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Physical Properties
- Molecular Weight
- Molar Volume
- Density
- Degree of Polymerization
- Crystallinity of Material
- Others
Thermal Properties
Mechanical Properties
- Strength
- Toughness
- Viscoelasticity
- Polymer molecules are not identical but are a mixture of many species with different
degrees of polymerization, i.e., with different molecular weights
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- Lamellar crystalline form in which the chains fold and make lamellar structure
arranged in a regular manner
- Amorphous polymers exist as long, randomly coiled, interpenetrating chains that are
capable of forming stable, flow-restricting entanglements at sufficiently high
molecular weights.
- Critical Molecular Weight — the minimum polymer chain length, Mc, for the
formation of stable entanglements; depends upon the flexibility of a polymer chain.
Molecular Weight Between Entanglements — Me. As a rule of thumb, Mc ~ 2Me.
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Polymer Mc Me
Polycarbonate 4,800 2,490
cis-Polyisoprene 10,000 5,800
Polyisobutylene 15,200 8,900
Polydimethylsiloxane 24,400 8,100
Poly(vinyl acetate) 24,500 12,000
Poly(methyl methacrylate) 27,500 5,900
Poly(a-methystyrene) 28,000 13,500
Polystyrene 31,200 18,100
REPTATION MODEL
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- The temperature that marks the transition from amorphous solid state to the melt
state.
- Isoviscous state — as a polymer is cooled from its melt state, viscosity increases
rapidly to a common (maximum) value, ca. 10^12 Pa-s (10^13 poise) at Tg for all
glassy materials, both low-molecular-weight and polymeric.
Vf = V - Vo
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4. Pendant groups — The presence of pendent group can change the glass
transition temperature.
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Tg = Tg,∞ − K/Mn
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• The polymers having simple structural chains as linear chains and slow cooling
rate will result in good crystallinity as expected.
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• Rigid and have high melting point, but their impact resistance is low.
- Amorphous polymers:
- For a solvent, it is important to state that it can penetrate the amorphous part more
easily than the crystalline part.
- Lamellae — consists of arrays of folded chains. The basic units of crystalline polymer
morphology.
- Spherulite — Contains arrays of lamellar crystallites that are typically oriented with
the chain axis perpendicular to the radial direction.
SEMI-CRYSTALLINE POLYMER
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• As the melt is cooled, the low-energy conformations are favored and chains are
free to organize into lamellar structure. The lowest energy conformation may be:
2. Helical — polymers with large substituent groups, including isotactic PP, and
other isotactic polymers, polymers of 1,1-disubstituted ethylenes like
polyisobutylene.
4.3.1. Strength
- Types of strength:
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- The polymers follow the following order of increasing strength: linear < branched <
cross-linked < network.
1. Molecular Weight: The tensile strength of the polymer rises with increase in
molecular weight and reaches the saturation level at some value of the molecular
weight. The tensile strength is related to molecular weight by the following
equation.
𝜎= 𝜎∞−A M
𝜎∞ is the tensile strength of the polymer with molecular weight of infinity. A is some
constant, and M is the molecular weight. At lower molecular weight, the polymer
chains are loosely bonded by weak van der Waals forces and the chains can move
easily, responsible for low strength, although crystallinity is present. In case of large
molecular weight polymer, the chains become large and hence are entangled, giving
strength to the polymer.
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2. Cross-linking: The cross-linking restricts the motion of the chains and increases
the strength of the polymer.
3. The crystallinity of the polymer increases strength, because in the crystalline phase,
the intermolecular bonding is more significant. Hence, the polymer deformation can
result in the higher strength leading to oriented chains.
- It measures the percentage change in the length of the material before fracture. It is a
measure of ductility. Ceramics have very low (<1%), metals have moderate (1–50%)
and thermoplastic (>100%), thermosets (<5%) value of elongation to break.
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- Young’s Modulus is the ratio of stress to the strain in the linearly elastic region.
Elastic modulus is a measure of the stiffness of the material.
Tensile Stress (σ )
E=
Tensile Strain (ε )
4.3.4. Toughness
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Toughness = ∫ 𝜎 d𝜀
- The toughness measures the energy absorbed by the material before it breaks.
2. Ductile polymers: possess elastic modulus similar to brittle polymers, but with
higher fracture toughness.
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- Yield strength of the plastic polymer is the corresponding stress where the elastic
region (linear portion of the curve) ends (Fig. 4.3.4.3).
- Tensile strength is the stress corresponding to the fracture of the polymer. The
tensile strength may be higher or lower than the yield strength (Fig. 4.3.4.3).
- The mechanical properties of the polymer are strongly affected by the temperature. A
typical plot of stress versus strain is shown in Fig. 4.3.4.4. From the plot, it is clear
that with increase in the temperature, the elastic modulus and tensile strength are
decreased, but the ductility is enhanced.
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4.3.5. Viscoelasticity
• elastic
• viscous
- Elastic deformation (Fig. 4.3.5.1), the strain is generated at the moment the
constant load (or stress) is applied, and this strain is maintained until the stress is not
released. On removal of the stress, the material recovers its original dimensions
completely, that is the deformation is reversible (Fig. A1.17), that is:
𝜎 = E𝜀
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𝜎 = 𝛾 d𝜀/dt
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• At high temperature but low strain rate, the viscous behavior is observed.
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- The stress required to maintain the constant strain value is decreased with time,
because the molecules of polymer get relaxed with time, and to maintain the level of
strain, somewhat lower value of stress is sufficient.
Erel(t) = 𝜎(t)/ 𝜀0
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𝝈 = 𝝈oe−t∕𝝉
where
𝜎 =stress at time t,
The relaxation modulus is found to decrease with increase in temperature and time as
shown in Fig. 4.3.6.1.
Now, consider the time t1. Measure the values of relaxation modulus at time t1 at
different temperatures, say T1, T2, T3 ... for the viscoelastic polymer and plot the
relaxation modulus versus temperature. A typical plot is shown in Fig. 4.3.6.2. The
glass transition temperature lies near the upper temperature extremity.
- Creep can be considered as the opposite of stress relaxation (lowering of the stress
with time maintaining the constant strain level) where the polymer suffers time-
dependent deformation (increasing strain with time) at constant stress level.
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ECreep(t) = 𝜎0/𝛆(t)
JCreep(t) = 𝛆(t)/𝜎0
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