Universitas Sultan Ageng Tirtayasa

TMT 619213
Teknologi Polimer
The Structure of Polymer

Dr. Ir. Amalia Sholehah

2021
Introduction
• Polymers in their solid state can
be roughly divided into two
categories:
• The amorphous state
• The semicrystalline state
• Many polymers cannot
crystallize → they exist in an
amorphous state.
• Crystallization of the polymer is
usually imperfect

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The Polymer’s Structure
• The chemical and structural aspects of polymers at three
different levels:
• The chemical structure (atomic composition) of the
monomer (primary structure)
• The single polymer chain (secondary level)
• Aggregation of polymer chains (tertiary structure)

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The Polymer’s Structure : Primary
• Primary structure refers to the atomic composition and
chemical structure of the monomer
• Basic to understand the structure and properties :
• The chemical bonding
• The functionality of monomers
• The polymerization mechanisms
• The chemical composition of monomers

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 The Polymer’s Structure : Secondary
Configuration
• The shape of the polymer
molecule will be
influenced by the nature
of the repeating unit and
how these units are linked
together:
• Configuration
Conformation
• Conformation

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The Morphology of Partially Crystalline
Polymer

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Thermal Transition
First Order Transition
𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃
𝜕𝐺
= −𝑆
𝜕𝑇 𝑃

𝜕𝐺
=𝑉
𝜕𝑃 𝑇

Second Order Transition

𝜕2𝐺 𝜕𝑆 𝑐𝑃
= = The slope of curve is different above and below Tg,
𝜕𝑇 2 𝑃
𝜕𝑇 𝑃
𝑇
however, no abrupt change of volume occurs at the
𝜕2𝐺 𝜕𝑉 glass transition → the structure is disoriented.
=− = −𝑉𝛽
𝜕𝑃2 𝑇
𝜕𝑃 𝑇

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Thermal Transition
• Semicrystalline polymers consist
both of crystalline and
amorphous areas.
• When heating a semicrystalline
or partially crystalline polymer,
both transitions can be
observed, i.e.
• a glass transition at a temperature Tg,
• a melting process at a temperature Tm

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Determination of Tg and Tm
• Static Methods
• Dynamic Methods

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The Melting Point (Tm)
• The melting temperature of polymers is influenced by
various aspects of the polymer composition as well as the
thermal history of the material.
• The significant parameters are conditions of crystallization,
chain flexibility, symmetry, interactions between chains or
chain segments, tacticity, branching, molar mass, and
comonomers

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The Glass Temperature (Tg)
• The temperature at which the glass transition occurs is
essentially determined by the mobility of the polymer
chains.
• The chain mobility is most strongly influenced by chain
flexibility, steric effects, tacticity, branching and
crosslinking, molar mass.

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