
awareness about heath and dangers of toxic substances, environmental
performance and sensitivity of wood preservatives are playing an in- Studies considering the tannins and furfuryl alcohol combination as
creasing role in their development and use (Shmulsky and Jones, 2011). an adhesive have resulted in the creation of almost totally biosourced
Researchers are looking for natural materials with herbal or animal foams. The first report of feasible tannin-furfuryl alcohol foams ap-
origins to replace old toxic wood preservatives (Singh and Singh, 2012). peared in 1994 (Meikleham and Pizzi, 1994). This was followed by
A lot of attempts carried out to improve the bio-durability or other numerous different studies implemented in order to eliminate these
properties of wood as well as wooden composites with tannin-based foams shortcomings and to better understand their characteristics to
preservatives. make them more efficient (Li et al., 2012a; Lacoste et al., 2013; Zhao
Laks et al. (1988) reported that tannins extracted from the bark of et al., 2010).
Pinus taeda have some limited effectiveness against fungal attack, but Tannin foams are made in three stages: mixing, expansion and
that they are more effective in the complexed form with copper (II) curing, respectively. In first stage, all ingredients including: tannin
ions. The association between tannins and boric acid could also be extract, furfuryl alcohol, formaldehyde, blowing agent, additives and
another remedy. Pizzi and Baecker (1996) used preservative solutions water are added and mechanically stirred until achieving a homo-
based on tannins and boron in which boric acid was used to induce geneous and notable viscous blend. In the second stage a potent acid as
hardening reactions of polyflavonoid tannins, promoting the formation a catalyst is added to the blend. Furfuryl alcohol acts as an agent for
of a cross-linked flavonoid oligomer network in the xylem structure. heat generation for its reaction with other ingredients and also for its
Equally, boric acid can be partially fixed into the wood by the trapping- self-polymerization reaction. By evaporating the solvent (physical
in the tannin polymer. blowing agent) as a result of rising temperature, tannin and furfuryl
The modification of mimosa tannin with a copper-ammonia com- alcohol starts to cure at the same time. Finally in the last step the
plex also appeared to promote the antidecay properties of treated wood, network of tannin, furfuryl alcohol and formaldehyde starts to harden
while unmodified tannin had no preventive effect on the fungal attack and stabilizing (Tondi and Pizzi, 2009).
(Yamaguchi and Okuda, 1998; Yamaguchi and Yoshino, 2001). In a Manufacturing companies of polyurethane and carbon foams have
new study it was, however, reported that impregnation of wood with some growing interest toward using tannin-furfuryl alcohol in their
the 5% or 10% aqueous solution of mimosa tannin can increase re- products, because with this new combination they can possibly solve
sistance of wood against white rotting fungus (Silveira et al., 2017). their products drawbacks like low fire resistance and the lack of en-
Termiticidal properties of tannins were also studied (Tascioglu et al., vironment presents friendliness (Basso et al., 2014). Because for-
2012); the woods treated with mimosa and quebracho tannins showing maldehyde presents numerous shortcomings and threats, recent re-
good resistance against the attack of subterranean termites at the high searches have succeeded to produce tannin-based foams without any
level of tannin loading inside the wood (∼80–100 kg of tannins in each formaldehyde and/or blowing agent addition (Basso et al., 2013).
cubic meter of wood). However, the tannin of the pine bark appeared to Since polyflavonoid tannins are phenolic materials, foams which are
have no effectiveness against termite damage. made of these materials are fire resistant as much as synthetic phenolic
The wood preservative based on the interaction of tannin and boron foams. These flavonoid-furanic foams are comprised of about 95% of
was promoted by the addition of hexamine (Thevenon et al., 2009, natural materials (Tondi et al., 2008). Some of the applications of these
2010). The tannin preservative can be rendered more waterproof by foams include acoustic absorbers (Lacoste et al., 2015), metal ion ad-
adding hexamine and consequently co-added boric acid can be fixed sorption (Tondi et al., 2009), floral foams (Basso et al., 2016), sandwich
well inside the wood. Treated samples with this innovative preservative panels (Zhou et al., 2013), crash protection, packaging etc. Many in-
were resistant against the attack of fungi, termites and boring beetle vestigations have also been carried out to improve tannin foams char-
even after aging periods (Tondi et al., 2012a, 2012b). On the other acteristics like hydrophobisation (Delgado-Sánchez et al., 2016), com-
hand the formation of harden preservative of tannin/hexamine + boric pressive strength and impact (Li et al., 2013), flexibility (Li et al.,
acid inside the wood yields improved mechanical and fire resistance 2012a) and mechanical integrity (Li et al., 2012b). For example, Li et al.
(Tondi et al., 2012c, 2014). The weathering resistance of treated wood (2012b) mentioned that the low mechanical strength of tannin foams is
with tannin-based co-polymers was also studied (Tondi et al., 2013b). It one of the barriers to their applications. Thus, they improved tannin
was concluded that since tannin is an aromatic compound, it suffers a foams compressive strength as much as 37% in comparison to con-
similar degradation as lignin during exposure to the exterior climatic ventional formulation. They added new substances including oligo-
factors. In another study, greater color changes than the controls as a meric precursors (hydroxyl terminated) and glutaraldehyde as a cross
result of weathering processes were detected in beech wood samples linker.
impregnated with mimosa tannins (Yalcin et al., 2017). Addition of More recently, promising results for the manufacture of foams have
polyethylene glycol and caprolactam to the tannin-based preservative been shown in the case of mixing hydrolysable and condensed tannins
was also tried to increase the elasticity of the polymer formed within with pulping by-products including lignosulfonate and Kraft black li-
the wood (Tondi et al., 2015, 2017; Hu et al., 2017). The wood quor for insulation of buildings (Merle et al., 2016a, 2016b).

Y. Shirmohammadli et al. Industrial Crops & Products 126 (2018) 316–332

7.2. Wood-plastic composites level of diabetic and cardiovascular illnesses (Yang et al., 2018). Tan-
nins can be added to compensate for some wines low tannin levels
Wood plastic composite (WPC) are created as a result of wood because now wines might not be kept anymore for aging for too long in
supply shortages in order to use recycled wood and plastics in a more oak barrels (García-Estévez et al., 2017).
useful way. They consist of a thermoplastic matrix and lignocellulosic
component for reinforcement. Furthermore, additional elements to 8.2. Fisheries
improve physico-mechanical characteristics of the composite can be
added (Ashori, 2008). As far as lignocellulosic components have hy- The outer layer of some fish eggs have glycoprotein as a constituent
droxyl groups, they cannot react with thermoplastics matrixes. For and at spawning time, when the eggs contact the water, they hydrates
creating interfacial interactions between lignocellulosic components and becomes sticky. This phenomenon (sticky surface) is very im-
and the plastic matrices it is necessary to use coupling agents. Coupling portant in a natural environment, because it allows the eggs to stick to
agents like maleic anhydride are able to form chemical bonds between the plants underwater and achieves an increase in the survival rate of
dissimilar compounds of WPC (organic wood and inorganic polymer) the species (Kynard et al., 2011). In order to incubate fish eggs artifi-
(Zhou et al., 2016a). cially, a vertical water flow hatching machine (Weiss jars) is used. In
Lignin has been used with plastics (e.g. polypropylene) in the this type of equipment the eggs need to circulate. To ensure a suitable
manufacture of WPC with good final products characteristics when level of circulation, the eggs stickiness of should be eliminated. If the
using proper coupling agent like reactive flexible segment (Xu et al., eggs stickiness is not eliminated, they will stick together and forms
2014). Also, Lee et al. (2015) manufactured a composite comprised of clumps (mass adhesion) or stick to the equipment parts resulting in the
polylactic acid, coffee, lignin and polypropylene. Their results showed destruction of the eggs (Siddique et al., 2016). The de-sticking process
that lignin can act successfully as a coupling agent and led to an im- improves embryonic development, eases the conditions of control, and
provement in physical, mechanical and thermal properties. improves the hatching percentage in the incubator (Al Hazzaa and
Pine cones which contain high amount of phenolic substances have Hussein, 2003). The eggs de-sticking process is an essential stage in the
been shown to be usable with polypropylene and showed that pine reproduction of some fish species such as white bass (Morone chrysops),
cones are capable to be used as a reinforcing filler in the manufacture of lake sturgeon (Acipenser fulvescens), etc. since they produce very good
WPC (Ayrilmis et al., 2010). Therefore, since contraindications of use meat while their eggs are very sticky. Thus, their breeding and re-
do not exist between tannin and plastics, also lignin showed good production can be of great economic importance.
properties with plastics in the WPC production. Due to the tannins and There are several chemical treatments to remove the jelly layer of
lignin similarity of chemical structure, it is suggested that the potential fish eggs (such as carbamide in saline solution, powdered milk dis-
exist for tannins too to be used in WPC production as coupling agents. solved in saline solution, sodium sulfite etc.) (Al Hazzaa and Hussein,
2003) and/or other methods like mechanical separation, scouring eggs
8. Food industry with clean water or abrasives (starch, clay, charcoal or bentonite)
(Demska‐Zakęś et al., 2005). One of the very frequent used methods in
8.1. Beverage 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
Tannins are added several times during winemaking to give color short time (Kujawa et al., 2010). In a study by Hosseini and Khara
stability, protections against oxidation, odor and mouth-feel, proteic (2015) they compared the impact of clay suspension and tannic acid for
material precipitation and flavor improvement (Parker et al., 2007). egg de-sticking of Beluga (Huso huso). The de-sticking process took
Phenols main addition in winemaking is by grapes skin and seeds which 45 min and 1.5 min for a clay suspension and a tannic acid treatment,
aid to make wine. More tannin addition to wine can be in the form of respectively. Furthermore, the hatching and survival percentage for
direct addition, storing in oak barrels or addition of oak flakes tannic acid-treated eggs was much higher than for the clay suspension
(Harbertson et al., 2012). Extraction of condensed tannins from the treatment, while tannic acid showed even lower fungal contamination.
seed and skin of grapes has showed that, skin tannin extraction yields In the de-sticking process the optimum concentration and exposure
more than seeds, thus the skin condensed tannins have a more im- time should be investigated for each fish species, since each fish species
portant effect in winemaking (Cerpa-Calderón and Kennedy, 2008). egg presents different sticking characteristics. High concentration and
Wine phenols oxidation reactions affect the wine taste, odor, and color exposure time can result in egg hardening and consequently high
changes. The polyphenols present are the one that most of the time are mortality of the embryos.
capable to prevent oxidation reactions and acts as natural wine pre-
servatives. 8.3. Packaging
Astringency means the puckering and drying of the mouth as a re-
sult of the saliva protein precipitation by phenolic compounds (García- In the past decades, oil derived polymers have been used extensively
Estévez et al., 2018). Since tannins precipitate proteins, they cause in the packaging industry (Shchipunov, 2012) and nowadays many
astringency in food, this being one of the main characteristics of red studies have been carried out to use natural materials in the packaging
wines (Picariello et al., 2018). This feeling can be more intense when of different goods still presenting the needed characteristics (Weber
drinking wine without eating. White wines have less phenols in their et al., 2002; Ghaderi et al., 2014). Some of the natural polymers-based
composition (about 500 mg/l) in comparison to red wine (about films which are used in the packaging industry include chitosan, chitin,
1500 mg/l), thus astringency is much more marked in red wines, being starch and cellulose (Tang et al., 2012; Rhim and Ng, 2007). Particu-
one of their characteristics. During the past decades peoples have larly, nano-sized cellulose has attracted lots of interest and has been
tended to consume less astringent wines and consequently phenolics extensively studied (Charreau et al., 2013).
proportions in wines have also decreased. Oxidation is a chemical reaction which results in the production of
Tannins which are used in winemaking are named "enological tan- free radicals, leading to a chain reaction which can cause cells damage.
nins" or " oenatannins" and can be obtained from different botanical A molecule which is able to prevent the chain oxidation reaction of
resources like oak wood, grape seed and skin, plant gall, chestnut, other molecules is called antioxidant (it is a free radical scavenger).
quebracho etc (Sanz et al., 2008). Anthocyanidins are considered as the Foods degradation results in the creation of free radicals, while poly-
main kind of condensed tannin which influence the color of the grapes phenols act as antioxidants preventing this phenomenon (Fang and
and consequently of wine. Wine antioxidant properties are known to be Bhandari, 2010). In different studies, it has been demonstrated that
beneficial for human health like being anti-cancer and lowering the tannins have antioxidant properties (Missio et al., 2017; Beninger and

Y. Shirmohammadli et al. Industrial Crops & Products 126 (2018) 316–332

Hosfield, 2003; Noferi et al., 1997). Using tannins in packaging to- lumps during storage and their elimination by using tannin is ad-
gether with other natural polymers like nanocellulose has been in- vantageous (Chibata et al., 1986). Furthermore, complexes of tannins
vestigated to prepare a natural polymer with antioxidant properties and protein in animal feed are of critical importance since they affect
which can be used for different applications like food/pharmaceutical the forage protein, diminish emissions of greenhouse gas from rumi-
packing, tissue engineering, wound dressing, etc (Zhou et al., 2016b). nants, decrease ammonia and urea excretion and inhibit bloat (Zeller
Missio et al. (2018) have prepared a completely natural and biode- et al., 2015). The influencing factors on the protein-tannin interaction
gradable nano-cellulose film which had a very hydrophobic structure include pH, temperature, tannin : protein ratio, their structural chem-
(excellent air impediment), was very heat resistant and showed gradual istry, etc. (Naczk et al., 1996).
and proper antioxidant releasing property. Such findings show a very Accumulated antibiotics are one of the substances which should be
promising future for tannin in the packaging industry. To expand its eliminated during water/wastewater treatment in order to prevent fu-
application some more studies are needed to better understand the ture antibiotic resistance (Dodd, 2012). This goal can be reached by
nanocellulose-tannin interaction, to optimize the combination percen- electrochemical treatments (Dirany et al., 2012), membrane bioreactor
tages of tannin and nano-cellulose for different purposes etc. (Kovalova et al., 2012) and activated carbons (Acosta et al., 2016).
Activated carbons are used in different fields such as air purification
9. Animal food and feeds (Choi et al., 2016), water/wastewater treatment (Zietzschmann et al.,
2016) and purification of pharmaceutical products (Li et al., 2015). In a
Different kinds of drugs and methods are used for ruminants in recent research work Selmi et al. (2018) reported that in terms of an-
order to control parasites. Among these, feeding the animals with plants tibiotic adsorption, mimosa tannin and agave americana fibers as pre-
which are high in tannins has been investigated as a step toward or- cursors of activated carbons resulted in a better performances than
ganic farming systems (Athanasiadou et al., 2000; Hoskin et al., 2000). commercial activated carbons.
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. 10.2. Metal ions recovery
Investigations have proven that another benefit of condensed tan-
nins are their ability to diminish cattle’s rumen deterioration of dietary Access to clean water for everyone is one of the main necessities and
protein and also enhance the amino acid absorption in the small in- rights in every society. In order to satisfy this need, water treatment has
testine. Thus, it is suggested to use tannins (about 2%–4.5% dry mass of been one of the essential stages to provide clean water without con-
food) to improve digestion of dietary protein by protecting proteins taminants (Ali and Gupta, 2006). Toxic metals contaminations, such as
against bacterial elimination of amino acids and inhibiting bloats in by lead, mercury, cadmium, and copper is lethal and should be elimi-
animals. Conversely, tannins shortcomings when using excessive tan- nated from the water matrix since if they are consumed, they will ac-
nins (> 5.5% dry mass of food), include: fiber digestion impairing and cumulate in the body and cause serious diseases. Current means of
tannins ability to bind proteins and carbohydrates, hence to decrease wastewater treatment (such as chemical precipitation, ion exchange,
nutrient availability for grazing animals. This should not be ignored and electrochemical methods) are expensive and usually do not provide
(Hervás et al., 2003; Goel et al., 2005). However, the mechanism by a treatment sufficient enough to satisfy the relevant regulations
which tannins decrease the digestion of ruminal protein and promote its (Luzardo et al., 2017). Amid various means of water treatment, ad-
utilization is not precisely understood. Condensed tannins have shown sorption has been known to be the most effective and economical one,
that they possess a more marked influence on animal's digestion, and especially for the treatment of contamination at low concentration
hydrolysable tannins can cause toxin manifestations as a result of hy- (< 100 mg L−1) in a large volume (Xu et al., 2017). The type of ad-
drolysis in cattle’s rumen (Goel et al., 2005). sorbent is of basic importance in the wastewater treatment process.
Generally, condensed tannins are able to enhance digestibility of Since tannins possess adjacent phenolic hydroxyls, they display specific
nitrogen in grazing ruminants. Furthermore, they increase growth of affinity to metal ions and the ability to chelate them (Slabbert, 1992; Oo
wool, production of milk, and amount of lambing in sheep and cattle, et al., 2009; Tondi et al., 2009). One of the problems with tannin in
reducing worm burdens and improve animal welfare (Mueller‐Harvey, watery matrices is their water solubility and in order to use tannins in
2006). Condensed tannins to feed animals can be obtained from farm water treatment industry, tannins should be insolubilized/immobilized.
legumes such as white and white and red clover (Min et al., 2003). In For this purpose some matrices such as nanocellulose, collagen, meso-
very high quantity, nutrients can act as a toxic and detrimental sub- porous silica, activated carbon, etc. have been used (Xu et al., 2017).
stance, but in required quantity they are very beneficial for health Moreover, condensed tannin gel adsorbent has been investigated suc-
(Lyman et al., 2008). Thus, these findings infer that more research is cessfully in order to gold (Ogata and Nakano, 2005), palladium (Kim
needed to optimize the dosage of different kinds of tannins for different and Nakano, 2005) (which is known as valuable metals), and lead
kinds of animals. (Zhan and Zhao, 2003) (which is a very toxic and accumulate in food
chain) recovery from aqueous solutions. Much recently the potentiality
10. Environmental applications of tannin extracted from pine tree bark was evaluated for antimony (Sb)
uptake from water solutions (Bacelo et al., 2018). The tannin was firstly
10.1. Adsorbents for proteins and antibiotics polymerized by the sodium hydroxide and formaldehyde. Then, the
produced adsorbent was assessed on the sequestration of different
Protein-precipitation and formation of insoluble complexes with species of Sb (III and V). The result showed that it was effective for both
tannins has been known since ancient times for leather tanning and in species, in diluted and heavily-contaminated waters.
the food industry. Phenolic hydroxyl and hydrophobic areas in the Bacelo et al. (2016) suggested that there is still room for innovation
proanthocyanidins react with the carbonyl groups and complex with about tannin-based biosorbents such as use of alternative tannin
the amino and amido groups of amino acids of proteins, respectively, to sources, optimization of chemical modifications, study the effect of
insolubilize them (Girard et al., 2018). Studying the complex of tannins competing ions or substances in solution, and etc.
and protein can be beneficial for altering food structure. Some research
investigated this potential to exploit this characteristic to include de- 11. Medicinal applications
livery of micronutrients (Links et al., 2016), to increase wheat gluten
strength (Girard et al., 2016) and to decrease glucose metabolism Since centuries ago, different kinds of plants which are reach in
(Amoako and Awika, 2016). Proteins in beverages such as wine, beer tannins have been used in traditional medicines all around the world
and juice affect using the taste and color negatively by creating small (Scartezzini and Speroni, 2000; De las Heras et al., 1998). An old

Y. Shirmohammadli et al. Industrial Crops & Products 126 (2018) 316–332

example of tannin use is green tea with antioxidant and antitumor ef- corrugated cardboard starch adhesives. The percentages of tannin ex-
fects (Yoshizawa et al., 1987; Perchellet et al., 1992). Tannins are tracts used are relatively small and their use is focused, in some
considered as astringent substances which means that they bond pro- countries, on corrugated cardboards for boxes for boat transport of
teins in order to form a protective layer (which happens in leather fruits through the moist air of the tropics, to avoid the boxes to fall
tanning). In the terms of topical application, this protective layer can apart. This application has been running for a few decades now.
improve curing speed of ulcers, wounds and burnings. This protective Medicinal applications are also known for a number of years such as
layer stops bleeding, prevent infection, shields against mechanical and the use of monoflavonoids in pharmacopea. These are specialized,
chemical irritation, bacterial, and micro-organisms (de Jesus et al., highly purified tannins, for pharmaceutical use. This is a field of
2012). Naturally hydrolysable tannins have been known to have more growing interest for a number of novel applications.
astringent characteristics than condensed tannins and show more of this Equally, metal ions recovery is now in industrial practice for many
ulcer curative feature. years. The most interesting example of this is the separation of the rare
Tannins are known to have anti-inflammatory effects which help to metal Germanium from Copper ore. The tannins complexes pre-
minimize symptoms of alimentary diseases such as esophagitis, gas- ferentially Germanium and thus this valuable resource can be isolated
tritis, enteritis, and inflaming bowel sickness (Ashok and Upadhyaya, from Copper, after which the tannins are burned to recover the metal.
2012). Hydrolysable tannins also have shown therapeutic effects Tannins are also extensively used for many years in the beverage
against Acyclovir-resistant herpes viruses when it is applied on the field. Thus, they are used to precipitate proteins in wine-making.
mucous membrane of the mouth (Quideau et al., 2004). Moreover, Equally, many people do not realize that highly purified tannin extracts
tannins have shown antibacterial (Akiyama et al., 2001), antiviral (Lu are added to beer and fruit juices to give them the taste that otherwise
et al., 2004) and antiparasitic (Kolodziej and Kiderlen, 2005) char- they would not have. The percentages are small, between 1% and 3%
acteristics. but thir utilization is extensive in the beverage field.
Recent study have indicated that extracts of Kakadu plum One of the older uses of tannin extracts is as corrosion inhibiting
(Terminalia ferdinandiana) leaf which are high in tannins have shown primers for metal coatings. This used started commercially in the UK in
inhibitory influence against microbial triggers of autoimmune in- the 1960’s. It was then discontinued and it is now coming to the fore
flammatory disorder (Courtney et al., 2015). This effect is because of again in a number of countries.
tannins action against bacteria which is one of causes of this kind of All the other applications described in this review are emerging
autoimmune disease. Reach tannin plants also have shown curative technology, some of them, such as fireproof foams, nearer than others
effects against pathogens causing diarrhea both in animals and humans to a possible industrial exploitation, but emerging technologies none-
and used instead of antibiotics to cure this disease (Würger et al., 2014; theless. Other technologies in this field are also under consideration,
Siqueira et al., 2012). but they are far less developed as yet than the ones described in this
As far as tannins can interfere with digestion and nutrient absorp- review.
tion, long term use of strongly astringent herbs is not recommended and
should be cautiously used in the patients with inflamed or ulcerated 13. Conclusions
gastrointestinal tract (Bone and Mills, 2013). Tannins also can result in
nausea which is probably as a result of protein binding in the stomach. Tannin is a bio-phenol with excellent antioxidant properties that
High levels of absorbed tannin in the blood can cause constipation, can be widely used in industry as a green and sustainable raw material.
hepatotoxicity or damages to other organs. Ruminants that are fed with In this review, the current industrial uses of tannins and also the po-
highly tannin containing plants are particularly susceptible to these tential applications of them are thoroughly investigated. The use of
effects. Furthermore several studies on the use of tannins as anticancer biosourced alternatives such as tannins using them instead of toxic
and antiviral agents have been reported a summary of which has been synthetic substances (such as phenol, diisocyanate, chromium, etc.) can
reported (Pizzi, 2008). ultimately lead to a healthier environment. Tannins extraction can be
economically affordable in the case of extracting them from plant parts
12. Status of the technologies, industrial scale applications, of high tannin contents and using proper extraction methods (time,
limitations temperature, solvent, particle size etc.). It should also be noted that
tannin is a renewable resource and there also are many sources for its
Some of the technologies described are already applied industrially, production.
some to a limited scale, while others are still emerging technologies. Tannins have a wide range of applications due to their chemical
Thus leather-making using vegetable tannin extracts is in operation characteristics and structure differences. In some applications, the
already from 1870, although the use of vegetable tannins is decreasing phenolic structure of tannin and in others its antioxidant properties,
for this application due to two factors: (i) the substitution of leather sometimes both, are important. Some tannin applications (such as
shoe soles by synthetic materials and (ii) the use of chrome salts tanning leather tanning) have a historical background, but research still con-
for soft leathers such as shoe uppers and other applications. It is this tinues to optimize and increase their efficiency.
decrease that has prompted interest in other possible applications of Tannin copolymers with other natural materials, such as lignin and
tannins. The second technology that is already applied industrially is for furan derivatives, have introduced new applications for tannins with a
wood adhesives for panel products. This application started to grow higher percentage of bio materials. As tannins play a prominent role in
industrially from the early 1970′s and there are now factories in South general defense strategies of plants, extensive research has been re-
Africa, Australia, two South American countries (Valenzuela et al., cently done to use them in protecting of perishable wood species
2012) and even in a couple of factories in Europe and Japan where against biological threats (against insects and fungi). Wood protection
tannin adhesives for wood panels are now used. The limitation in their with tannins can be carried out either alone or in combination with eco-
use in this field is the enormous volume of oil derived adhesives used in friendly pesticides. The co-polymerization of tannins with other poly-
this field. Literally, there is not enough extraction factories around to mers (like furan components, caprolactam, etc.) not only can be con-
satisfy possible demand to substitute synthetic oil derived adhesives. In sidered as yielding a simple preservative, but also can act as a mod-
the last few years some new tannin extraction factories have indeed ifying polymer to improve physico-mechanical properties of wood.
been built or are under construction, namely in Sumatra and in Chile,
but while the potential for tannin extraction is huge the growth of Acknowledgments
additional factories is slow. An area where limited industrial utilization
is occurring, now for several years is as fortifiers and waterproofer of The authors would like to gratefully acknowledge the financial

Y. Shirmohammadli et al. Industrial Crops & Products 126 (2018) 316–332

contribution of Iran national science foundation. Proceedings of ECOWOOD 2006-2nd International Conference on Environmentally-
Compatible Forest Products.
Boutevin, B., Caillol, S., Burguiere, C., Rapior, S., Fulcrand, H., Nouailhas, H., 2010.
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