KHOA CÔNG NGHỆ HOÁ HỌC VÀ THỰC PHẨM
BỘ MÔN CÔNG NGHỆ HOÁ HỌC
CÔNG NGHỆ SẢN XUẤT CHẤT DẺO (TPLA425503)
CHƯƠNG 4. Mối quan hệ giữa cấu trúc và tính
chất cơ-nhiệt.
TS. Huỳnh Nguyễn Anh Tuấn
KHOA CÔNG NGHỆ HOÁ HỌC VÀ THỰC PHẨM
BỘ MÔN CÔNG NGHỆ HOÁ HỌC
CÔNG NGHỆ SẢN XUẤT CHẤT DẺO (TPLA425503)
CHƯƠNG 4. Relation of Structure to Thermal and
Mechanical Properties
TS. Huỳnh Nguyễn Anh Tuấn
NỘI DUNG MÔN HỌC 3
Chương 1: Lịch sử hình thành và phát triển của chất Chương 8: PE và PP
dẻo Chương 9: PVC, PTFE và cao su CR
Chương 2: Bản chất hóa học của chất dẻo Chương 10: PS, Polybutadien và cao su SBR
Chương 3: Trạng thái kết khối trong Polymers Chương 11: Polyvinyl actetate và Acrylic Plastics
Chương 4: Mối quan hệ giữa cấu trúc và tính chất cơ – Chương 12: Polycarbonate và Cellulose Plastics
nhiệt Chương 13: Polyamide và Polyimide
Chương 5: Mối quan hệ giữa cấu trúc và tính chất hóa Chương 14: Polyurethanes and Polyisocyanurates
học Chương 15: Nhựa Phenolic
Chương 6: Mối quan hệ giữa cấu trúc và tính chất Chương 16: Nhựa UPE, Epoxide và Vinylester
quang – điện
Chương 7: Chất độn
TS. Huỳnh Nguyễn Anh Tuấn
TS. Hồ Phương
1. INTRODUCTION 4
• Ba yếu tố quyết định xem một polymer sẽ ở trạng thái thủy tinh (glassy), cao su (rubbery) hay tạo sợi (fibre-
forming) dưới một tập hợp điều kiện nhất định là: tính linh hoạt của chuỗi, lực hút giữa các chuỗi và độ đều đặn
của polymer.
• Các tham số này phát sinh từ ảnh hưởng của chúng
đến :
1. Nhiệt độ chuyển thủy tinh
2. Khả năng kết tinh của vật liệu
3. Điểm nóng chảy của tinh thể.
2. FACTORS AFFECTING THE GLASS TRANSITION TEMPERATURE 5
• Tg is that at which molecular rotation about single bonds becomes restricted influence the
ease of rotation:
(1) Factors which affect the inherent or intrinsic mobility of a single chain.
(2) Those factors effect on the proximity considered on its own. and interaction of many
polymer chains.
2. FACTORS AFFECTING THE GLASS TRANSITION TEMPERATURE 6
• Rotations in simple molecule:
1) When the specific groups
or atoms come close to those
on the adjacent carbon atom
there is usually a repulsion.
2) Intramolecular hydrogen
bonding may cause attraction
rather than repulsion: large
energy requirement.
2. FACTORS AFFECTING THE GLASS TRANSITION TEMPERATURE 7
Figure 4.3 depicts the
change in height of
rotational energy
bamers with bond
rotation of
methylsuccinic acid.
2. FACTORS AFFECTING THE GLASS TRANSITION TEMPERATURE 8
• The intrinsic chain flexibility is determined by the nature of the chain backbone and by the
nature of groupecs dirtly attached to the backbone.
1) chains based on aliphatic C-C and C-0 bonds are quite flexible.
2) ring structures such as the p-phenylene group into the main chain has a marked stiffening
effect.
3) single C-C bond is also impeded by the substitution of attached hydrogen atoms by methyl or
other hydrocarbon groups.
4) The size of the group attached to the main chain carbon atom can influence the
glass transition point.
5) Inclusion of double bonds reduce the glass transition temperature: cis-1,4-poIybutadiene
when compared with polyethylene
2. FACTORS AFFECTING THE GLASS TRANSITION TEMPERATURE 9
6) Secondary bonding due to dipole forces, induction forces and dispersion forces or hydrogen
bonding between chains can affect the mobility of a chain: PVC, poly(vinylidene chloride).
7) Hydrogen bonding has a similar effect to that of polar groups: nylon 6, which differs from
polyethylene by the presence of -CONH- groups.
8) The molecular weight of a polymer will have some
effect on the glass transition temperature.
9) The glass transition temperature of a random copolymer
usually falls between those of the corresponding homopolymers
10) The greater the degree of cross-linking
the higher the transition temperature
3. FACTORS AFFECTING THE ABILITY TO CRYSTALLISE 10
• The polymer will crystallise, rubbery behaviour may be limited since the orderly arrangement
of molecules in the crystalline structure by necessity limits the chain mobility.
• The ability of a material to crystallise is determined by the regularity of its molecular structure.
• Structural irregularities can occur in the following ways:
(1) By copolymerisation.
(2) By introduction of groups in an irregular manner.
(3) By chain branching.
(4) By lack of stereoregularity.
(5) By differences in geometrical isomerism.
3. FACTORS AFFECTING THE ABILITY TO CRYSTALLISE 11
• Copolymerisation provides a very effective way of reducing the regularity and hence the ability
to crystallise.
A chlorinated polyethylene which also
contains a few sulphonyl chloride groups
is a commercially available rubber
The treatment of poly(vinyl alcohol) (Hypalon).
with formaldehyde to give poly(vinyl formal) will
prevent crystallization because of the structural
irregularities produced.
12
• Branching can to some extent reduce the ability to crystallise. The frequent, but irregular,
presence of side groups will interfere with the ability to pack. Ex: HDPE, LDPE…
• In recent years the significance of stereoregularity has become more appreciated.
The regular syndiotactic and isotactic structures are
capable of crystallization whereas the atactic polymer
cannot normally do so. In the case of polypropylene
the isotactic material is a crystalline fibre-forming
material. It is also an important thermoplastic which
can withstand boiling water for prolonged periods.
Atactic polypropylene is a ‘dead’ amorphous
material.
13
• Related to stereoregularity is the possibility of cis, trans isomerism. The molecule of natural
rubber is a cis-1,4-polyisoprene whilst that of gutta percha is the trans isomer.
4. FACTORS AFFECTING THE CRYSTALLINE MELTING POINT 14
• To a large extent the factors which determine
the position of the glass transition temperature
of a polymer (chain stiffness and
intermolecular forces) also determine the
melting point of a crystalline polymer.
• The glass transition temperature of many
polymers is about two-thirds that of the
crystalline melting point when measured in K.
5. SOME INDIVIDUAL PROPERTIES - Melt Viscosity 15
• The melt viscosity of a polymer at a given temperature is a measure of the rate at which the
chains can move relative to each other.
• Low chain flexibility, polymers such as polytetrafluoroethylene, the aromatic polyimides, the
aromatic polycarbonates and to a less extent poly(vinyl chloride) and poly(methyl
methacrylate) are highly viscous in their melting range as compared with polyethylene and
polystyrene.
• Molecular weight: higher the molecular weight the greater the entanglements and the greater
the melt viscosity.
• The greater the branching: the lower the melt viscosity.
Yield Strength and Modulus 16
• The yield strengths and elastic moduli of amorphous polymers well below their glass transition
temperature it is observed that the differences between polymers are quite small.
• The molecular weight have little effect.
• The crystalline polymers wider differences are to be noted. Many polyethylenes have a yield
strength below 2000lbf/in2 (14 MPa) whilst the nylons may have a value of 12000lbf/in2 (83
MPa).
• The intermolecular attraction, the molecular weight and the type and amount of crystalline
structure all influence the mechanical properties.
Yield Strength and Modulus 17
• The mass per unit volume, is a function of the weight of individual molecules and the way they
pack.
• Amorphous hydrocarbon polymers: 0.86 – 1.05
• PVC : 1.4
• Polymer can crystallise: higher densitiy. Ex. PTFE (about 2.2).
• Polyethylenes made by different processes often differ in the degree of branching and thus can
crystallise or pack to varying events.
• The amorphous ethylene-propylene rubbers have lower densities than either polyethylene or
isotactic polypropylene.
• Hãy tra cứu tỷ trọng của một vài loại PE và PP?
Impact Strength 18
• Brittle or a tough material ?
• Polystyrene, poly(methy1methacrylate) and unmodified unplasticised PVC: brittle, breaking
with a sharp fracture.
• Low-density polyethylene and plasticised PVC: tough
• Material exhibits brittle fracture or appears tough depends on the temperature and the rate of
striking.
• Amorphous polymers: below the glass transition temperature: break with a brittle fracture;
tougher as the glass transition temperature is approached; above the glass transition: cease to
have significance.
• Crystalline materials: depend on the degree of crystallinity, The size of the crystalline
