Review

Received: 14 June 2024 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/pi.6697

Natural polymers for emerging technological

applications: cellulose, lignin, shellac and silk
Mihai Irimia-Vladu* and Niyazi Serdar Sariciftci

Abstract
In an effort to stave off the growth of electronic waste (e-waste) that poses a critical environmental dilemma, scientists often
look into nature as an unending inspirational pool of materials and chemical processes that ensure functionality, performance
and safe dissolution at the end of life cycle. This short review highlights only four organic polymer materials of natural origin
(i.e. cellulose, lignin, shellac and silk) from the very large pool of natural (bio)polymeric materials and looks not only into the
recent developments at the industrial scale but also into the emerging niche applications of these materials, while highlighting
their implementation into electronics and sensor development. This review exemplifies that natural polymeric materials have
great potential for the development of eco-friendly electronics, in other words the class of industrial products that has carefully
considered the important issues of biocompatibility, biodegradability (even compostability), cost of production and energy
expanded in production (i.e. the carbon footprint).
© 2024 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Keywords: natural polymers; biopolymers; cellulose; lignin; shellac; silk

INTRODUCTION they can be digested by bacteria and microorganisms at the

Natural biopolymers, the most abundant organic compounds in end of their life cycle, and are therefore viewed as sustainable
the Earth biosphere, are polymers that are freely produced platforms that can support the sustainable technological
in nature by the cells of living organisms, either plants or animals. advancement of our civilization.1,3 This aspect is crucially impor-
They consist of monomeric units that are covalently bonded in lin- tant in our modern world where the utilization of energy
ear and branched chains to form larger molecules. According to resources, the carbon footprint and the environmental impact of
their chemical structure, the main classes of biopolymers are: industrial technologies need careful attention.8–10
(i) nucleic acids (DNA, RNA), (ii) polyamides (proteins and With regard to the sustainable development goals of the United
poly(amino acid)s), (iii) polysaccharides (cellulose, starch, natural Nations,11 it is not responsible and sustainable to continue the
gums, xanthan), (iv) polyisoprenoids (natural rubber, gutta polyolefin-based plastic industry on the long run. Therefore, a cir-
percha), (v) polyphenols (lignin, humic acids), (vi) organic poly- cular economy is envisioned in the plastic industry, which is very
oxoesters (polyhydroxyalkanoic acids, polymalic acids, cutin, popular and used for regulating the recycling of plastics. On the
shellac), (vii) polythioesters (polymercaptoalkanoic acid, other hand, it is very difficult to bring in a 100% recycling rate.
polyhexanedithiol-sebacate) and (viii) inorganic polyesters. With each passing day it will be expensive and increasingly more
Although many of the above-mentioned classes of polymers are difficult to have a clean environment using polyolefins.
actively studied in relation to novel developments in medicine Therefore, it is highly desirable to have materials which are bio-
and pharmaceutics formulations, the present article focuses on degradable and can offer products similar to those produced from
the naturally occurring polymers of high-volume availability, petroleum, but with enhanced capabilities. What else is more
i.e. cellulose, lignin, silk and shellac. The interest in biopolymers attractive than biopolymers? Poly(lactic acid) for example is
in the scientific community has risen in the past few years, espe- already entering mass production worldwide as a replacement
cially since they are seen as a viable alternative to nonbiodegrad- for polyolefins in consumable products, mainly packaging. There
able, petroleum-based plastics,1–3 the latter group surpassing are many other biopolymers which can be suitable as substitutes
already the production milestone of 400 million tons/year.4,5 It is for mass-produced polyolefin-derived polymers. Those materials
estimated that ca 8300 million tons of plastic have been produced are clean for nature, due to their biodegradability when discarded
by mankind since the emergence of the chemical industry, and
nearly 6300 million tons of plastic have been discarded into the
environment.6,7 Considering the important aspect of utilization * Correspondence to: M Irimia-Vladu, Linz Institute for Organic Solar Cells (LIOS),
of a large fraction of plastics for short-term applications only, Institute of Physical Chemistry, Johannes Kepler University Linz, Altenberger
Str. 69, 4040 Linz, Austria. E-mail: [email protected]
mankind is still struggling to find appropriate solutions for han-
dling plastic waste. Many of the naturally occurring polymers, or Linz Institute for Organic Solar Cells (LIOS), Institute of Physical Chemistry,
polymers derived from natural sources have the advantage that Johannes Kepler University Linz, Linz, Austria
1

© 2024 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any
medium, provided the original work is properly cited.
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in the environment. As a result, an accumulation of plastic waste the process of photosynthesis, is estimated to be ca 1 trillion
could be curbed by employing such a strategy. tons/year, making it the most widely available biopolymer to
Cellulose, lignin, silk and shellac are examples of biopolymers mankind.13 Cellulose is naturally produced not only by all plants
that have been established as key materials for many industrial- on land, but also in the oceans, in the process of fixation of carbon
scale applications in different sectors. In this respect, utilization dioxide, as for example in unicellular plankton and algae. The
of these biopolymers as textile materials, as bases for novel chem- composite material wood is nothing but an outstanding high-
ical production, as biomedical materials, as food production strength and durable material composed of cellulose as main
ingredients and as other high-value-added products is summa- component, together with lignin and hemicelluloses (Fig. 1).14
rized, with an individual highlight of the employment of each The composition of some well-known sources of natural cellulose
one in the emerging field of bioelectronics. is presented in Table 1,15,16 which shows that the two major
sources of natural cellulose are wood and cotton, both having a
chemical composition depicted as cellulose I in Fig. 2.17
CELLULOSE AND LIGNIN Some prominent players in the global cellulose market include:
The biomass reserves of the Earth have been estimated to be Weyerhaeuser Company, Honeywell International, DuPont de
approximately 1.85–2.4 trillion tons and given the increased Nemours, Inc., Invista, Daicel Corporation, Nylstar, Zhejiang Fulida,
global concern over the effects of greenhouse gas emission, such Lenzing, Fiber Visions Products and Eastman Chemical, with many
biomass has emerged as an abundant and sustainable alternative more trading companies in the world involved in handling cellu-
source of energy and chemicals.12 The biomass is constituted of lose products.
three main components: cellulose, hemicellulose and lignin. Cel- However, despite the usage of cellulose for millennia by man-
lulose is a natural biopolymer that can be regarded as a linear kind as energy source and in clothes production, the employment
macromolecular chain of 1,4-linked ⊎-D-glucopyranose, occurring of pure cellulose in high-added-value applications is sporadic, due
in every cell of all plants on Earth. It is a completely nontoxic, in part to its insolubility in water as well as in most organic sol-
renewable and biodegradable material that exhibits a great vents, its hygroscopic character and its inability to melt without
chemical variability and can be divided into natural and synthetic decomposition. As a consequence, synthetic nanocellulose has
cellulose depending on the source of production. Cellulose repre- attracted increased attention in recent years, due to its customiz-
sents also a massive source material for the fabrication of environ- able chemical and physical properties of the material that suit
mentally friendly and biocompatible products. The production of various applications. In effect, the worldwide production of cellu-
cellulose from glucose, which itself is produced in plant cells by losic fibers (including here the above mentioned synthetic

Figure 1. Descriptive presentation of the structure of lignocellulosic biomass and its three main constituents: cellulose that accounts for ca 40–50 wt% of
the biomass is a linear homopolymer of glucose linked through ⊎-1,4-glycosidic bonds; hemicellulose that accounts for ca 25–35 wt% of the biomass is a
heteropolymer of C5 and C6 sugars linked through different glycosidic bonds; and lignin that accounts for ca 15–20 wt% of the biomass is an aromatic
heteropolymer comprising various phenylpropanoid units. Fibrils of cellulose surrounded by hemicellulose and lignin constitute the microfibrils that bun-
dle together in macrofibrils, which represent the main component of the cell walls of plants. Reproduced with permission from Ref. 14.
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Table 1. Chemical composition some plants of industrial relevance. Reproduced from Ref. 16

Composition (%)

Source Cellulose Hemicellulose Lignin Extract

Hardwood 43–47 25–35 16–24 2–8

Softwood 40–44 25–29 25–31 1–5
Bagasse 40 30 20 10
Coir 32–43 10–20 43–49 4
Corn cobs 45 35 15 5
Corn stalks 35 25 35 5
Cotton 95 2 1 0.4
Flax (retted) 71 21 2 6
Flax (unretted) 63 12 3 13
Hemp 70 22 6 2
Henequen 78 4–8 13 4
Istle 73 4–8 17 2
Jute 71 14 13 2
Kenaf 36 21 18 2
Ramie 76 17 1 6
Sisa 73 14 11 2
Sunn 80 10 6 3
Wheat straw 30 50 15 5

nanocellulose) amounts to 7.3 million tons/year,18 with the main that differentiate it from wood- or plant-derived cellulose. In this
industries handling cellulosic fibers being aerospace and defense, respect, the purity of BC is much higher than that associated with
automotive, paper and pulp, construction, electrical/insulation, plant-based cellulose because the fewer steps necessary for pro-
textile and fireproofing. In the class of synthetic nanocellulose duction are translated in a final product devoid of polymer con-
(with particle sizes of between 1 and 100 nm), one can distinguish taminants, which is unfortunately a characteristic of the latter
two products depending on the fabrication route, i.e. cellulose cellulose type.22 Moreover the degree of crystallinity of BC is
nanocrystals (CNC), which are obtained by acid treatment, and much higher than that of plant-based cellulose, with a value
cellulose nanofibrils (CNF), obtained by mechanical disintegra- approaching 90%.23 The water retention of BC is outstanding,
tion. Crystalline cellulose depicted as cellulose II in Fig. 2 is an given by the fact that the hydroxyl groups in the glucose units
important industrial product since it represents the precursor of can interact efficiently with water molecules, leading to ca 90%
viscose, as well as various cellulose esters and ethers. water retention capability. The advantageous mechanical proper-
The fabrication of CNF takes place in sequential operations, ties of BC, coupled with its biocompatibility, nontoxicity, formabil-
depicted schematically in Fig. 3.19 Because of the exhaustive steps ity, softness, cost-effectiveness and ability to be derived
necessary to obtain the refined final product, the process of car- synthetically to incorporate secondary components, such as anti-
bon nanofibril production is difficult to be scaled up to the level biotics, into its pores, have led to BC as the candidate of choice for
of industrialization. In addition, lowering the amount of energy many applications on human tissue, like for example plasters
expended in the process remains a formidable obstacle. for wound healing (Fig. 4).21
In addition to being extracted from wood and plants, nanocellu- The usage of cellulose in electronics applications is not yet
lose can be synthesized by bacteria (i.e. bacterial cellulose, BC) established industrially, despite recent reports in the literature
and by electrospinning cellulose nanofibers (i.e. ECNF). Among that take advantage of the unique film-forming and outstanding
the four types of nanocellulose, CNC and CNF have a wider indus- dielectric properties of cellulose.24–30 Advantageously, nanocellu-
trial relevance since their fabrications are regarded as top-down lose can be patterned photolithographically, opening in this way
processes, being produced by disintegration of cellulose fibers the avenue for practical industrial exploitation in the electronics
into nanoscale particles. BC and ECNF production on the other field.31 In a recent report, trimethylsilyl-derivatized nanocellulose
hand are bottom-up processes, generated by a buildup of nanofi- (TSMC) synthesized in ionic liquids32 was employed as robust
bers from low-molecular-weight sugars by bacteria (Fig. 4) or from dielectric for high-performance organic field effect transistors
dissolved cellulose by electrospinning, respectively. The assembly (OFETs) and complementary inverters24 (Fig. 5). Panels (a)–(e) in
of cellulose nanofibers by bacteria involves two steps, illustrated the red frame of the Fig. 5 present the robust dielectric properties
schematically in Fig. 4: (i) the assembly of cellulose molecules of TMSC, which functions either as a stand-alone insulator or as a
extruded from the same extrusion pore into a single elementary thin capping layer for an inorganic aluminium oxide dielectric.
nanofiber with a diameter of ca 1.5 nm and (ii) the congregation The high purity of the synthesized material is translated into a rel-
of multiple elementary nanofibers into a ribbon-like nanofiber of atively flat capacitance over a wide frequency window spanning
3–4 nm in thickness and 70–80 nm in width in the cross-section, from kHz to mHz, and a loss angle always lower than 0.1 which
which is further woven into a three-dimensional network with is a remarkable behavior, as demonstrated in panel (e). The break-
the appearance of a pellicle floating at the surface of culture down field of 4.4 MV cm−1 extracted from the measurement
media.20,21 BC has unique structural and mechanical properties shown in panel (d) compares favorably with synthetic polymers
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Figure 2. Intermolecular and intramolecular hydrogen bonds in the two allomorph structures of cellulose, cellulose I and cellulose II: intramolecular 2
(OH)


O-6 (orange dash lines), intramolecular O(3)H–O pyranosidic (blue dash lines), intermolecular O(6)H–O(30) (green dash lines) and intermolecular
O(2)H–O(2) and O(6)H–O(20) (red solid lines). Reproduced with permission from Ref. 17.

like benzocyclobutene whose breakdown field was reported as vapor-phase acid hydrolysis (i.e. desilylation) through a simple
being 4.5 MV cm−1.33,34 Panels (a)–(d) in the blue frame of Fig. 5 exposure for 90 s to vapor of 2.5 mol L−1 hydrochloric acid solu-
show the outstanding dielectric behavior of TMSC employed as tion. The process involves a reduction of the film thickness by
capping layer for inorganic dielectric aluminium oxide. Both the about 70% that affects nonetheless the quality of the film surface.
transfer and output characteristics are virtually hysteresis free Nevertheless, the noise margin of the complementary inverters
and the OFETs display a minimal leakage current in the range of fabricated with regenerated cellulose film via the desilylation
nA throughout the measurement window. Perhaps the most out- method still displays an exceptional value of 82% at 2.5 V operat-
standing role of TMSC is displayed in the complementary ing voltage.25
inverters fabricated with pentacene and fullerene C60, shown in Lignin is the second most accessible biopolymer to mankind
panels (a)–(c) in the green frame of Fig. 5. In this respect, world after cellulose, with an estimated immediate availability of ca
record values of static gain in excess of 1000 V V−1 were recorded 100 million tons/year, being in fact an undesired byproduct of
(with record values up to 1600 V V−1). In addition, the inverters the paper and pulp as well as cellulose production industries.36
displayed a world best value of noise margin of 92.5% at a supply It is worth pointing out that in reality lignin is not the second most
voltage of 4 V, which surpasses all the previous reports concern- widespread biopolymer produced by nature, that being chitin
ing other combinations of dielectrics and semiconductors.35 Inter- with a total steady-state availability in nature estimated to come
estingly, TSMC film can be transformed into pure cellulose by close to 100 billion tons as part of the shells of living organisms
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Figure 3. Schematic diagram of the fabrication sequence of more than 50 types of CNF. Reproduced with permission from Ref. 19.

Figure 4. Schematic representation of the steps involved in the production of a BC-based wound healing material. Reproduced with permission from
Ref. 21.
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Figure 5. Red frame: (a) Schematic of fabricated OTFTs, containing glass substrate (light blue), aluminium gate electrode (gray), TMSC dielectric layer
(green), organic semiconductor (pentacene or C60) (navy blue) and source and drain electrodes (Au or Al) (gray). The insets show the chemical structure
of TMSC and an AFM image of pentacene on TMSC. (b) Example of electrical measurements of a metal–insulator–metal in sandwich sequence Al/TMSC/Al
with an overlapping electrode area of 0.1 cm2 and a TMSC layer thickness of 72 nm, showing the current density curve. (c) Current density curve in com-
parison to a bilayer inorganic–organic dielectric of 28 nm Al2O3 and 30 nm TMSC. (d) Capacitance versus voltage displaying also the breakdown field of an
Al/TMSC/Al sandwich structure. (e) Dielectric permittivity (left axis) versus frequency and loss angle (right axis) versus frequency curves of a capacitor with a
single layer of TMSC. Blue frame: Examples of transistor characteristics of C60- and pentacene-based OFETs with channel length L = 25 μm and channel
width W = 2 mm on a combination dielectric consisting of 28 nm Al2O3 and 25–30 nm TMSC. Output and transfer characteristics of (a, c) C60 and (b, d)
pentacene OFETs. Green frame: (a) Voltage transfer characteristics (VTCs) and inverter gains of a complementary inverter structure for supply voltages
between 4 and 7 V. The inset presents the circuit schematic of the complementary inverter. (b) Noise margin (NM) and mismatch ΔVM of the threshold
voltage VM as a function of the supply voltage, with the error bars of the NM also displayed. (c) Determination of the NM at VDD = 4 V using the ‘maximum
equal criterion’ by finding the maximum size of a square that fits between the inverter curve and the mirrored inverter curve. Reproduced with permission
from Ref. 24.

(i.e. freshwater and saltwater arthropods). Nevertheless, to date precursor for bioethanol production. Therefore, increased atten-
chitin has found no large-scale industrial applications, other than tion has been given recently to lignin valorization and to enlarg-
being the precursor of chitosan, with the latter production in the ing the market for lignin applications.
range of 4000 tons/year. Lignin on the other hand is available in The process of valorization of lignin requires that the biopoly-
the amount mentioned above and its total value is estimated to mer be separated from cellulose, and several such industrial pro-
surpass $900 million by 2025.36 Lignin has attracted recently cesses are presented in Fig. 7. Depending on the catalyst
increased interest for a plethora of industrial applications that will employed in the separation process, different reactive intermedi-
be enumerated in the following. Lignin is the biopolymer that is ates can be formed on the lignin backbone and these intermedi-
responsible for the overall rigidity of cell walls and is generated ates can then experience further reactions either with other lignin
in nature during radical coupling of phenylpropanoid units, such units or with chemicals present in solution. The two most com-
as p-coumaryl, coniferyl and sinapyl monolignols. Chemically, lig- mon and well-known methods for the industrial extraction of lig-
nin can be regarded as a polyaromatic macromolecule and can be nin are the kraft (black pathway in Fig. 7)37 and the sulfite (light-
divided into two categories, sulfur-containing and sulfur-free lig- blue + gray pathway in Fig. 7)37 processes, with the processes
nin, as shown in Fig. 6. Among the listed types of lignins, the most having been described in detail elsewhere.14 Both processes
prominent globally are the lignosulfonates (ca 88%), followed by involve aqueous solutions for the extraction of lignin from the lig-
kraft lignins (ca 9%). Nevertheless, an emerging category is repre- nocellulosic mixture. However, novel methods of extraction make
sented by the organosolv lignins with a prominence of ca 2% use of organic solvents and process temperatures up to 250 °C in
globally especially since it is employed in the production of order to fractionate the biomass.38 These methods are coupled
bioethanol. However, the production of lignin far surpasses the under the organosolv lignin pathway (red pathway in Fig. 7). An
demand for its use as a fuel, either to be burnt directly with a sig- ultimate improvement to the process of lignin extraction involves
nificantly lower efficiency than petroleum per kilogram or as a the addition of aldehydes such as formaldehyde to the acid-
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Figure 6. Various types of lignin and their current volumes on the world market. Reproduced with permission from Ref. 36.

catalyzed organosolv process, which substantially improves the subsequently responsible for the occurrence of hysteresis effects
quality of the final product (blue pathway in Fig. 7).39 in transistor characteristics.53,54
Table 2 presents the main material categories derived from lig-
nin, the reported products and their practical applications. How-
ever, in recent years, several other emerging applications have SHELLAC AND SILK
been reported for lignin in different fields.36 In this respect, lignin Shellac and silk are both biopolymers of animal origin with a long
is intensively studied for its depolymerization pathways, synthesis history in production, trade and development. They are arguably
of chemically active sites, functionalization of hydroxyl groups the only two biopolymers of animal origin in the world that have
and production of lignin graft copolymers. Among the novel at the present time an industrial significance, with production vol-
materials and compounds derived from lignin are lignin-based umes in thousands of metric tons per year.
carbon fibers, phenolic materials, oxidized compounds, hydrocar- Silk production, textile weaving and textile trade represented a
bon compounds, urethanes and epoxy resins, fire retardants and milestone in the development and advancement of human civili-
antioxidants, lignin-derived sequestering agents and lignin-based zation on Earth, with historic Chinese reports documenting silk
nanomaterials.40–44 Emerging applications (although being cur- commerce as early as 2700 BC.55,56 Silk originates from various
rently in the stage of proof of concept) are in the biomedical insect and spider species (e.g. silkworms, spiders, flies and silver-
and energy storage fields. In the biomedical field, lignin has found fish) and is composed of two different proteins, sericin and fibroin,
applications as microcarrier capsules on which many valuable among which the latter is an FDA-approved material for some
therapeutic agents could be physically attached or encapsulated. medical applications. Silk fibroin has in fact a large spectrum of
In this respect, lignin nanotubes and lignin nanowires are pro- applications, including the textile industry, biomedicine, catalysis
posed as vehicles for the delivery of DNA and therapeutic and many more. Each silk-producing insect and spider species
agents.45 In addition, active research is underway in the areas of produces silk of a particular amino acid composition, which gives
tissue engineering, immunomodulation, anticancer and antimi- the silk particular mechanical properties.57 Among the known
crobial hydrogel formulations based on lignin molecules.46–48 In silks, spider silk has a highest tensile strength, extensibility and
the energy storage field, lignin has found many usages in various toughness; however, such silk does not have an industrial signifi-
components of batteries and supercapacitors aimed at not only cance due mostly to limited availability. Mulberry worm silks are
improving efficiency but also reducing toxicity, and creating a the ones commonly employed for textiles manufacturing and bio-
more cost-effective and sustainable (ecological) product.49–51 medical applications, with the total market of silk surpassing
Lignin demonstrated recently its suitability for the development 200 000 metric tons in 201658,59 that represented a world record.
of sustainable OFETs.52 However, that report remains isolated in Although many countries in the world are specialized in silk pro-
the electronics field and requires significant attention in order to duction stemming from mulberry silkworms, India and China
reach the level of industrial interest. Figure 8 presents the output share ca 98% of the global silk market. Among the companies act-
and transfer characteristics of kraft lignin acting as a stand-alone ing as top players in the world, one can name China Silk, Silk Road
dielectric on plain aluminium gate with both C60 (Fig. 8(a),(b)) Holding Group, Jiangsu Huajia Silk, Guangdong Silk-Tex Group, Jai
and pentacene (Fig. 8(c),(d)) semiconductors. Texart, Garimaa Silks, Guangxi Jialian Silk, Zhejiang Jiaxin Silk, Mia-
The major problem remaining to be solved is the limited solubil- nyang Tianhong Silk, Guangxi Guihe group, Jiangsu Xinyuan Silk,
ity of lignin in organic solvents. As a report demonstrated,52 the Jiangsu Soho International, Guangxi Huahong Silk and Zhejiang
alternative method of solubilizing lignin in ionic-rich liquids Cathaya International.
(i.e. alcohol–ammonia mixtures) has the undesired effect of trap- Structurally, silk contains about 75% of a triangular cross-
ping mobile ions in the dielectric film of lignin, which are sectional shape fiber called fibroin and about 25% of gum in a
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Figure 7. Typical methods for lignin isolation and its subsequent chemical modifications. The kraft process (top pathway, black line); the sulfite process
(light-blue/gray pathway); aldehyde-stabilized lignin (bottom pathway, navy blue). The proposed final structures of extracted lignins resulting from all of
these reaction pathways are displayed on the right. Reproduced with permission from Ref. 14.

form of a globular protein called sericin.60 The sericin protein processing of the silk involves immersion of the cocoons in hot
coats the fibroin fiber and acts as a protective layer. The produc- water to soften the sericin and allow unwinding of the fiber and
tion of natural silk fiber from farm and wild silkworms is presented intertwining it with other fibers in separate yarns.60
in Fig. 9. The process of secreting the natural silk fiber by the silk The mechanical properties of natural silk fibers are simply
caterpillar occurs at a rate of 25 cm min−1, and the cocoon itself astonishing, placing them in the range of materials representa-
is formed of a single fiber that approaches 3 km in length. The tive of every high-end synthetic fiber or wire, shown
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Table 2. Lignin-derived material categories, functional products and their proposed applications. Adapted and reproduced with permission from
Ref. 36

Material category Lignin type Products Potential applications

Aromatic macromolecules Klason, kraft, organosolv Lignin monomers and dimers, aromatic Industrial chemicals, biobased
and fine chemicals phenols, alkyl phenols, aromatic adhesives, multifunctional
aldehydes, aromatic alcohols, acids, materials, building blocks for
aryl ketones, antioxidants, biobased products
dispersants, polyurethanes, phenolic
resins, vanillin
Carbon materials, biofuels Kraft, sulfite, soda, Biochar, bio-oil, syngas, activated Lightweight polymer composites,
organosolv carbon, carbon fibers, carbon black adsorbents, electrochemical
devices, automotives
Polymer and nanomaterials Kraft lignin, organosolv, 3D printing resin (cationic surfactant), Biomedical applications, tissue
straw lignin scaffolds, lignin nanotubes, engineering, drug delivery
hydrogels, lignin nanotubes
Energy storage Kraft lignin, Klason Li-ion, Na-ion batteries (electrodes), Energy devices, batteries, fuel cells
supercapacitors, solar cells
Building materials Kraft lignin, Klason Bitumen, cement additive, dispersant, Construction pavements, cement
reinforcement panels
Specialized applications Kraft, sulfite, soda, Soil conditioner, controlled release Agriculture, textiles, soil reclamation,
organosolv agent in fertilizers and pesticides, water purification, fire
sequestering agent, contaminant suppression
absorbent, fire retardant

Figure 8. Transfer and output characteristics of kraft lignin solubilized in a mixture of methanol and ammonia, and deposited via doctor blading on plain
aluminium gate electrode for OFETs: (a, b) fullerene, C60, semiconductor; (c, d) pentacene semiconductor. Reproduced with permission from Ref. 52.
9

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www.soci.org M Irimia-Vladu, NS Sariciftci

Spooling

Reproductive
cocoons Floss silk

Continuous
Silkworm Sericulture silk
Cocoons
eggs
Frisons Chrysalis

Industrial
cocoons
Chrysalis in Unreeled
cladding cotton
Figure 9. Flow chart of natural silk production. Reproduced with permission from Ref. 60

descriptively in Fig. 10.61 In terms of strength-to-weight ratio it is transistors.64–69 Not surprisingly, the bulk of the work on silk as a
important to keep in mind that the spider silk strength of dielectric material for OFET and organic light-emitting transistor
ca 1.1 GPa is similar to that of high-tensile engineering steel fabrication originates from research groups in Asia, having as
(i.e. ca 1.3 GPa), while the former has a relative density of ca incentive the desire to find new markets and applications for silk.
1.3 compared to that of the latter of ca 7.8, when reeled at Figure 12 demonstrates that by employing a thin interfacial layer
20 mm s−1 at 25 °C. At the same time, the toughness of spider between the organic semiconductor and silk, i.e. 2 nm of penta-
silk is ca 165 ± 30 kJ kg−1, which is substantially higher than that cene, the growth of C60 in larger grain sizes is largely favored,
of polyaramid fiber Kevlar 81 (ca 33 kJ kg−1). Drawing the silk which translates in an increase of the drain current by almost
fiber from the Bombyx mori silkworm at different speeds has two orders of magnitude, i.e. from 8.5 × 10−7 to 4.5 × 10−5 A
the advantage of allowing the control of fiber mechanical prop- and an afferent improvement of field effect mobility by two
erties, and generates fibers of desired properties that can be tai- orders of magnitude, from 0.014 to 1 cm2 V−1 s−1.64 As a matter
lored according to the desired application (Fig. 10(b)). Figure 10 of fact, in recent years many reports have emerged concerning
(c),(d) shows the mechanical properties of spider silk in compar- the application of silk in advanced technological applications,
ison to the respective values of other known materials, either i.e. photonics, thin-film and conformal electronics, field effect
natural or synthetic. transistors and light-emitting transistors. These advances set the
Although the global market of silk is predominated by its fiber stage for the fabrication of eco-friendly, sustainable and bioactive
application for textile manufacturing, silk has emerged recently electronic devices. The advantages of the substrate properties of
as a material of choice for a plethora of other applications, sche- this all-natural biopolymer can be exploited as an alternative to
matically exemplified in Fig. 11. rigid substrates, enabling the fabrication of degradable devices at
Figure 11 presents the two possible avenues of silk implementa- a controlled biodegradation/dissolution rate,70–72 opening in this
tion in novel technological applications: one including natural silk way a viable pathway for sustainable high-tech manufacturing.
and the other involving genetically engineered silk. Genetically If silk is a material known since as early as 2700 BC,55,56 shellac is
engineered silk has the advantage of precise control exercised itself an engineering material known for several millennia. Shellac
by the designer over the mechanical, morphological and struc- was as a matter of fact mentioned even in Mahabharata, the
tural features of silk, which can be used to generate novel material revered Indian novel written in verses that was completed during
forms and platforms for a wide range of applications. Natural silk a period between 400 BC and AD 400. In this respect, shellac can
sutures are nowadays replaced by other degradable polymer be considered the first material reported in a written publication.
system-based fibers (most notably poly(lactic acid) and In the Mahabharata incidence, an Indian prince offers to a beloved
poly(lactic-co-glycolic acid)); however, silk sutures are still used wife a residence palace fully varnished with shellac. This particular
for eye and lip surgery, intraoral surgery and for some skin utilization of shellac remained over the centuries its major appli-
wounds. Other medical applications of silk exemplified in Fig. 11 cation, with shellac-producing centers scattered in the south
comprise drug delivery systems, and fiber-based products for lig- and the center of the Asian continent, i.e. India, Thailand, China,
ament, bone and tissue repairs. Emerging applications for silks are Myanmar and Bangladesh. Several companies are involved world-
in the areas of environmentally compatible systems; photonics wide in shellac production and trading; however, there is only one
(as implantable optical systems for diagnosis and treatment); as company in the world, i.e. AF Suter, with its branches in India,
well as electronics (as transient substrates for flexible, conform- Germany and UK, that oversees the entire industrial process,
able, implantable, biodegradable and even resorbable electronic i.e. harvesting, processing and commercialization of various
displays for improved physiological recording).62,63 custom-made applications. Major markets of shellac are varnish
In the area of electronics, we highlight in this short review the formulations for woods, coating (glazing) for pharmaceutic drugs
usage of silk as an organic dielectric material for field effect (mainly as barrier coating, enteric coating and taste masking for
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Figure 10. Mechanical properties of silks. (a) Toughness (energy taken up by the material before breaking) and relative tensile strength (maximum stress
that a material can withstand while being stretched or pulled before breaking) of reeled spider dragline silk. (b) Comparison of the stress–strain curve of
spider silk and silkworm silk from Bombyx mori caterpillar obtained at different drawing speeds. (c) Stress versus strain curves for major ampullate
(MA) gland silk (red line) and viscid silk (blue line) from the spider A. diadematus. Einit stands for initial stiffness. (d) Tabulated data from multiple sources
and based on data from the spider A. diadematus. Reproduced with permission from Ref. 61.

bitter pills) and coating barrier for the prevention of moisture trees, the kusum tree is the one that is recognized to give the
release for citrus fruits, where shellac is given the food ingredient highest yield along with low base color levels of shellac.73
number E 904 in the European Union. Additionally, shellac is a The explanation for the difference in yield is given by the life cycle
gastro-resistant polymer which means it provides protection at of the lac insect, which feeds on the sap of the tree (therefore the
lower pH levels (in the stomach) but dissolves at higher pH in preference for a specific tree), produces shellac as part of its own
the small intestine, hence its prominent usage as an enteric coat- metabolism and secrets it on the branches of the trees as encrus-
ing material. In total, the amount of shellac commercialized in the tation. The deposit acts as a source of food for the larvae immedi-
world exceeds 20 000 tons/year, and importantly it is wholly a ately after their emergence from the laid eggs, and offers at the
natural product; there is no synthetic alternative to shellac in the same time housing, i.e. protection to the strong UV radiation
world. experienced in certain areas of the globe. Given the multiple pos-
Shellac biopolymer is laid on the branches of host trees by the sibilities (tree species and strains of insects), the final shellac prod-
female lac bug, a minuscule insect of 0.5 mm in size that lives in uct comes in a multitude of colors and intricate compositions. The
colonies on the branches of host trees. Among the most common encrustation deposited by lac insects represents the original bio-
lac insects are Kerria lacca and Kerria chinesis and their preferred polymer, known in shellac nomenclature as sticklac. It is crudely
host trees that support the growth of colonies are: kusum (Schlei- purified directly at the producers by cleaning it from impurities
chera oleosa), dhak (Butea monosperma) and ber (Ziziphus mauriti- and then solubilizing it in water in order to remove the water-
ana) in India, rain tree (Albizia saman) in Thailand and pigeon pea soluble anthraquinone derivatives in the form of laccaic acids (col-
(Cajanus cajan) in both China and Thailand. In addition to these orants). The removal of the red colorant produces the next shellac
tree species, also various Hibiscus tree species support the growth product known as seedlac. The remaining brownish color of the
of shellac-laying insect colonies. Among the above-mentioned seedlac can be further reduced in various processing steps
11

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Figure 11. Generating new materials and opening new applications for silks. Left: native silk processing. Top right: engineered silk production starting from
either reconstituted native silk proteins or genetically engineered silks. A wide range of materials and various applications (bottom right) can be generated
from silks through processing into hydrogels, fibers, sponges, films and many other forms (middle right). Reproduced with permission from Ref. 61.

Figure 12. Electrical characteristics of fullerene C60 semiconductor on (red frame) Au gate electrode–silk dielectric and (blue frame) Au gate electrode–
silk dielectric with 2 nm of pentacene as interlayer to favor the growth of larger C60 crystallites. (a) Output characteristics; (b) transfer characteristics;
(c) quasi-static capacitance versus voltage curve recorded at a sweep rate of 0.8 V s−1. Reproduced with permission from Ref. 64.
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involving activated carbon and even hypochlorite bleaching. A sche- pentacene (p-type) and C60 (n-type) semiconductors. Shellac dis-
matic of the production process of shellac is presented in Fig. 13. plays remarkable dielectric properties, demonstrated by a relatively
The three main constituents forming the complex structure of flat capacitance over a measurement window of 8 orders of magni-
Shellac are aleuritic, jalaric and shellolic acids, presented in tude, from 10 kHz to 0.1 mHz, while having an outstanding break-
Fig. 14; however, the full list of components comprises more than down field of ca 9 MV cm−1 (Fig. 15, blue panel). All these
40 chemicals.74,75 accolades come in conjunction with an outstanding film-forming
Among the constituents, resins sum up to ca 70–85% of the total characteristic, exemplified in Fig. 15 (green panel), where a
weight, waxes ca 3–8% and various other molecules ca 5–10% of spin-coated film of shellac has a root-mean-square (r.m.s.) surface
shellac. The hydrophobic nature of shellac is mainly imparted by roughness of only 0.4 nm, while a drop-cast film of shellac has a sur-
aleuritic acid, but the wax content adds to the water-repelling and face roughness of ca 1 nm. Figure 15 (orange panel) presents the
barrier properties of shellac too. For hydrophobicity purposes, wax- results of a recent study where a commercially available dewaxed
containing shellac is theoretically better than wax-free shellac; in shellac (obtained from the shellac producer AF Suter) was employed
addition, waxes also help in rendering shellac a better film-formation as a matrix for the embedment of inorganic nanoparticles, sepiolite,
property since they interfere with different substrates and impact montmorillonite (MMT), vermiculate and halloysite with the end goal
the adherence with the substrate. Hence dewaxed versions are gen- of creating thin films of high dielectric constant.79 Due to its admira-
erally the formulations typically offered to customers, and waxes are ble film-forming characteristics and low interface trap density at the
added separately depending on the type of target applications. interface with the organic semiconductors pentacene and C60, the
Fresh shellac is easily soluble in various alcohols; however, water sol- OFETs with MMT and shellac as dielectric layer operate at low volt-
ubility is possible only in weakly alkaline solutions. Stability of shellac ages of about 3 to 4 V, while exhibiting hysteresis-free behavior in
is negatively impacted if stored for more than 2 years at tempera-
tures above 20 °C, since it undergoes a slow polymerization and
esterification reaction between the carboxyl and hydroxyl groups
of two neighboring component molecules (see Fig. 14). As a conse-
quence of this reaction, both the hydrophobicity of shellac and its
solubility in alcohol solution diminishes. Therefore, extreme care
must be taken when ordering shellac from chemical suppliers, espe-
cially when the age of shellac and the storage conditions are
unknown or not reported; in general, storing shellac at cold temper-
atures (refrigeration) ensures product stability.
Although the major applications of shellac are in the food and
pharmaceutical industries,76 given by its nontoxic, even edible char-
acteristics, shellac has been reported recently also in various emerg-
ing technological fields, i.e. electronics and sensor fabrication,77–86
microfluidics87–89 and health monitoring devices.90–93 In one of the
earliest demonstrations of shellac as dielectric for OFETs, commer-
Figure 14. Three main constituents of shellac. The full composition of
cially available, wax-containing shellac (obtained from the chemical shellac includes more than 40 molecules, among them esters of aleuritic,
supplier Sigma-Aldrich) was employed as gate dielectric for low-volt- jalaric, shellolic and butolic acids, as well as colorants and waxes. Drawing
age-operating, hysteresis-free OFETs (Fig. 15, red panel) with both courtesy of Rahul Mourya, AF Suter Inc.

Figure 13. Schematic of shellac production. The insets show photographs the shellac plantations in forms of kusum trees and seedlac deposited on a
13

tree branch. Courtesy of Rahul Mourya, AF Suter Inc.

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www.soci.org M Irimia-Vladu, NS Sariciftci

Figure 15. Red panel: (a) Transfer characteristics of fullerene C60 OFET using shellac as both a substrate and dielectric layer. (b) Transfer characteristics for
a similar structure with pentacene semiconductor. Blue panel: Electrical measurements of metal–insulator–metal structures with shellac sandwiched
between top and bottom aluminium electrodes. (a) Relative permittivity and loss angle as a function of probing; (b) J–V characteristics for a 150 nm
spin-coated film of shellac that has breakdown field as high as 9 MV cm−1. Green panel: AFM images of shellac deposited via: (a) drop-casting, resulting
in a 0.5 mm thick shellac film, r.m.s. roughness ca 1 nm; and (b) spin-coating, resulting in a 30 nm shellac film, r.m.s. roughness ca 0.4 nm. Reproduced
with permission from Ref. 77. Orange panel: Transfer and output characteristics of OFET devices with clay–shellac homogeneous mixture as gate dielec-
trics and (a, b) pentacene semiconductor and (c, d) fullerene C60 semiconductor. The dielectric constant of various mixtures of shellac and MMT spanned
between 5.3 and 7.7, depending on the intake of MMT nanoparticles. Reproduced with permission from Ref. 79.
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Schematic of the lignocellulosic biomass www.soci.org

both transfer and output characteristics. The study also demon- 14 Bertella S and Luterbacher JS, Trends Chem 2:440–453 (2020).
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wide from 2017 to 2022 (in Million Metric Tons). Statista Statista Inc. Avail-
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ACKNOWLEDGEMENTS 34 Paeck M, Woehrmann M, Teopper M and Lang KD, 2019 IEEE 69th Elec-
tronic Components and Technology Conference (ECTC), IEEE, Las
Financial support from the project ‘EINSTEIN’, grant number
Vegas, NV (2019). https://doi.org/10.1109/ECTC.2019.00285.
101136377 (HORIZON-WIDERA-2023-ACCESS-03) is gratefully 35 Huang TH, Lai HC, Tzeng BJ and Pei Z, Org Electron 13:1365–1369
acknowledged. We also gratefully acknowledge the Wittgenstein (2012).
Prize of the Austrian Foundation of Advancement of Science 36 Bajwa DS, Pourhashem G, Ullah AH and Bajwa SG, Ind Crops Prod 139:
(FWF) for Prof. Serdar Sariciftci (project number Z 222-N19). 111526 (2019).
37 Sixta H, Handbook of Pulp. Wiley-VCH, Weinheim (2006).
38 Nitsos C, Rova U and Christakopoulos P, Energies 11:50 (2017).
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