Literature Review of Nanoparticle

Reinforced Polymer Composites

Name: Darpan Theng

Reg. No: 200933026

Title: Nanoparticles reinforced polymer/metal composites

Submitted on: 10-11-2023.

Submitted to: Dr. Yogeesha Pai.

DEPT.OF AERONAUTICAL AND AUTOMOBILE ENGINEERING

MANIPAL INSTITUTE OF TECHNOLOGY, MANIPAL-576104

Nanocomposites represent a unique blend of two or more phases, each with distinct
compositions or structures, where at least one phase falls within the 10 to 100 nm range. The
nanoscale fillers, characterized by a few atoms per particle, exhibit properties divergent from
the bulk material and establish robust interactions with the matrix. The separation of filler
particles operates at molecular dimensions, thereby modifying the properties of polymers. In
polymer nanocomposite research, the primary objective is to enhance the strength and
toughness of polymeric components by incorporating molecular or nanoscale fillers.
Composites demonstrating composition and structure changes over a nanometer scale
showcase remarkable property enhancements compared to conventional counterparts. These
enhancements include increased modulus, heightened gas barrier, elevated heat distortion
temperature, resistance to small molecule permeation, improved ablative resistance, increased
atomic oxygen resistance, and retention of impact strength.

There are three main methods of preparation:

1. Sol-gel method: Combination of hydrolysis and poly-condensation of the

intermediates

Sol-gel infiltration technique

2. In-situ Intercalative polymerization: Method for polymer clay mineral hybrids

3. In-situ polymerization: Nanometer-scale inorganic fillers or reinforcements are
dispersed in the monomer.

NP is a tiny 1D, 2D, or 3D particle with dimensions ranging between 3 and 100nm in all
directions where the most commonly observed shapes are nanorods, nanocages, and
nanoshells. A wide range of properties, e.g., optical, electrical, mechanical, structural, etc.,
can be significantly tuned by controlling the size and surface area of the NPs.
 Clustered Nanoparticles and Uniformly Distributed in the Matrix

In terms of nanocomposites, these NPs can be divided into three major categories: metal NPs,
ceramic NPs, and polymer NPs:

1. Metal Nanoparticles: These NPs possess properties like appreciable surface area-to-
volume ratio as compared to the bulk equivalents, large surface energies, increased
number of kinks, plasmon excitation, quantum confinement, short-range ordering,
high stability, and high reactivity. These particles are mainly created with the help of
two methods: Top-down and Bottom-up methods.
2. Ceramic Nanoparticles: A porous inorganic system, composed of ceramic materials
that are typically derived from metal oxides, hydroxide, sulfate, phosphates,
and carbonates. Besides, sometimes metalloids and their oxides, for example, silicon,
calcium, titanium, etc., are used to form ceramic nanoparticles. Ceramic NPs are
classified into two categories: oxide-based (Alumina, silica, ZnO, etc.) and non-oxide-
based (graphene, SiC, carbon black, etc.)

Methods of preparing nanoparticles.

Matrix types:

1. Metal Matrix: Nanoparticle-reinforced metal matrix nanocomposites occupy a large

portion of automotive, aerospace, and military industries along with their
conventional applications as a structural material. This kind of matrix brings high
mechanical strength, elastic modulus, ductility, thermal stability, stiffness, wear,
creep, etc., to a material which can be easily tailored using different nanoparticles.
2. Ceramic Matrix: Ceramic matrix utilizes conventional ceramic materials as a base
material aiming for the overall improvement of properties with the use of different
nanoparticle reinforcement. The scopes of improvements can be toughness,
brittleness, mechanical unreliability of monolithic ceramics, and thermal shock
resistance.
Ceramic matrix polymer nanocomposites are the type of composites where the
ceramic materials work as the matrices. Nanoparticle reinforcements can be
incorporated through different routes. The common routes for the preparation of
ceramic matrix polymer nanocomposites are (a) conventional powder method, (b)
polymer precursor route, (c) spray pyrolysis, (d)chemical vapor deposition, (e)
chemical vapor infiltration, (f) physical vapor deposition, and (g) sol-gel method. In
this section, the working principle, applications, advantages, and disadvantages of
ceramic matrix nanocomposites have been described.

Ceramic Nanoparticle synthesis

One of the major applications one can use for nanoparticle-based composites is vibration
damping. The most common composite is the alumina-reinforced rubber. In forced vibration
methods, the dynamic properties (or viscoelasticity) of a rubber compound are determined by
measuring its response to a sinusoidally varying strain. Elastomers that do not strain-
crystallize need reinforcement to obtain adequate tensile properties. The mechanism of the
reinforcement is believed to be both chemical and physical. Reinforcement of nanoparticles
into elastomers significantly improves their damping characteristics and dynamic mechanical
properties. The nanoparticle size and the high aspect ratio yield an extraordinary
enhancement of the properties of rubbery materials.
 Spray pyrolysis methodology

Another application is in electronics as a dielectric material where its properties can be

altered. The prevalent method for augmenting the dielectric permittivity of polymers involves
dispersing insulating ceramic powders with high dielectric permittivity, such as barium
titanate (BaTiO3) and lead titanate (PbTiO3), into the polymer matrix to create composites.
Achieving a substantial dielectric permittivity value necessitates the incorporation of a
significant quantity of fillers. However, this high filler loading leads to a compromise in
flexibility and the development of inhomogeneous composites.

Varied concentrations of Ti nanoparticles

Some of the recent innovations include UV-curable or photocurable gold nanoparticle

polymer nanocomposites. These kinds of curing have had several advantages over the most
commonly used curing procedures like fast curing, high final conversion, and spatiotemporal
selectivity of the reaction. Another factor contributing to increased polymerization near gold
nanoparticles is the well-established high affinity of amines for gold surfaces. It is widely
recognized that there is a greater concentration of amine at the surface of nanoparticles
compared to the surrounding solution. This circumstance could potentially enhance the
polymerization rate around nanoparticles, given that the amine plays a role in the free-radical
production mechanism. The difference observed may be attributed to the dipolar response of
metallic nanoparticles. The presence of nanoparticles alters the local distribution of the
electromagnetic field, causing a modification in the overall system.

Supercapacitors have gained significant importance as a new class of energy storage systems
due to their rapid charge-discharge rates, extended lifespan, and high-power capacity. They
are utilized in various applications, including backup energy sources, green transportation in
hybrid electric vehicles, and emergency power supplies. Nanocomposites with high specific
capacitance and long lifespans are commonly employed in supercapacitor manufacturing
because the nanoparticles present in these composites offer shorter ionic diffusion pathways,
resulting in lower energy dissipation.

Supercapacitors are generally categorized into two types: electrical double-layer capacitors
and pseudo capacitors. The electrical double-layer capacitor forms as a result of a double
layer on the electrode surface, while the pseudo capacitor stores charge on the material's
surface and within the bulk, utilizing a combination of the double-layer mechanism and
faradaic reactions. As a result, the pseudo capacitor can store 10-100 times more charge
compared to the double-layer capacitor.

For the construction of a supercapacitor, an electrode made of a carbon nanotube (CNT) –

ZnO nanocomposite is employed, along with an electrolyte composed of PVA (polyvinyl
alcohol) – phosphomolybdic acid (PMA) gel. The deposition of ZnO nanodots onto the CNT
films was achieved using the ultrasonic spray pyrolysis technique

Basalt nanoparticle reinforced composites: Basalt, when combined with carbon, polyamide,
glass, and aramid fibers, serves to enhance performance in various applications. Basalt fiber
stands out due to its high modulus, impressive resistance to fire, and resilience against
exposure to acids and alkalis, making it a valuable component in the composites industry.
The key advantages of basalt fiber include advanced mechanical properties and exceptional
heat resistance. Experimental evidence indicates that basalt can endure temperatures as high
as 600 degrees Celsius without compromising its mechanical properties and with minimal to
no weight loss. This resilience positions basalt as a robust choice for demanding conditions in
composite materials. These particles are mostly made through a ball milling process. The
process of ball milling is based on the principle of energy release at the point of contact of
balls as well as with friction that is a result of high grinding action. The inclusion of
nanoparticles is evident in improving the tensile stress-strain characteristics of the epoxy
polymer. Nanocomposites show a heightened tensile modulus. This increase in modulus is
anticipated due to the inherently high modulus of basalt. Moreover, the even dispersion of
these nano-fillers within the matrix contributes to enhanced fracture resistance. As the tensile
load increases, the matrix attempts to elongate in its typical manner.
 Scanning Electron Microscopy of basalt nanoparticle reinforced composite.

Alumina nanoparticles reinforced composites: Alumina (Al2O3) nanoparticles are

extensively employed as engineering ceramic fillers due to their capability to enhance
composites with high elastic modulus, excellent wear resistance, chemical corrosion
resistance, stability, and retained strength at elevated temperatures. Despite these advantages,
challenges such as heightened brittleness and particle accumulation during fabrication impose
limitations on their use. To comprehend stress transfer behavior and improvements in
mechanical properties, numerous experimental and theoretical studies have investigated fiber
and particle-loaded composite materials. Recently, short-fiber-reinforced thermoplastics have
gained popularity due to their not only superior mechanical properties but also ease of
production through rapid, cost-effective extrusion compounding, and open molding
processes. The gradual decrease in tensile strength is noted with the introduction of alumina
in the composite, while an increase is observed with the incorporation of fibers. This decline
in strength is attributed to the agglomeration of nanoparticles as their concentration increases,
leading to a higher surface area available for the entrapment of macro-sized air bubbles from
the atmosphere.

Microscopic techniques play a crucial role in analyzing nanocomposites. These techniques

include scanning electron microscopy (SEM), atomic force microscopy (AFM), and
transmission electron microscopy (TEM). SEM is valuable for studying the surface
morphology of nanocomposites, but it requires the surface to be electrically conductive. In
cases where the sample is non-conductive, a thin layer of gold or carbon is coated on the
surface. SEM offers a resolution of around 1-2nm.

TEM, on the other hand, is preferred for its superior resolution, typically in the range of 0.1-
0.2nm. It provides detailed insights into the nanocomposite structure, revealing core-shell
configurations, morphology influenced by doping effects, particle size, the impact of gelling
agents, dispersion of nanoparticles, layering within the structure, and surface roughness.
However, one drawback of TEM is the challenging sample preparation, which necessitates
achieving a very low film thickness.
Atomic force microscopy (AFM) is used for surface imaging of both conducting and non-
conducting materials at the atomic resolution level. It operates by measuring the forces
between atoms on the sample surface and the AFM tip. AFM can work in various modes,
including contact mode, tapping mode, and conductive mode. It provides data in 2D, 3D, and
line profiles, which offer insights into the dispersion of nanoparticles, the height of
nanoparticles within the matrix, and the height of the matrix itself. Additionally, AFM can be
used to determine the surface roughness of nanocomposite membranes.

X-ray Diffraction (XRD): From XRD measurement crystalline phase and Crystallite size will
be characterized using a powder X-ray diffractometer. To know about the phase
determination and for unit cell information of nanocomposites under investigation Powder,
X-ray Diffraction (XRD) is used. This technique is employed to determine the particle size
using Scherrer's formula:

𝐷=𝐾𝜆𝛽𝑐𝑜𝑠𝜃,

D (nm) is the mean size of the crystalline domains,

K is the dimensionless shape factor whose value is close to unity,

𝜆 is x-ray wavelength,

β is line broadening referring to FWHM and

θ is Bragg angle. This equation is used when nanocomposites have a definite crystalline
structure only.

Zinc Oxide-based nanoparticles: Nano-sized zinc oxide (ZnO) was synthesized by sol-gel
method and mixed with polyvinyl alcohol (PVA) to produce nanocomposite films. Zinc oxide
(ZnO) has garnered significant attention owing to its versatile properties. It functions as a direct
wide band gap semiconductor (Eg ≈ 3.4 eV) with a substantial exciton binding energy. ZnO
also exhibits robust ultraviolet and visible photoluminescence. Given these essential
characteristics, ZnO finds applications in various fields, including photocatalysis, gas sensors,
varistors, and low-voltage phosphor materials. On the other hand, polyvinyl alcohol (PVA) is
a semi-crystalline polymer, and the crystalline index of PVA is contingent upon the synthetic
process and physical aging. The crystalline nature of PVA arises from the robust intermolecular
interaction among PVA chains facilitated by intermolecular hydrogen bonding. The
improvement in modified ZnO nanoparticles reinforced composite was superior to unmodified
particle-reinforced epoxy composite at the same nanofiller content (2 wt.%). The mechanical
properties including the tensile strength, tensile modulus, compressive strength, flexural streg
th, and flexural modulus were significantly increased in the case of modified ZnO nanoparticles
reinforced composite at 2 wt.% nanoparticle concentration.

The flexural properties of both unmodified and modified ZnO/epoxy nanocomposites were
investigated. It was observed that the flexural strength and modulus of these nanocomposites
increased as the particle content was raised up to 2 wt%. However, when the particle content
was further increased from 2 to 3 wt%, both the flexural strength and modulus started to
decline.
 Un-modified and modified ZnO nanoparticles with PVA.

Among all nanocomposites and pure PVA, the loaded ZnO in PVA demonstrated a low
dielectric constant and dielectric loss, along with a high conductivity value. This is attributed
to its shorter relaxation time, suggesting its potential use in electromagnetic induction (EMI)
shielding and microwave absorption applications.

The main limitations and challenges associated with the synthetic methods of ceramic matrix
polymer nanocomposites are:

1. Conventional powder method: This is a commonly used method to synthesize ceramic

matrix polymer nanocomposites, but it is expensive. Agglomeration and low
dispersion problems are significant challenges to achieve an optimal second phase
powder grain distribution in the matrix powder. In addition, there are environmental
problems associated with the release of nano-sized powder particles during this
process.
2. Polymer Precursor Method: Although the polymer advance route is an alternative to
the conventional powder method, it is suitable for limited matrix materials.
Unreactive precursors or by-products can damage the quality and properties of
nanocomposites, so it is necessary to improve its applicability. Spray pyrolysis: Spray
pyrolysis has gained popularity, but its low performance limits its use in certain fields.
Challenges include determining the growth temperature and dealing with unwanted
oxidation problems to expand its range of applications.
3. Chemical Vapor Deposition: This technique has a wide range of applications, but has
problems such as soot formation, poor adhesion between layers and substrates, and
low production rates, which must be addressed to increase its usefulness.
4. Chemical Vapor Intrusion: Chemical vapor intrusion is a possibility and can introduce
toxic, corrosive and explosive reagents into the environment. In addition, its slow
deposition and high residual porosity make it difficult in many applications.
5. Physical vapor deposition: As with other vapor-based methods, physical vapor
deposition has problems with feasibility, slow performance, frequent maintenance
requirements, and expensive cooling systems. Improvements are needed to diversify
its application areas.
The main limitations and challenges associated with synthesis methods for polymer matrix
polymer nanocomposites are:

1. Intercalation of polymer or prepolymer from solution: This method is suitable when

processing is not a critical issue and has no particular disadvantages. In situ
intercalation polymerization: this method requires activation, which affects its
efficiency. In addition, it contains layered materials and optimized swelling is
essential for success.
2. Intercalation of castings: In this method, agglomeration can be a challenge that can
prevent the desired mechanical properties from being achieved. Maintaining precise
thermodynamic control can also be difficult in some cases.
3. Model Synthesis: Controlling the interaction between the model and the material can
be difficult and the upper limit of the model dimension must be well defined.
4. In Situ Polymerization: Thermodynamic conditions must be maintained for this
process because the final result can vary due to differences in heat treatment.
However, this challenge has diminished in recent years.
5. Sol-gel process: In some nanoscale applications, the materials involved can be
sensitive to the surrounding atmosphere, leading to changes in functionality or
structural form, especially in biomolecular applications. In such cases, additional
steps are required, although this is not a general limitation of the sol-gel process.

Future of nanocomposites: The number of commercial applications of nanocomposites has

been growing at a rapid rate. The following areas have the applications of nanocomposites:

1. Drug delivery systems

2. Anti-corrosion barrier coatings
3. UV protection gels
4. Lubricants and scratch-free paints
5. New fire-retardant materials
6. New scratch/abrasion-resistant materials
7. Superior strength fibers and films.

Improvements in the mechanical property have resulted in a major interest in

nanocomposite materials in numerous automotive and general/industrial applications.
The popularity of nanocomposites comes from the fact that it provide a marked
increase in oxygen, carbon dioxide, moisture, and odor barrier properties, increased
stiffness, strength, and heat resistance, and maintain film clarity and impact strength.
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