PTE 502: Polymer Processing Engineering Technology IV

Lecturer: Engr. Dr. Innocent O. Arukalam

Review of effects of polymerization on polymeric engineering materials

Polymerization is the process of creating a large molecule called polymer by
chemically bonding many small molecules called monomers together.
Polymerization significantly affects polymeric engineering materials by
determining their final molecular structure. By controlling the molecular
structure of polymeric engineering materials, polymerization influences
properties such as the mechanical strength (tensile strength, flexural strength,
compressive strength, impact strength, and hardness, among others), thermal
properties (glass transition temperature, crystallization temperature, melting
temperature, thermal conductivity, thermal expansion and degradation
temperature) physical properties (density, permeability, refractive index) plus
viscosity and chemical characteristics, which are crucial for their performance
and application.
Again, by controlling polymerization parameters such as monomer types,
reaction conditions (temperature, pressure, solvent), and the polymerization
method, engineers can tailor properties like molecular weight distribution,
crystallinity, and branching to achieve desired characteristics.
Key effects of polymerization on polymeric material’s properties
(i) Degree of Polymerization: A high degree of polymerization generally leads
to high molecular weight, which in turn leads to increased tensile strength
and impact resistance. However, there is a critical point beyond which
these properties would dominish.
(ii) Molecular Weight Distribution: The polymerization process controls the
average molecular weight and the breadth of the molecular weight
distribution. Higher molecular weights often lead to improved
processability and strength.
(iii) Monomer Selection: The choice of monomers for polymerization is
fundamental to determining the polymer's chemical structure and
properties.
(iv) Polymer Molecular Architecture: Polymerization technique dictates the
arrangement of monomers into chains, and influences whether the
polymer can be linear, branched, or cross-linked. This molecular
architecture directly influences the polymeric material's overall behaviour.
(v) Copolymer Composition and Structure: When different monomers are
used in copolymerization, the resulting structure and composition can be
tailored. For example, the ratio of styrene and butadiene in styrene-
butadiene rubber (SBR) changes its stiffness, while block copolymers create
distinct domains that yield unique properties like thermoplastic
elastomers.
(vi) Crystallinity and Cross-linking: The extent of crystallinity and the density
of cross-linking are determined during polymerization. High cross-linking
leads to a more rigid, thermoset material, whereas lower cross-linking
allows for thermoplastic behaviour and flow.
(vii) Thermal Stability: Factors such as bond strength, the presence of
aromatic units, and secondary forces like hydrogen bonds, which are
influenced by polymerization, significantly affect the polymer's resistance
to thermal degradation and its operating temperature range.
(viii) Functional Groups: The type and placement of functional groups,
introduced via specific monomers or post-polymerization modification, can
dramatically alter a polymer's reactivity, polarity, solubility, resistance to
chemical attack and other chemical properties.
(ix)Polymerization Reaction Conditions: Adjusting temperature, pressure, and
the use of specific initiators, solvents or other media can significantly
influence the reaction rate, efficiency, and outcome of the polymerization
reaction.
(x) Polymerization Method: Techniques like bulk, solution, suspension, or
emulsion polymerization each offer different ways to control heat and
viscosity, affecting the final polymer's purity and characteristics.
In summary, polymerization is not just the formation of a polymer material but
the engineering of its molecular structure, which directly translates into
tailored macroscopic properties for specific engineering applications.
Review of effects of molecular weight and chain structures on polymeric
engineering materials
High molecular weight (HMW) polymers are macromolecules with a large
number of repeating monomer units, resulting in high molecular size. High
molecular weight in polymers enhances mechanical properties, physical
properties, toughness, impact resistance, creep resistance, viscosity, and
resistance to flow and solvents due to increased chain entanglement and the
need for more energy to break bonds.
Whereas polymer structure, encompasses linear, branched, or cross-linked
chain formations, and significantly influences these properties, with branching
or cross-linking further restricting chain movement, increasing stiffness, and
affecting thermal behavior and melt flow characteristics.
Effects of High Molecular Weight and chain structures on Polymeric Materials
(i) Increased Entanglement: Longer polymer chains with higher molecular
weights become more entangled, leading to physical cross-links that
restrict flow and improve mechanical properties.
(ii) Improved Mechanical Properties: Higher molecular weight generally leads
to superior mechanical properties like impact resistance because more
energy is needed to break bonds and cause failure.
(iii) Higher Viscosity: Polymers with high molecular weight exhibit higher melt
viscosities, making them more resistant to flow at high temperatures, and
thus, processing becomes more difficult.
(iv) Reduced Solubility: Higher molecular weight can decrease solubility due
to increased cohesive energy density.
(v) Improved Creep Resistance: Polymers with higher molecular weights
deform less over time under a consistent force.
(vi) Enhanced Chemical Resistance: Longer chains require more damage to
the backbone before the overall strength of the material is compromised,
increasing its resistance to degradation.
(vii) Thermal Properties: High molecular weight can affect the glass transition
temperature and thermal decomposition temperature.

Note: For practical implications in manufacturing, a balance is often struck

between molecular weight and processability. While high molecular weight
improves performance, lower molecular weight grades are often chosen for
ease of processing.
For applications requiring high mechanical performance, high molecular weight
polymers are preferred. However, for ease of manufacturing or specific
functional characteristics, lower molecular weight versions may be selected.

Review of Composites material

The word “Composite” means “made of two or more different parts”. Thus, a
composite is a combination of two or more different materials that are mixed together
in an effort to obtain optimum properties better than the individual parent material. In
other words, composites are engineered or naturally occurring materials made from
two or more constituent materials with significantly different physical or chemical
properties which remain separate and distinct within the finished structure.
In a composite, one material is called matrix (which is a continuous phase) and
surrounds the other phase called filler (which is the dispersed phase). However, we
can have two or more matrices and a filler, or two or more fillers and a matrix, or
multi matrix and multi filler, depending on the desired end properties. The properties
of composites are a function of the properties of the constituent phases: their relative
amounts, and the geometry of the dispersed phase. “Dispersed phase geometry” in this
context means the shape of the particles and the particle size, particle distribution and
orientation.
Composites, due to their heterogeneous composition, provide unlimited possibilities
of deriving any characteristic material behavior. This unique flexibility in design
tailoring plus other attributes like ease of manufacturing, especially molding to any
shape with polymer composites, repairability, corrosion resistance, durability,
adaptability, cost effectiveness, etc. have attracted the attention of many users in
several engineering and other disciplines. Every industry is now vying with each other
to make the best use of composites. One can now notice the application of composites
in many disciplines starting from sports goods to space vehicles. This worldwide
interest during the last four decades has led to the prolific advancement in the field of
composite materials and structures.

Types and classifications of composites

According to matrix materials, there are three main types of composite materials,
namely Polymer Matrix Composites (PMCs), Metal Matrix Composites (MMCs) and
Ceramic Matrix Composites (CMCs).
Another classification of composites is based on the nature of filler material. Thus, we
have Fibre-reinforced composites, Laminar composites and Particulate composites.

Polymer Matrix Composites (PMCs)

Polymer-matrix composites (PMCs) consist of a polymer resin as the matrix, with
fillers as the dispersed phase. In other words, when a polymer matrix is combined with
filler materials (which could be reinforcing or non-reinforcing), a 3D structure is
formed called polymer composite material. These materials are used in the greatest
diversity of composite applications, as well as in the largest quantities, in light of their
room temperature properties, ease of fabrication, lightweight, ductile nature and cost.
In polymer composites some concepts are very fundamental and must be taken into
consideration as they have direct effect on the properties of the resulting materials.
These include size, shape, volume fraction, and state of dispersion of the fillers. These
factors affect most properties of the polymer composites.
Based on response to thermal energy, there are two types of polymers – thermoplastics
and thermosets. Thermoplastics have low heat resistance, and therefore tend to lose
their strength at elevated temperatures. Examples of thermoplastic polymers used in
polymer matrix composites include polyethylene, polypropylene, polystyrene,
polyamides. On the other hand, the thermoset polymers are more thermally stable.
Examples include epoxy, polyester, aromatic polyamides, phenolics, etc. However, to
improve dimensional stability and heat resistance, fillers (which could be reinforcing
or non-reinforcing) are added. Additionally, with incorporation of fillers, certain
properties such as rigidity, toughness and creep resistance have improved; thus,
placing plastics in the important composite materials bracket.
Nonetheless, in this context, the various classifications of PMCs are discussed
according to reinforcement type (i.e., glass, carbon, and aramid), along with their
applications and the various polymer resins that are employed.

Glass Fiber-Reinforced Polymer (GFRP) Composites

Fiberglass is simply a composite consisting of glass fibers, either continuous or dis-
continuous, contained within a polymer matrix; this type of composite is produced
in the largest quantities. Glass is popular as a fiber reinforcement material for several
reasons:
1. It is easily drawn into high-strength fibers from the molten state.
2. It is readily available and may be fabricated into a glass-reinforced plastic
economically using a wide variety of composite-manufacturing techniques.
3. As a fiber it is relatively strong, and when embedded in a plastic matrix, it
produces a composite having a very high specific strength.
4. When coupled with the various plastics, it possesses a chemical inertness that
renders the composite useful in a variety of corrosive environments.
The surface characteristics of glass fibers are extremely important because
even minute surface flaws can deleteriously affect the tensile properties. There are
several limitations to this group of materials. In spite of having high
strengths, they are not very stiff and do not display the rigidity that is necessary
for some applications (e.g., as structural members for airplanes and bridges). Most
fiberglass materials are limited to service temperatures below at higher temperatures,
most polymers begin to flow or to deteriorate. Service temperatures may be extended
to approximately by using high-purity fused silica for the fibers and high-temperature
polymers such as the polyimide resins. Many fiberglass-reinforced plastics
applications are familiar: automotive and marine bodies, plastic pipes, storage
containers, and industrial floorings. The transportation industries are utilizing
increasing amounts of glass fiber-reinforced plastics in an effort to decrease vehicle
weight and boost fuel efficiencies. A host of new applications are being used or
currently investigated by the automotive industry.

Carbon Fiber-Reinforced Polymer (CFRP) Composites

Carbon is a high-performance fiber material that is the most commonly used
reinforcement in advanced (i.e., nonfiberglass) polymer-matrix composites. The
reasons
for this are as follows:
 1. Carbon fibers have the highest specific modulus and specific strength of all
reinforcing fiber materials.
2. They retain their high tensile modulus and high strength at elevated
temperatures; high-temperature oxidation, however, may be a problem.
3. At room temperature, carbon fibers are not affected by moisture or a wide
variety of solvents, acids, and bases.
4. These fibers exhibit a diversity of physical and mechanical characteristics,
allowing composites incorporating these fibers to have specific engineered
properties.
5. Fiber and composite manufacturing processes have been developed that are
relatively inexpensive and cost effective.
Carbon fiber-reinforced polymer composites are currently being utilized extensively
in sports and recreational equipment (fishing rods, golf clubs), filament-wound
rocket motor cases, pressure vessels, and aircraft structural components—both
military and commercial, fixed wing and helicopters (e.g., as wing, body, stabilizer,
and rudder components).

Aramid Fiber-Reinforced Polymer Composites

Aramid fibers are high-strength, high-modulus materials that were introduced in
the early 1970s. They are especially desirable for their outstanding strength-to-
weight ratios, which are superior to metals. Chemically, this group of materials is
known as poly(paraphenylene terephthalamide). There are a number of aramid
materials; trade names for two of the most common are Kevlar™ and Nomex™.
Mechanically, these fibers have longitudinal tensile strengths and tensile moduli that
are higher than other polymeric fiber materials. However, they are relatively
weak in compression. In addition, this material is known for its toughness, impact
resistance, and resistance to creep and fatigue failure. Even though the aramids are
thermoplastics, they are, nevertheless, resistant to combustion and stable to relatively
high temperatures; the temperature range over which they retain their high
mechanical properties is between –200 oC and 200 oC. Chemically, they are
susceptible to degradation by strong acids and bases, but they are relatively inert in
other solvents and chemicals.
The aramid fibers are most often used in composites having polymer matrices;
common matrix materials are the epoxies and polyesters. Since the fibers are
relatively flexible and somewhat ductile, they may be processed by most common
textile operations. Typical applications of these aramid composites are in ballistic
products (bullet-proof vests and armor), sporting goods, tires, ropes, missile cases,
pressure vessels, and as a replacement for asbestos in automotive brake and clutch
linings, and gaskets.

Metal Matrix Composites (MMCs)

Metal matrix composites (MMCs) are composites which comprise of metal as the
matrix and ceramic or another metal as the filler. These materials may be utilized at
higher service temperatures than their base metal counterparts. Furthermore, the
reinforcement may improve specific stiffness, specific strength, abrasion resistance,
creep resistance, thermal conductivity, and dimensional stability. Some of the
advantages of these materials over the polymer-matrix composites include higher
operating temperatures, nonflammability, and greater resistance to degradation by
organic fluids. Metal-matrix composites are much more expensive than PMCs, and,
therefore, their (MMC) use is somewhat restricted.
The superalloys, as well as alloys of aluminum, magnesium, titanium, and copper, are
employed as matrix materials. The reinforcement may be in the form of
particulates, both continuous and discontinuous fibers, and whiskers; concentrations
normally range between 10 and 60 vol%. Continuous fiber materials include carbon,
silicon carbide, boron, aluminum oxide, and the refractory metals. On the other hand,
discontinuous reinforcements consist primarily of silicon carbide (SiC) whiskers,
titanium dioxide (TiO2), chopped fibers of aluminum oxide (Al2O3) and carbon, and
particulates of silicone nitride (Si3N4), silicon carbide and aluminum oxide. In a sense,
the cermets fall within this MMC scheme.
Some matrix–reinforcement combinations are highly reactive at elevated
temperatures. Consequently, composite degradation may be caused by high-
temperature processing or by subjecting the MMC to elevated temperatures during
service. This problem is commonly resolved either by applying a protective surface
coating to the reinforcement or by modifying the matrix alloy composition.
Normally the processing of MMCs involves at least two steps: consolidation or
synthesis (i.e., introduction of reinforcement into the matrix), followed by a shaping
operation. A host of consolidation techniques are available, some of which are
relatively sophisticated; discontinuous fiber MMCs are amenable to shaping by
standard metal-forming operations (e.g., forging, extrusion, rolling).
Automobile manufacturers have recently begun to use MMCs in their products. For
example, some engine components have been introduced consisting of an
aluminum-alloy matrix that is reinforced with aluminum oxide and carbon fibers;
this MMC is light in weight and resists wear and thermal distortion. Metal-matrix
composites are also employed in driveshafts (that have higher rotational speeds and
reduced vibrational noise levels), extruded stabilizer bars, and forged suspension
and transmission components.
The aerospace industry also uses MMCs. Structural applications include advanced
aluminum alloy metal-matrix composites; boron fibers are used as the reinforcement
for the Space Shuttle Orbiter, and continuous graphite fibers for the Hubble
Telescope.
Examples of MMCs include Fe-Cr/Al2O3, Ni/Al2O3, Fe/MgO.
Generally, MMCs are characterized by Super plasticity, Lower melting points,
Increased strength and hardness, Improved magnetic properties, Increased electrical
resistivity, etc.

Ceramic matrix composites (CMCs)

These are a subgroup of composite materials that consist of ceramics as matrix and
reinforced with either another ceramic or metal fibers. Ceramics can be described as
solid materials which exhibit very high melting points, good corrosion resistance,
stability at elevated temperatures and high compressive strength, render ceramic-based
matrix materials a favourite for applications requiring a structural material that doesn’t
give way at temperatures above 1500 ºC. Naturally, ceramic matrices are the obvious
choice for high temperature applications.
High modulus of elasticity and low tensile strain, which most ceramics possess, have
combined to cause the failure of attempts to add reinforcements to obtain strength
improvement. This is because at the stress levels at which ceramics rupture, there is
insufficient elongation of the matrix which keeps composite from transferring an
effective quantum of load to the reinforcement and the composite may fail unless the
percentage of fiber volume is high enough.
Thus, the motivation to develop CMCs is to overcome the problems associated with
the conventional technical ceramics like alumina, silicon carbide, aluminum nitride,
silicon nitride or zirconia where they fracture easily under mechanical or thermo-
mechanical loads because of cracks initiated by small defects or scratches.
The low toughness of ceramics besides other properties have remained a stumbling
block for their wider use in industry. In order to overcome these limitations,
components such as whiskers, fibres, platelets or particles are incorporated into the
ceramic matrix in order to increase fracture toughness and other properties.
The reinforcements deflect the crack and/or provide bridging elements, hindering
further opening of the crack. Consequently, the incorporation of high strength fibres
into ceramic matrices has allowed the preparation of advanced composites with high
toughness and superior failure characteristics compared to the sudden failures of
ceramic materials.
Examples of CMCs include Al2O3/SiO2, SiO2/Ni, Al2O3/TiO2, Al2O3/SiC.
They are characterized by: Better toughness, Increased ductility Increased strength
and hardness.
Influence of Fiber Length on the Properties of Composites
The mechanical characteristics of a fiber-reinforced composite depend not only on
the properties of the fiber, but also on the degree to which an applied load is
transmitted to the fibers by the matrix phase. Thus, some critical fiber length is
necessary for effective strengthening and stiffening of the composite material. This
critical length lc is dependent on the fiber diameter d and its ultimate (or tensile)
strength σf and on the fiber–matrix bond strength (or the shear yield strength of the
matrix, whichever is smaller) τ according to
σ f .d
lc = (i)
2τ
As fiber length l increases, the fiber reinforcement becomes more effective. Fibers for
which l ≥ lc (normally l > 15lc) are termed continuous; discontinuous or short fibers
have lengths shorter than this. For discontinuous fibers of lengths significantly less
than the matrix deforms around the fiber such that there is virtually no stress
transference and little reinforcement by the fiber. These are essentially the particulate
composites as described above. To affect a significant improvement in strength of the
composite, the fibers must be continuous.
Influence of Fiber Orientation and Concentration
The arrangement or orientation of the fibers relative to one another, the fiber
concentration, and the distribution all have a significant influence on the strength and
other properties of fiber-reinforced composites. With respect to orientation, two
extremes are possible:
(1) a parallel alignment of the longitudinal axis of the fibers
in a single direction, and
(2) a totally random alignment.
Continuous fibers are normally aligned, whereas discontinuous fibers may be aligned,
randomly oriented, or partially oriented. Better overall composite properties are
realized when the fiber distribution is uniform.

Longitudinal
direction

Transverse
direction

(b) (c)
(a)
Schematic representations of (a) continuous and aligned, (b) discontinuous and aligned,
and (c) discontinuous and randomly oriented fiber-reinforced composites.

Elastic Behavior—Longitudinal Loading

Let us now consider the elastic behavior of a continuous and oriented fibrous
composite that is loaded in the direction of fiber alignment. First, it is assumed that the
fiber–matrix interfacial bond is very good, such that deformation of both matrix
and fibers is the same (an isostrain situation). Under these conditions, the total load
sustained by the composite Fc is equal to the sum of the loads carried by the matrix
phase Fm and the fiber phase Ff or
F c =Fm + F f (ii)
From the definition of stress, F=σA, and thus expressions for
Fc, Fm and Ff in terms of their respective stresses (σc, σm and σf ) and cross-sectional
areas (Ac, Am and Af) are possible. Substitution of these into Equation (ii) yields
σ c Ac =σ m A m +σ f A f (iii)
and then, dividing through by the total cross-sectional area of the composite,
we have
Am Af
σ c =σ m + σf (iv)
Ac Ac
Am Af
where and are the area fractions of the matrix and fiber phases, respectively. If
Ac Ac
Am
the composite, matrix, and fiber phase lengths are all equal, is equivalent to the
Ac
Af
volume fraction of the matrix, Vm and likewise for the fibers, V f = . Equation (iv)
Ac
now becomes
σ c =σ m V m +σ f V f (v)
The assumption of an isostrain state means that
ϵ c =ϵ m=ϵ f (vi)

and when each term in Equation (v) is divided by its respective strain, we have
σc σm σf
= V m+ V f (vii)
ϵ c ϵm ϵf

Furthermore, if composite, matrix, and fiber deformations are all elastic, then
σc σm σf
=Ec , =E m and =Ef ; the E’s being the moduli of elasticity for
ϵc ϵm ϵf
the respective phases.
Substitution into Equation (vii) yields an expression for the modulus of elasticity of a
continuous and aligned fibrous composite in the direction of alignment (or
longitudinal direction), Ecl as
Ecl =Em V m + E f V f (viii)
or
Ecl =Em (1−V ¿¿ f )+ E f V f ¿ (ix)
since the composite consists of only matrix and fiber phases; that is, V m +V f =1.
Thus, Ecl is equal to the volume fraction weighted average of the moduli of
elasticity of the fiber and matrix phases. Other properties, including density, also
have this dependence on volume fractions.
It can also be shown, for longitudinal loading that the ratio of the load carried by the
fibers to that carried by the matrix is
Ff Ef V f
= (x)
F m Em V m

Example problem 1.0

A continuous and aligned glass fiber-reinforced composite consists of 40 vol. %
of glass fibers having a modulus of elasticity of 69 GPa and
60 vol. % of a polyester resin that, when hardened, displays a modulus of 3.4 GPa.
(a) Compute the modulus of elasticity of this composite in the longitudinal
direction.
(b) If the cross-sectional area is 250 mm 2 and a stress of 50 MPa is applied in this
longitudinal direction, compute the magnitude of the load carried by each of
the fiber and matrix phases.
(c) Determine the strain that is sustained by each phase when the stress in part (b)
is applied.
Solution
(a) The modulus of elasticity of the composite is calculated using Eqn (viii):
Ecl =Em V m + E f V f
Ecl = (3.4 GPa x 0.6 + 69 GPa x 0.4) = 2.04 GPa + 27.6 GPa = 29.64 GPa
(b) Using Equation (x),
F f E f V f 69 GPa X 0.4
= = =13.53. Therefore, F f =13.53 F m
F m Em V m 3.4 GPa X 0.6

but F c =Fm + F f , and F c =σ Ac

therefore, F c =Fm +13.53 F m; F c =Fm ( 1+13.53 ) =14.53 F m

Hence, F c =14.53 F m
2 −6
F c =σ Ac =50 MPa X 250 mm =50,000,000 X 250 X 10 =12,500 N
Thus, 12,500 = 14.53 Fm; Fm = 12,500/14.53 = 860.29 N
Ff = 13.53 X 860.29 = 11,639.72 N
σm σf
(c) Recall that ϵ =E m and ϵ =Ef
m f

Therefore, stress for both fiber and matrix phases must first be calculated.
Then, by using the elastic modulus for each (from part a), the strain
values may be determined.
F
For stress calculations, σ = A . This implies that phase cross-sectional
areas are necessary, and can be determined from the relations below:
Am A
V m= and V f = f .
Ac Ac
Am =V m X A c = 0.6 X 250 mm2 = 150 mm2
A f =V f X A c = 0.4 X 250 mm2 = 100 mm2

m F860.29 N
Therefore, σ m= A = 2
=5.74 MPa
m 150 mm
σ m 5.74 MPa
ϵ m= = =0.00169
E m 3.4 GPa

F f 11,639.72 N
¿ σ f= = 2
=116.40 MPa
Af 100 mm
σ f 116.4 MPa
ϵf = = =0.00169
Ef 69 GPa

Therefore, strains for both matrix and fiber phases are identical, which
they should be according to Equation (vi).

Elastic Behavior—Transverse Loading

A continuous and oriented fiber composite may be loaded in the transverse direction; that
is, the load is applied at 90 oC angle to the direction of fiber alignment. For this situation
the stress to which the composite as well as both phases are exposed is the same, or
σ c =σ m =σ f =σ (xi)

This is termed an isostress state. Also, the strain or deformation of the entire composite is
ϵ c =ϵ m V m + ϵ f V f (xii)

σ
but, since ϵ=
E
σ σ σ
= V + V
Ect E m m Ef f
(xiii)
where Ect is the modulus of elasticity in the transverse direction. Now, dividing through
by σ yields
1 Vm Vf
= +
Ect Em E f
(xiv)

Em Ef Em Ef
which reduces to Ect = =
V m E f +V f E m (1−V ¿¿ f ) E f +V f E m ¿
(xv)

Some applications of composites

1. Automotive Engineering. Composites are used in exterior body panels,
frameworks/chassis, bumpers, drive shafts, suspension systems, wheels,
steering wheel columns and instrument panels of automotive vehicles.
2. For marine applications. GFRPs are being used for the last 3-4 decades to
build canoes, yatchs, speed boats and other workboats.
3. Composites also have extensive uses in electrical and electronic systems.
For example, composite antenna dishes, Leadless ceramic chip carriers
are reinforced with Kevlar or Kevlar-glass coweave polyimides to reduce
the incidence of solder joint microcracking.
4. Biomedical applications. The light artificial limbs and external bracing
systems made of CFRP provide the required strength, stiffness and
stability in addition to lightness.
5. Sports accessories such as skis, tennis and badminton rackets, fishing
rods, vaulting poles, hockey sticks, surf boards.