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Dr. S.

Ray_Chem Engg_NIT Agratala

1/17/2013

Structure-processing-property relationships

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Structure-processing-property relationships

Structure-property relationships in polymers


Structure and properties of the polymer depends on: The nature of bonds in monomers (chemical bonding) The type of monomers that are capable of forming polymers (functionality of monomers) The mode of linking of monomers (polymerization mechanisms) The chemical composition of monomers and the properties conferred on monomers as a result of their chemical composition

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Structure-property relationships in polymers


Primary structure refers to the atomic composition and chemical structure of the monomer the building block of the polymer chain. An appreciation of the nature of the monomer is fundamental to understanding the structureproperty relationship of polymers. The chemical and electrical properties of a polymer are directly related to the chemistry of the constituent monomers. The physical and mechanical properties of polymers, on the other hand, are largely a consequence of the macromolecular size of the polymer, which in itself is related to the nature of the monomer.

Chemical bonds
Chemical bonds may be classified as primary or secondary depending on the extent of electron involvement. Valence electrons are involved in the formation of primary bonds, hence these are strong bonds. Valence electrons are not involved in the formation of secondary bonds leading to weak bonds. 1. Primary bonds a. Ionic electron transfer to attain the inert gas electron configuration b. Covalent - involve the sharing of valence electrons. 2. Secondary bonds a. Dipole arises if the electrons shared by two atoms spend more time on one of the atoms due to differences in electro-negativity. b. Hydrogen - a particularly important kind of dipole interaction c. Induction forces due to induced relative displacements of the electrons by permanent dipole. d. Van der Waals (dispersion) instantaneous fluctuating dipoles exist even in non-polar materials, the orientations of fluctuating dipoles in proper alignment results intermolecular attractions

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Structure-processing-property relationships
1-Primary bonds : the covalent bonds that connect the atoms of the main chain hain 2- Secondary bonds : non covalent bonds that hold one polymer chain to another including hydrogen bond and other dipole dipole attraction 3-Crystalline polymer : solid polymers with a high degree of structural order and rigidity 4- Amorphous polymers : polymers with a low degree of structural order 5-Semi crystalline polymer : most polymers actually consist of both crystalline domains and amorphous domains with properties between that expected for a purely crystalline or purely amorphous polymer 6-Glass : the solid form of an amorphous polymer characterized by rigidity and brittleness

Amorphous

Crystalline

Structure-processing-property relationships

Intermolecular Interactions defining polymer structure and properties

Van de Waals Forces ~ 2-20 kJ/mol


1. Dipole-Dipole Interaction
ED = 2 1 2 3 R6 KT
2 2

~ 13-21 kJ/mol

2. Induced Dipole-Dipole Interaction

EI =

1 1 + 2 2
2 2

~ 6-13 kJ/mol

3 I 1 I 2 1 2 6 3. Dispersion Interaction E L = 2 I 1 + I 2 R

~ 0.8-8 kJ/mol

dipole moment, polarizability, I ionization energy, R intermolecular distance

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Hydrogen Bonding
-X-H Y~ 4-5 (<1 nm)

~ 20-40 kJ/mol Proton Acceptor

Proton Donor Proton Donors: Proton Acceptors:


Oxygen

Nitrogen

Why are nylons strong and tough? Why nylons have high melting temperature (~250C)?

Hydrogen bonding in Nylon 66

Ionic Interactions Polyeletrolytes or Ionomers

Polyelectrolyte multilayers on silicon wafer

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Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Chemical bond energies

Structure-property relationships in polymers


Effect of Bonding on polymer properties
The primary bonds between the chains are strong mostly covalent bonds that you would expect to produce a Strong Stiff high melting temperature material. The secondary bonds mean that chains can move with respect to each other easily which makes polymers relatively Weak low stiffness low melting temperature

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Functionality of monomers

The functionality of a molecule is simply its interlinking capacity, or the number of sites it has available for bonding with other molecules under the specific polymerization conditions. A molecule may be classified as monofunctional, bifunctional, or polyfunctional depending on whether it has one, two, or greater than two sites available for linking with other molecules.

Structure-property relationships in polymers


The structural units resulting from the reaction of monomers may in principle be linked together in any conceivable pattern. Bifunctional structural units can enter into two and only two linkages with other structural units. This means that the sequence of linkages between bifunctional units is necessarily linear. The resulting polymer is linear The reaction between polyfunctional molecules results in structural units that may be linked so as to form nonlinear structures. In some cases the side growth of each polymer chain may be terminated before the chain has a chance to link up with another chain. The resulting polymer molecules may be branched. In other cases, growing polymer chains become chemically linked to each other, resulting in a cross-linked system

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Structure-property relationships in polymers


The chemical composition and atomic arrangement of an organic molecule confer certain properties on the molecule, one such property is the polarity. In a diatomic molecule formed from two like atoms (e.g., H2 ), the electron pair linking the two atoms is equally shared and the molecule is said to be non-polar. But when molecules are formed from two unlike atoms (e.g., CO), the distribution of the electron cloud is concentrated on the more electronegative atoms and there is a separation of positive and negative charge and the molecule is polar.

Polarity affects the intermolecular attraction between chain molecules, and thus the regularity and symmetry of polymer structure. The properties such as the solubility and electrical nature of polymers, which depend on polymer structure, are intimately related to polarity 15

Structure-property relationships in polymers

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Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Structure-property relationships in polymers


Polar Side Groups Polar side groups like Chlorine or Flourine can increase the strength of the secondary bonding. Bulky side groups like those on polypropylene increase the entanglement like barbed wire increases the entanglement of wire.

Polymer PVC PP PS MDPE

Density g/cc 1.35 0.950 1.05 0.936

UTS k-lb/si 7.5 5.0 6.5 2.5

EL % 45 150 1.5 750

E k-lb/si 385 300 413 90

Structure-property relationships in polymers

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Structure-property relationships in polymers


Effect of Backbone
The all carbon backbone of PE is very flexible. The addition of N or O on the backbone can make the polymer stiffer (harder to uncoil and slide past other chains (Nylon) The existence of ring structures on the chain makes the polymer stiff.
Polymer PVC PP PS MDPE Nylon PC Density g/cc 1.35 0.950 1.05 0.936 1.14 1.2 UTS k-lb/si 7.5 5.0 6.5 2.5 12 10 EL % 45 150 1.5 750 15-300 120 E k-lb/si 385 300 413 90 230-550 345

Structure-property relationships in polymers

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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Structure-property relationships in polymers


The shape of the polymer molecule (molecular architecture) will be influenced naturally by the nature of the repeating unit and the manner in which these units are linked together Configuration Arrangement fixed by primary valence bonds; can be altered only through the breaking or reforming of chemical bonds Conformation Arrangement established by rotation about primary valence bonds

Predominant specie Diene Polymerization - 1,2, and 1,4 additions: In 1,2 addition the resulting polymer unsaturation is part of the pendant group, while in 1,4 addition the unsaturation is part of the backbone, thus in 1,4 addition, the backbone has a rigid structure and rotation is not free around it.
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Structure-property relationships in polymers


In addition to the molecular shape fixed by chemical bonding, variations in the overall shape and size of the polymer chain may occur due to rotation about primary valence bonds (conformation). A polymer molecule may assume a large or limited number of conformations depending on: Steric factors Whether the polymer is amorphous or crystalline Whether the polymer is in a solution state, molten state, or solid state A single isolated polymer chain in dilute solution having four successive chain atoms; the first three of these define a plane, and the fourth can lie anywhere on the indicated circle which is perpendicular to and dissected by the plane. However, all bonds have to overcome certain rotational energy barriers whose magnitude depends on factors such as steric hindrance, dipole forces, etc., accordingly, some positions will certainly be more probable than others The thermal energy of the molecular environment provides the energy required to overcome the rotational energy barrier, consequently, the shape (flexibility) of a polymer molecule is temperature dependent.

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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Structure-property relationships in polymers


Polyethylene
CH2CH2 n

Polytetrafluoroethylene
CF2CF2 n

CH3-CH2-CH2-CH3

~+15
stable

gauche(+) gauche(-)

~-15
stable 23

Polymer Tacticity
The different possible spatial arrangements are called the tacticity of the polymer. For monosubstituted ethylene, such as a vinyl polymers, every other carbon atom is a chiral center and are referred to as pseudochiral centers If the R groups on successive pseudochiral carbons all have the same configuration, the polymer is called isotactic When the pseudochiral centers alternate in configuration from one repeating unit to the next, the polymer is called syndiotactic. If the pseudochiral centers do not have any particular order, but in fact are statistical arrangements, the polymer is said to be atactic.
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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Polymer Tacticity
In Fisher projections the R groups are placed either up or down. a) all up (or all down) indicates the isotactic structure:

b) alternating up and down indicates syndiotactic:

c) random up and down indicates atactic:

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H C H 3C

Cl

Polymer Tacticity

Cl C H 3C

CH2CH3

CH2CH3

X=CH3 Y=H

isotactic

syndiotactic

isotactic PP

syndiotactic PP

Atactic (non-atactic)

atactic PP

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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Polymer Tacticity structure-property relationship

The isotactic and syndiotactic (also known as stereo-regular) polymers are both crystallizable because of their regularity along the chain. However, their melting temperatures are not the same. Atactic polymers, on the other hand, are usually completely amorphous unless the side group is so small or so polar as to permit some crystallinity.

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Structure-property relationships in polymers


The same bonding forces (intra- and intermolecular) operate in both low- and high-molecular weight materials, however, polymers have unique properties. The unique properties exhibited by polymers and the difference in behavior between polymers and their low-molecular weight analogs are attributable to their large size and flexible nature. The properties that depend on molecular weight are: mechanical properties: tensile strength, compressive strength, elongation at break, modulus, impact strength other properties: softening point, solution viscosities melt viscosities, solubility

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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Structure-property relationships in polymers

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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

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Molecular Weight of Polymers


1. Molecular Weight (MW) = Degree of Polymerization (DP) M0
CH2CH2 1000

MW = 1000 M0 (28) g/mol = 28,000 g/mol

2. Average Molecular Weights of Polymers


A set of values {M1, M2, . . ., Mn}. The probability of each value is {P1, P2, . . ., Pn}. The average is
i =1
i =1

Pi M i
i =1

Pi M i . So, the average depends on the probability.

Pi

Number-average Molecular Weight

Mn

= xi M i =

NiM i = Ni

Number-average DP
1 w iM i

DP n = M n / M 0
Weight-average DP

Weight-average Molecular Weight

Ni M i N i M i2 Mi = M w = wi M i = Ni M i Ni M i

DP w = M w / M 0
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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Molecular weight averages


To create a solid with useful mechanical properties the chain must be long !! One may describe chain length in terms of polymer average molecular weight, which can be defined in several ways:

1. A number-average molecular weight Mn : divide chains into series of size ranges and then determine the number fraction Ni of each size range Mn = Mi Ni / Ni where Mi represents the mean molecular weight of the size range i, and Ni is the fraction of total number of chains within the corresponding size range

2. A weight average molecular weight Mw is based on the weight fraction wi within the size ranges: Mw = Mi W i / W i

(1) The number-average molecular weight for a discrete distribution of molecular weights is given as

where N is the total number of molecular-weight species in the distribution. (2) The weight-average molecular weight is given as

Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Molecular Weight of Polymers

Z-average Molecular Weight (melt elasticity)


w Mi wi M i2 = N i M i3 i = M z = zi M i = w M M i w M 2 i i i i NiM i

Viscosity-average Molecular Weight (viscosity)


+a NiM1 i Mv = NiM i 1/ a

a is viscosity parameter between 0.5 and 1.0

Generally:

Mn< Mv Mw< Mz
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A measure of the molecular-weight distribution (MWD) is given by the ratios of molecular -weight averages. For this purpose, the most commonly used ratio is Mw/Mn, which is called the polydispersity index or PDI.

PDI= Mw/Mn
Mw/Mn = 1 monodisperse Polymer sample consisting of molecules all of which have the same chain length Mw/ Mn > 1 polydisperse Polymer consisting of molecules with the variety of chain length

Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Molecular Weight of Polymers

wi = 1
4.0

M n = 100,000 g/mol M p
3.0

2.0

M v = 165,000 g/mol M w = 199,900 g/mol

104 wi

1.0

M z = 299,850 g/mol
0

200,000

400,000

600,000 800,000 1,000,000

Mi (g/mol)

Molecular Weight of Polymers


Molecular Weight Distribution (MWD)

MWD = M w Mn

Perfectly Monodisperse MWD = 1.0 Monodisperse (general term) 1.0 < MWD 1.1 Polydisperse MWD > 1.1 Living polymerization: 1.0 < MWD 1.1 Radical polymerization: 1.5 < MWD 2.0 Condensation polymerization: MWD ~ 2 Ziegler-Natta polymerization: 5 < MWD < 30

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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

An Example Polymer - Polyethylene


CH2=CH2 ethylene
CH2CH2 n

polyethylene (PE) MW = 105 g/mol N = 7143 CH2 a = 0.154 nm

extended chain Lex = Na = 1100.0 nm = 1.1 m

Rg (radius of gyration) random coil Rg = N0.5a = 13.0 nm

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An Exercise

Suppose that you want to travel from place A to place E, visiting your friends along the way. Unfortunately your friends live only on the eastern and western coasts, leading to a somewhat unconventional journey.

Start 1: A 2: B 3: C 4: D

Destination 2: B 3: C 4: D 5: E

Miles 210 90 620 2790

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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

An Exercise - continued
Number-average

M n = xi M i = = 927.5 miles

N i M i 1 210 + 1 90 + 1 620 + 1 2790 = 1+1+1+1 Ni

The number-average of the miles traveled in the four legs of the journey is 928 miles. This is the average distance traveled in each leg of the journey. It places equal emphasis on each leg.

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An Exercise - continued

Mass-average

Ni M i N i M i2 = = = M w wi M i Mi Ni M i Ni M i 2 2 2 1 210 + 1 90 + 1 620 + 1 27902 = = 2215.8 miles 1 210 + 1 90 + 1 620 + 1 2790


The mass-average of the miles traveled in the four legs of the journey is 2216 miles. This average places a greater emphasis on the leg of the journey with the largest "mass" - that is the fourth leg in which you travel 2790 miles. It is more representative of the major part of your journey.
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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Property - Molecular Weight Dependence


1. Glass Transition MW Dependence

PMMA
Tg (C)

Tg =Tg

10-4 Mn

K Mn

K is a polymer-related constant.

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Property - Molecular Weight Dependence


2. Viscosity MW Dependence

3.4

topological entanglement

1.0

Mc critical MW

M < Mc, no entanglement M > Mc, entanglement


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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Property - Molecular Weight Dependence Entanglements affects solubility of polymers


Polymers chains tends to entangle beyond critical length and when entangled, polymers cant move laterally but move along their lengths (think chowmein) Polymers that are long enough to entangle need to disentangle before dissolution Solvent diffuses into the solid and swells the material, allowing space for movement and then slow longitudinal diffusion allows single chains to dissolve

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States of Thermoplastics Polymers


Thermoplastics Polymers

Amorphous
e.g. polystyrene, polyacrylates, etc.

Liquid Crystalline
thermotropic or lyotropic, main-chain or side-chain LC polymers (LCPs)

Crystalline
e.g. polyethylene, polypropylene, etc.

Amorphous: No long range order, only short range order. Like gas and liquid. Important parameter: Glass Transition Temperature (Tg) Glassy state (hard) Tg Rubbery state (soft)

Crystalline: Long range order, including positional, orientational, and conformational orders. Like crystals or solids. Important parameter: Melting Point (Tm)

crystallization melting
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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

7 Crystalline melting temperature (Tm ) : temperature at which crystalline Polymer converts to a liquid or crystalline domains of a semi crystalline Polymer melt (increased molecular motion ) 8- Glass transition temperature (T (Tg ) : temperature at which an amorphous polymer converts to a liquid or amorphous domains of a semi crystalline polymer melt 9 Thermoplastics (plastics ) :polymers that undergo thermally reversible Interconversion between the solid state and the liquid state 1010- Thermosets : polymers that continue reacted at elevated temperatures generating increasing number of crosslinks such polymers do not exhibit melting or glass transition 1111- Liquid crystalline polymers : polymers with a fluid phase that retains some order 1212- Elastomers : rubbery , stretchy polymers the effect is caused by light crosslinking that pulls the chains back to their original state

Glass phase (hard plastic)


9

Log-stiffness

8 7 6 5 4 3

Leathery phase

Rubber phase (elastomer)

Liquid

Temperature

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Dr. S.Ray_Chem Engg_NIT Agratala

1/17/2013

Melting versus Glass Transition


Melting Glass Transition

Property of the crystalline region Property of the amorphous region Below Tm: Ordered crystalline solid Below Tg: Disordered amorphous Above Tm: Disordered melt solid with immobile molecules A first-order transition Above Tg: Disordered melt A second-order-like transition

-like

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Higher Order Polymer Structures Second Order Structures - Conformation


extended chain random coil folded chain chain helix

Third Order Structures Micromorphology

non-entangled

entangled

fringe micelle crystal chain-folded crystal

Fourth Order Structures Macromorphology


crystalline spherulites double gyroid of ABC terpolymers
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Polymer Processing Engineering

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