Chapter 2

Review of Literature

Cardanol

Cardanol, extracted from natural cashew nutshell oil (CNSL), emerges as a pivotal green
industrial material. CNSL, an agricultural by-product obtained through pyrolysis or
supercritical carbon dioxide extraction from cashew shells, primarily consists of cashew acid,
cardanol, cardiac phenol, and dimethyl cardiac acid initially noted by Stadeler in 1847 (refer
to Fig. 1).

Figure 1: Components and products from CNSL

In recent years, cardanol has gained prominence due to its widespread application in coatings,
adhesives, and plasticizers. Its pale yellow oily liquid form is insoluble in water but readily
dissolves in organic solvents like ether, petroleum ether, and chloroform.
Studies by Dowson, Paul, and Loev have sorted out that cardanol have a chemical structure
of a monophenol derivative, and a 3-alkylphenol with side chains containing up to three
unsaturated bonds. Its chemical composition, characterized by phenolic compounds, hydroxyl
groups, and double bonds, facilitates easy chemical modifications. Possessing traits of both
aromatic and aliphatic compounds, cardanol exhibits high-temperature resistance, flexibility,
excellent hydrophobicity, and low permeability, suggesting its potential to replace phenol in
numerous applications.

Reviews have extensively detailed cardanol's composition, separation, purification, chemical

reactions, and applications. This comprehensive review delves into cardanol's role as a
fundamental ingredient in various polymer and polymer composites, including benzoxazine
resins, phenolic resin, polyurethanes (PUs), epoxy resin, vinyl ester polymers, polyamide,
and cyanate ester resins.

Cardanol, a naturally occurring substituted phenol, is capable of participating in various

reactions for the production of fine chemical products and polymers. This renewable and
cost-effective substance has the potential to replace phenol in numerous applications with
comparable or superior outcomes. Cashew phenolic amine, derived from the reaction of
cashew phenol, aldehydes, and polyamine, serves as a commercial epoxy curing agent. It
exhibits effectiveness at room or low temperatures, enabling solidification on wet surfaces,
although its application range is constrained due to the oxidizability of cashew phenol's
phenolic hydroxyl, resulting in a deeper color of the curing agent.

To address this limitation, a cardanol-based curing agent with a light color (MBCBE) was
synthesized and compared with phenalkamine (refer to Fig. 2). MBCBE showed lower
reactivity, but when used to modify epoxy resin materials, it improved toughness and shear
strength without affecting storage modulus and glass transition temperature.

Figure 2: Synthesis of MBCBE

Cardanol-based curing agents not only enhance physical properties but also alter chemical
resistance. Studies by Aggarwal et al. on cardanol-based epoxy resin materials demonstrated
superior chemical resistance in comparison to paints formulated with unmodified epoxy resin,
regardless of pigments, fillers, and additives. Additionally, research suggests that the
anticorrosive behavior of these paints is related to their strength and permeability properties.

Epoxidized cardanol, a commercial curing agent derived from the phenolation of aliphatic
chains and the reaction of phenol hydroxyl groups with epichlorohydrin, was used to
synthesize biobased aromatic epoxy materials (NC-514). The thermal stability of NC-514
cardanol-based epoxy resin materials was slightly lower than DGEBA modified epoxy resin
materials (refer to Fig. 3).

Figure 3: Chemical Structure of Epoxidized cardonal based curing agents

Kanehashi et al. synthesized a cardanol-based epoxy coating using thermal polymerization,

showcasing shorter hardening times and better chemical stability compared to commercial
cashew coatings. Other studies investigated the effects of various additives, diluents, and
curing agents on the curing behavior of epoxy resins.

Furthermore, novel cardanol-based phenalkamines (PAA1, PAA2, PAA3) were synthesized

using poly-condensing phenolic compounds, indicating decreased reactivity from
DGEBA/PAA3 to DGEBA/PAA1, with an associated increase in the toughness of the cured
epoxy resins.

The study also covers the synthesis of mono-functional cardanol-based epoxy resin systems,
investigations into co-epoxides of bisphenol A and cardanol, and the incorporation of
cardanol-BS modified layered double hydroxide into epoxy resins to improve flame
retardancy. The use of polyepoxide cardanol glycidyl ether (PECGE) as a diluent showed
improved characteristics in epoxy resin synthesis, enhancing mechanical properties, and
investigations into lignin and cardanol-based novolac epoxy resins demonstrated excellent
mechanical, thermal, and flame-retardant performances.

Epoxy Resin

Epoxy resins are renowned for their exceptional chemical resistance, toughness,
durability, and adhesion, rendering them suitable for diverse applications. Their high
resistivity and relatively low dissipation factors, coupled with robust mechanical properties,
contribute to their versatility. Epoxy resins find utility as coatings, adhesives, and composites.
Notably, they exhibit compatibility with a broad spectrum of curing agents, allowing for
tailored customization of their properties. These resins are characterized by the presence of
one or more epoxide or oxirane groups, and they can be categorized into three main types:
cycloaliphatic epoxy resins, epoxidized oils, and glycidated resins. Among them,
commercially significant epoxy resins are predominantly derived from the glycidation of
bisphenol A with epichlorohydrin, yielding a diverse array of products with varying
properties.

Figure 4: Epoxide Functional Group (above) & Cycloaliphatic epoxy resins(below)

 Figure 5: Bisphenol A Epoxy Resin

The landscape of epoxy resin production and utilization has undergone significant
transformations since its commercial debut in 1947. In the 1950s through the 1970s, the
market witnessed the proliferation of new epoxy types, boasting at least 25 distinct varieties
by the late 1960s. Presently, epoxy resins play a pivotal role across diverse industries, finding
applications in coatings, electrical and electronic insulation, adhesives, composites, and
construction. In 1994, the total epoxy market reached approximately 443 million pounds,
with coatings accounting for slightly over half (53%) of the usage. The remaining portion
was distributed across structural markets within the listed areas. The growth trajectory of
epoxies has been consistently upward, with epoxy adhesive production escalating from 18
million pounds in 1980 to 40 million pounds by 1994 (Goodman, 1998).

Renowned for their high performance, epoxy resins excel in coatings, adhesives,
plastics, and structural applications. Noteworthy attributes encompass chemical resistance,
superior adhesion, low cure shrinkage, and excellent electrical properties. Epoxy resins offer
a versatile range of products adaptable to specific needs, fostering growth and diversified
usage across various industries (Sandler & Karo, 1994).
Silver

Silver nanoparticles are added to paint for their antimicrobial properties, inhibiting the
growth of bacteria and fungi. This makes the paint suitable for environments requiring
cleanliness, like healthcare facilities. The nanoparticles also contribute to anti-fouling
surfaces, reducing the adhesion of contaminants and providing self-cleaning features.
Additionally, silver nanoparticles enhance paint durability, prevent mold and mildew growth,
and inhibit odor formation. While these properties offer numerous benefits, it's essential to
consider potential environmental and health impacts and adhere to regulations governing
their use in consumer products.

Silver nanoparticles (Ag NPs) exhibit antibacterial activity through the release of
silver ions (Ag+), particularly when interacting with microbial cells in aqueous biological
media. The oxidative dissolution of Ag+ ions from Ag NPs, prompted by the presence of O2
in these media, contributes to their bactericidal effectiveness. The physico-chemical
properties of Ag NPs, including size, shape, and surface properties, play a crucial role in
determining their interaction with biological media and bacterial cells. Surface properties,
such as charge and surface area to volume ratio, along with the form of silver in the
nanoparticles (ionic, nano, or aggregated), and factors like size, shape, and oxidation
potential, collectively influence the antimicrobial efficacy of silver nanoparticles at both the
molecular and cellular levels. (Pareek et al., 2018)

Silver nanoparticles exhibit an affinity for molecular groups containing sulfur and
phosphorus, prevalent in bacterial membranes and within bacterial cells. These nanoparticles
have the capability to release silver ions, causing damage to transmembrane electron
transportation and hindering DNA replication. Notably, silver nanoparticles are actively
utilized as antimicrobials incorporated into biomaterials and coatings across various
applications to mitigate surface microbial biofilm formation (Neves et al., 2014).

In another study, it was observed that the incorporation of silver nanoparticles at a

concentration of 10 ppm led to a 22% average increase in surface temperature and drying
velocity. This concentration level indicated an optimal nanoparticle amount. The introduction
of silver nanoparticles resulted in reduced drying times, suggesting an accelerated drying
process. Furthermore, these nanoparticles influenced the composition of paint during drying,
 potentially enhancing the final coating quality and chemical interactions (Lotfizadeh et al.,
2017).

References:

Jia, Puyou., Song, Fei., Li, Qiaoguang., Xia, Haoyu,. Li, Mei,. Shu, Xugang., Zhou,
Yonghong. (2019).
Recent Development of Cardanol Based Polymer Materials-A Review. Journal of
Renewable Materials, 7(7), 601-619.
https://doi.org/10.32604/jrm.2019.07011
Lotfizadeh, H., Rezazadeh, S., Fathollahi, M. R., Jokar, J., Mehrizi, A. A., & Soltannia, B.
(2018).
The Effect of Silver Nanoparticles on the Automotive-based Paint Drying Process: An
Experimental Study. International Journal of Advanced and Multidisciplinary Engineering
Science, 2(1), 7–14.
Neves, P. B. A. das, Agnelli, J. A. M., Kurachi, C., & Souza, C. W. O. de. (2014). Addition
of Silver Nanoparticles to Composite Resin: Effect on Physical and Bactericidal Properties
In Vitro. Brazilian Dental Journal, 25, 141–145.
https://doi.org/10.1590/0103-6440201302398
Pareek, V., Gupta, R., & Panwar, J. (2018).
Do physico-chemical properties of silver nanoparticles decide their interaction with
biological media and bactericidal action? A review. Materials Science and Engineering: C,
90, 739–749.
https://doi.org/10.1016/j.msec.2018.04.093
Sandler, S. R., & Karo, W. (1994). Epoxy resins. In Elsevier eBooks (pp. 87–128).

https://doi.org/10.1016/b978-0-08-092555-4.50007-4