Polymer Engineering

Assignment # 2
Submitted By:
MUHAMMAD SHOAIB

ROLL NO

FA17-CHE-045-A

Submitted To:
Dr Zulfiqar Ali

Submission Deadline:
23. Nov 2020

Comsats University Islamabad, Lahore Campus

Title: Nano Composites and their Importance

Question 1
Composites:
A composite material is made by combining two or more materials, often ones that have
very different properties. The two materials work together to give the composite unique
properties. Composites occur naturally and can be synthesized artificially, for example;

 Natural Composite: wood is a natural Composite.

 Artificial Composite: Mud bricks, made in furnaces at high temperature, is an example
of artificial composite.

Nanocomposites:
Nanocomposites are the heterogeneous/hybrid materials that are produced by the
mixtures of polymers with inorganic solids (clays to oxides) at the nanometric scale. Their
structures are found to be more complicated than that of micro composites. They are highly
influenced by the structure, composition, interfacial interactions, and components of individual
property. Nanocomposites have many types some of them are;

 Graphene nanocomposites
 Polymer clay nanocomposites

Question 2
Composites significance in our daily life:

Composites have permeated our everyday lives: They are used in the cars we drive, golf clubs
we swing, pipes that remove wastewater from our neighborhoods and much more. Some
applications, such as rocket ships, probably wouldn’t get off the ground without composite
materials. Composites offer many benefits. Key among them are strength, light weight, corrosion
resistance, design flexibility and durability. Although, the resulting product is more efficient, the
raw materials are often expensive, some of the daily uses of these advanced and modern
materials are:

 Composite materials are very attractive for all kinds of sports activities.
 A large increase in composites can be found in the construction of maintenance-free
composite doors.
 They are usually integrated in the interior and the exterior housing is typically made of
unreinforced plastics.
Question 3
Difference between composites and nanocomposites:
Composite materials are prepared from the combination of two or more different
materials with distinct chemical or physical characteristics. The resultant composite exhibits
properties which are distinct to its constituent materials, which remain separate and distinct
within the finished structure and are not held together by formal chemical bonds. In
nanocomposites, either one of the constituents has dimensions on the nanoscale (<100 nm) or
instead the composite structure exhibits nanosized phase separation of the individual
components.

Question 4
What are the effects of nanoparticles?
Nanoparticles can pass through different cell membranes of mammalians and be absorbed
in them, and their absorption rates depend on their size. Then size of the nanoparticles and their
distribution, aggregation, and sedimentation in the cells are the most important parameters in
determining their absorption rates. Small nanoparticles and thick interphase improve the strength
of nanocomposites. However, a poor strength is observed by big particles and thin interphase.
Therefore, both radius and thickness parameters affect the tensile strength of nanocomposites.

Moreover, it is found that the strength of nanocomposites reduces when the size of
nanoparticles grows, due to aggregation/agglomeration. Accordingly, it is essential to isolate and
disperse the nanoparticles in polymer matrix at small size to achieve the best performances.
Since nanoparticles naturally tend to aggregation/agglomeration, modification of their surface or
functionalization of polymer chains can prevent the accumulation.

Question 5
Types of Nanocomposites:
 Ceramic-matrix nanocomposites
 Polymer- matrix nanocomposites
 Polymer-silicate nanocomposites
 Elastomeric nanocomposites
 Bio nanocomposites

Types of Nanoparticles:
 Carbon based nanoparticles
 Ceramic nanoparticles
 Metal nanoparticles
  Semi-conductor nanoparticles
 Polymeric nanoparticles
 Liquid based nanoparticles

Polymer clay nano composites

Question 6
Importance of clay nanocomposites:
 The most common use of polymer-clay nanocomposites has been in mechanical
reinforcement of thermoplastics, especially polyamide-6 and polypropylene.
 The use of polymer-clay nanocomposites for flame retardant applications is becoming
more common, especially as it is realized that the clay nanocomposite can replace part of
the flame-retardant package while maintaining fire safety ratings at a lower flame-
retardant loading. This results in a better balance of properties for the nanocomposite
material compared to the non-nanocomposite flame retardant product, and in some cases,
better cost for the flame-retardant resin, especially if the organoclay is cheaper than the
flame retardant it is replacing.
 Another common application of clay nano composite is for gas-barrier materials. Clay
nanoparticles create a complex network in the polymer matrix, such that various gases
either diffuse very slowly or not at all through polymer chains and pinholes in thin films
or thicker polymer parts. The success of clay nanocomposites to impart decreased
diffusivity of oxygen and water has led to their use in food/liquid packaging to keep
foods fresher longer.

Nature of clay nano composites:

Polymer-clay nanocomposites are formed through the union of two very different
materials with organic and mineral pedigrees. The hybrid compositions, however, exhibit large
increases in tensile strength, modulus, and heat distortion temperature as compared with the
pristine polymer. The composites also have lower water sensitivity, reduced permeability to
gases, and a similar thermal coefficient of expansion. All of these property improvements can be
realized without a loss of clarity in the polymer. Further, it has been found that clay
nanocomposites impart a level of flame retardance and UV resistance not present in the pure
polymer.

Techniques for manufacturing clay nanocomposites:

Commonly, there are four conventional processing techniques to make clay
nanocomposites:
Solution intercalation:
In this method the polymer or prepolymer is dissolved in a solvent and the clay is
dispersed in the same solution. The clay is swollen in the solvent and the polymer chains
intercalate between the layers. The intercalated nanocomposite is obtained by solvent removal
through vaporization or precipitation. Clays can be swollen easily in solvents such as water,
acetone, chloroform and toluene. The polymer chains are absorbed onto the delaminated sheets.

In situ polymerization:
In this method the organoclay is swollen in monomer liquid or monomer solution. The
monomers diffused into the inner layer spacing are polymerized by the heat or radiation, by the
diffusion of an initiator or by the organic initiator present on the organic modifier of clay. The
polymerization is carried out within the clay galleries as well as extra galleries. The growth of
polymer chains results to the exfoliation and formation of disordered structure.

Melt intercalation:
Clay is mixed within the polymer matrix in molten temperature. The conventional
methods such as extrusion and injection molding are used for dispersion of clay layers within the
polymer matrix. This method is effective technique for the preparation of thermoplastic
nanocomposites. The polymer chains are intercalated or exfoliated into the galleries. Clays are
organically modified and polymer chains are surface modified with more polar functional groups
to enhance their compatibility and therefore promote the exfoliation. In melt intercalation
method no solvent is required and it has many advantages for the preparation of nanocomposites
and is a popular method for industry.

In situ direct synthesis:

In this method the clay layers are synthesized in situ in the presence of polymer chains.
The polymer and clay primary materials are dissolved in an aqueous solution. Typically,
magnesium hydroxide, silica and lithium fluoride as clay building blocks are mixed with
polymer in a solvent. The gel or slurry is refluxed usually at high temperatures followed by
washing and drying. The nucleation and growth of clay layers are taking place on the polymer
chains and the polymer chains are trapped in the clay inter layers.

Nature of clays:
Clays have layered structure. The layers are built from tetrahedral sheets in which a
silicon atom is surrounded by four oxygen atoms and octahedral sheets in which a metal like
aluminum or magnesium is surrounded by eight oxygen atoms. The tetrahedral and octahedral
sheets are fused together by sharing the oxygen atoms. Unshared oxygen atoms are present in
hydroxyl form. Two main arrangements of tetrahedral and octahedral sheets fused together make
the one-layer structure of clay. For instance, the intrinsic incompatibility of hydrophilic clay
layers with hydrophobic polymer chains prevents the dispersion of clay nanolayers within
polymer matrix and causes to the weak interfacial interactions. Incompatibility and weak
interfacial interactions hinder the exfoliation and preparation of dispersed stable nanocomposite
with improved properties.

Modification of clays:
Modification of clay layers with hydrophobic agents is necessary in order to render the
clay layers more compatible with polymer chains. This is a surface modification which causes to
the reduction of surface energy of clay layers and match their surface polarity with polymer
polarity. The organoclays with lowered surface energy are more compatible with polymers and
polymer molecules are able to intercalate within their interlayer space or galleries under well-
defined experimental conditions.

The surface modification of clay layers can be achieved through a cation exchange
process by the replacement of sodium and calcium cations present in the inner layer space or clay
galleries by alkylammonium or alkyl-phosphonium cations. In addition to the surface
modification and increasing the hydrophobicity of clay layers, the insertion of alkylammonium
or alkyl-phosphonium cations into the galleries causes to some degree of increasing in the inner
layer spacing which promotes the following intercalation of polymer chains into the galleries
during nanocomposite preparation. Also, the alkylammonium or alkyl-phosphonium cations can
provide functional groups which interact with polymer chains or initiate the polymerization and
therefore increase the interfacial interactions.

Characterization techniques for clay nanocomposites:

In the preparation of a polymer/clay nanocomposite it is important to know the degree of
intercalation/exfoliation and its effect on the nanocomposite moderate properties. In other word
there is need to analyze the micro structure of the prepared nanocomposite. Two common
techniques which are widely used to characterize the micro structure of nanocomposite as well as
pure clay or pure organoclay are;

X-ray diffraction (XRD) analysis:

Clays and organoclays show a characteristic peak in XRD analysis due to their regular
layered structures. The peak is indicative of the platelet separation or d-spacing in clay structure.
Using the peak width at half maximum height and peak position (2θ) in the XRD spectra the
inner layer space can be calculated utilizing Bragg’s law:

Sin θ = n λ / 2d

Where λ is wave length of X-ray radiation used in the diffraction experiments, d is the space
between layers in the clay lattice and θ is measured diffraction angle.
Transmission electron microscopy (TEM)
A direct way to visually observe the nanostructure of nanocomposites and clay d-spacing is
to the use of transmission electron microscopy (TEM) technique. TEM micrographs allow a
qualitative understanding of the internal structure, exfoliation or spatial distribution of layers
within the polymer matrix and their structural defects.

Conclusion:
In conclusion, we can say that the biggest advantage of modern composite materials is that
they are light as well as strong. By choosing an appropriate combination of matrix and
reinforcement material, a new material can be made that exactly meets the requirements of a
particular application. Composites also provide design flexibility because many of them can be
molded into complex shapes/nanocomposites. The downside is often the cost. Although the
resulting product is more efficient, the raw materials are often expensive.

However, the key parameter to achieve successful nanocomposite materials, being fully
dispersed or exfoliated, is to comprehensively understand how to select the manufacturing
processes, appropriate materials and conditions that satisfy the optimum performance for specific
systems.

Moreover, Both XRD and TEM techniques are essential tools for evaluation of the
nanocomposite structure and complementary show the structural features of polymer/clay
nanocomposite microstructure. XRD provides almost quantitative and TEM provides qualitative
information’s about the exfoliation and d-spacing of clay layers in the polymer matrix compared
to that of in pure clay material. Also, other techniques such as those based on thermal analysis,
can be used to evaluate the interfacial interactions between clay layers and polymer chains.