CHEMICAL ENGINEERING PRINCIPLES

IN POLYMER PROCESSING
CH 62045
Prof. Swati Neogi

Class Guideline
• Attendance Policy:
– 100% attendance is desirable
– No unexcused absence
– Up to four excused absence




Guest Lecture & Field Trip:
Guest lecture will be arranged from time to time
Field trip to industries will be arranged
Attendance is mandatory

Class Guideline
• Assignment and class tests:
• Regular homework assignments will be given
• Students are expected to maintain a notebook for
assignments and are required to bring the assignment
notebooks everyday in the class
• Surprise checking of the assignments will be conducted
• Surprise class tests will be taken.

Grading Policy
Assignments, class tests, teacher’s evaluation: 20%
Theory: weightage 0.75
Mid term:
30%
Final Exam:
50%
-----------------------------------------------------------------------Total:
80%
Tutorial: weightage: 0.25
Two term paper
Field trip/Guest lecture

Following is the list of books which can be consulted for the course: – – – Principles of Polymer Processing by Tadmor & Gogos Polymer Processing:Principles and modeling. Avenas. Take class notes.Text Book • No single text book will cover the entire subject. Class notes are prepared based on several books. by Agassant. & Carreau Plastics Engineering by R. Sergent. J Crawford .

Course Information • • • • Credit: 3-1-0 Course Objective (Handout) Course outline (Handout) Tentative Lecture Schedule (Handout) .

Principles to describe polymer processing Polymer Basics (i) What are polymers (ii) How do they differ form other materials (iii) Why are they different (iv) Properties (v) Applications Module 1 .Course Objective Learn to use CHE.

Course Objective Learn to use CHE. Principles to describe polymer processing Chemical Engineering principles (i) Transplant Equations Polymer Rheology (ii) Polymer flow analysis (iii) Heat transfer & viscous heat dissipation (iv) Devolatiligation & mass transfer Module 2 .

Principles to describe polymer processing Polymer processing technology (i) Extrusion (ii) Injection molding (iii) Blow molding (iv) Calendaring (v) Thermoforming (vi) Spinning Module 3 Manufacturing of polymers is beyond he scope & objective .Course objective Learn to use CHE.

3: Polymer properties (3) 1.2: Characterizing parameters (4) 1.Course Overview Module 1: Fundamentals of Polymer (# of Lectures: 10) 1.1: Introduction ( 2) 1.5: Polymer additives (1) .

1: Introduction to polymer processing (1) 2.Course Overview Module 2: Chemical Engineering Principles for Polymer Processing (# of lectures: 14) 2.4: Heat transfer and viscous heat dissipation in polymer processing (3) 2. diffusivity and devolatilization during polymer processing (2) .2: Polymer Rheology (3) 2.5: Mass transfer.3: Mass and Momentum equations for isothermal polymer flow analysis (5) 2.

Course Overview Module 3: Polymer Processing Technologies ( # of Lectures: 18) 3.1: Extrusion (10) 3. Thermoforming.3: Calendaring . Other(2) .2: Injection Molding(6) 3.

Module 1: Course Outline – – Introduction of polymer (L2) • Definition • Advantages • Classification of polymer • Applications Characterization parameters L(3) • Molecular • Chemical composition • MW/MWD • Macroscopic • • • Topology Orientation Phases » » Crystalline Amorphous .

Module 1: Course Outline – Polymer properties (L4) • Thermal Properties – – • Melting point Glass transition Mechanical Properties – – – – – – – Strength Modulus Elongation Toughness Impact Creep Permeability .

5 . Shear rate Shrinkage/cooling Polymer swelling/memory effect Polymer Additives (L0.5) Material selection and design guidelines (L0.Module 1: Course Outline – Chemical Properties – – – – – – • Melt properties – – – – – – Oxidation Thermal stability Degradability Chemical resistance Flammability/flame resistance UV resistance Flow Characteristics Viscosity vs.

1: Introduction .Module 1: Fundamentals of Polymer Section 1.

C2H4 • General name of following series of compounds RCOOH.Some Organic Basics • Name following organic compounds and write down the structure. HO-R. – CH4.C2H2. C3H8. R-NH2. C2H6. HO-R-OH write the product of following reaction: RCOOH +RNH2 --------RCOOH +HOR -------------RCOOH + HO-R-OH --------- .

Processing with additives Finished Product Polymers .

• Polymers are seldom used in their neat form. . polymers. Resin. they are called resins. called mers. building blocks. resins. • When in form ready for further working.Polymer. and Plastics • A polymer is any substance made up of many of repeating units. plastics are used interchangeably. • Frequently. The resulting material is usually referred to as a plastic. most often compounded with various additives.

Development of Plastics • • • • • • • • • • • 1868 cellulose nitrate 1909 phenol-formaldehyde 1927 cellulose acetate and polyvinyl chloride 1929 urea formaldehyde 1931 Duprene 1935 ethyl cellulose 1936 acrylic and polyvinyl acetate 1938 nylon 1942 polyester and polyethylene terephthalate 1943 silicone 1947 epoxy and polypropylene .

Basic Concept .

Basic Concept • • • • • • • • • Polymer is large molecule having repeating unit Repeating structural units joined by covalent bonds Molecular weight can be up to 10000 Monomers should have reactive functional group or double bond Basic linear chain is called backbones Molecular weight can be up to 10000 Extensive formability and ductility Light weight. low cost Higher chemical reactivity .

by blending different polymers . and/or O. F and Si • Low strength compared with metals. lower melting point • Properties can be tailormade by choosing different monomers. N.Basic Concept • Compound of hydrogen and carbon.

Forces In Polymer • Primary force – Covalent bonds within chain • Secondary Force: – Vander walls force between chains – Hydrogen bonding – Dipole-dipole interactions • Chemical bonds between chains as in thermoset polymers .

number of repeating units .molecule with minimum functionality of two that reacts to form the structural units of the polymer Oligomer .macromolecule generated through sequential reaction of a small number of elementary units Repeating unit . .Nomenclature • • • • • • • • • • Monomer . tetramer . .structure composed of the minimum number of structural units necessary to generate the polymer Degree of polymerization .) Polymer . trimer.short chain synthesized from reaction of several monomers (dimer.

COMMON MONOMERS AND POLYMERS • Vinyl and Vinyledene monomer and their polymer • Ester forming monomers and Polyester. Polycarbonate • Amide forming monomers and Polyamide .

Common Vinyl and Vinyledene monomers and Polymers .

Common Ester. Carbonate and Amide Polymers .

Monomers Among Top 50 chemicals April 10. 1995 Chemical and Engineering News .

086 – *1998 (106 lb) .924 • • • Polyvinyl chloride and copolymers: 14.940 g/cm3): 7.940 g/cm3): 7.578 – Linear low density (<0.502 Polypropylene: 13.Production of Thermoplastics • Polyethylene – Low density (<0.940 g/cm3): 12.327 • Acrylonitrile-butadiene-styrene: 3.227 – High density (>0.825 Styrene polymers – Polystyrene: 6.

581 Unsaturated polyester: 1.Production of Thermosets • Phenolic 3.940 – – – – Urea: 2.713 Epoxy: 639 Melamine: 290 – *1998 (106 lb) .

Production of Synthetic Fibers • Noncellulosic fibers – – – – • Polyester :3.800 Acrylic :346 Cellulosic fibers – Acetate and rayon :365 – *1998 (106 lb) .911 Nylon :2.847 Olefin :2.

Production of Synthetic Rubber • Styrene-butadiene rubber: 960 • Polybutadiene: 580 • Ethylene-propylene: 321 • Nitrile: 89 • Polychloroprene: 72 – *1998 (106 lb) .

Applications: Packaging • Food wrapping • Bottles • Blister packs • Trash bags and grocery sacks • Shrink wrap • Foam packing .

arms) • Artificial organs (heart. bridges. feet. valves) • Dental fillings. and coatings • Disposable surgical clothes and instruments • Eyeglass frames and lenses .Applications: Medical • Catheters • Hip joint replacements • Artificial limbs (legs. blood vessels.

ski poles. vaulting poles. masts. surfboards. helmets.Applications: Recreational • Boat hulls. kayaks. and pads . and automobiles • Athletic shoes • Skis. ski boots. dune buggies. and ski lift chairs • Golf ball covers and golf club shafts • Bicycle parts. Boat hulls. and oars • Bobsleds. and sails • Rackets. golf clubs.

Applications: Entertainment • Stereo and television components • VCR tapes and housings • Cases for radios. tapes. and CDs • Toys . tape players.

Applications: Textile • Clothing • Carpets • Non-woven fabrics • Diapers and other disposables • Upholstered fabrics for furniture • Draperies and wall paper material .

Applications: Construction and Home • Moldings • Sprinklers and pipes • Counter tops • Sinks. and plumbing fixtures • Flooring (vinyl and carpeting) • Paint . shower stalls.

trim. monorail. body panels. and seats • Aerospace components • Train. and light rail cars • Seat covers and dashboard covers • Truck bed liners • Gas tanks .Applications: Transportation • Automotive Automotive bodies.

Applications: Industrial • Pipes. and tanks • Gears and housings • Adhesives and coatings • Vibration damping pads • Electrical circuit boards • Wire insulation and connector devices • Gaskets and sealants . valves.

Applications: Information Technology • Photoresists for microprocessor fabrication • Interlayer dielectrics for microprocessor • fabrication • Alignment layers for liquid crystal displays • Lubricants for computer hard disks .

Class Assignment • Write at least two more application of polymer for each sector from your own observation • Write structures indication mponomer for – PP – PE – Nylon .

Review of Lecture 1 • What is polymer and plastics • Characteristics of polymer • Characteristics of monomer required to undergo polymerization • Types of monomer • Examples of polymers using each type of monomers • Application of polymers-different areas .

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Based on availability – – Synthetic • Adhesives • Fibres • Coatings • Plastics • Rubbers Natural • Polysaccharides – – • Proteins – – • Adhesives Fibres Adhesives Fibers Polyisoprene – Rubbers .Classification of Polymer 1.

• Based on reaction Mechanism Addition (Chain) Polymer – • Break a double bond • PE.Classification of Polymer 2.PP Condensation (Step) Polymer – Elimination of by product (except epoxies and polyurethanes) • PET. PBT. Nylon .

Based on molecular Structure – – – Linear Chain Branched Chain Network or gel Polymer .Classification of Polymer 3.

• • Based on Morphology Amorphous Crystalline/semicrystalline 5. • • Based on molecular composition Homopolymer Copolymer • • Alternate Copolymer: ABABAB Block Copolymer:AAAAAABBBBBBBAAAAAAABBBBB – • SBS (styrene-Butadiene-Styrene) Graft Copolymer: B B B AAAAAAAAAAAAA -High Impact Polystyrene. HIPS(Polystyrene with grafted polybutadiene) .Classification of Polymer 4.

Based on processing and response to temperature -thermoplastic -melts/softrens with temperature and can be reproccessed -thermoset -does not melt/softened with heat .Classification of Polymer 6.

Classification by Application • • • • • Plastics Fibers Elastomers Coatings Adhesives .

polymer.Lessons learned in Section 1. oligomer. plastics.1 • • • • What is polymer Different monomer and their polymer Unique characteristics of polymer Terms related to polymer such as monomer. resins • Applications of polymers • Classification of polymers: different scheme of classification .

Polyethylene terepthalate vii.Assignment: Section 1. Polystyrene ii. Find at least 10 polymers from your surroundings and everyday use and write the name of polymer and chemical structure and classification and basis of classification . 1. Polymethylacrylate iv.1 1. Polyethylene iii. Polypropylene vi. i.Polycarbonate ix. Nylon 6.6 2. Write down the abbreviation. Polymethylmethacrylate v. chemical structure of monomer and chemical Structure of polymer formed. Name three common vinyl polymer and write down their structure 4. Write the classification scheme of polymers with Examples 3. Polyvinyledene fluoride viii. Classify these polymers based on reaction mechanism.

Name three common vinyl polymer and write down their structure 4.Assignment: section 1. Write the differences between polymer. Write different applications of polymer listing some specific polymers for specific applications . resin and plastics 6. Find at least 10 polymers from your surroundings and everyday use and write the name of polymer and chemical structure and classification and basis of classification 5.1 3.

Module 1: Fundamentals of Polymer Section 1.2: Characterizing Parameters .

Characterizing Parameters • Molecular – Chemical composition – MW/MWD • Macroscopic – Topology – Orientation – Phases • Crystalline structure • Amorphpous Structure .

Determines morphology • Pendant groups such as Benzene ring. Determines strengths • Dipole-dipole force as in PVC. bulky side chains .Chemical Composition • Chemical composition: – Chemical nature of the monomers and the resulting nature of backbones • Chemical Composition Determines – Strength of the covalent bond – Intermolecular forces. Polyester • Hydrogen Bonding when polymer contains –OH and NH groups – How closely they are packed.

) – How much flexibility • Presence of non flexible groups in the backbone such as amide.sulfone. Carbonyl .Chemical Composition(contd. p-phenylene.

Think!!!!!! • How chemical composition will affect following properties? – – – – – – – Melting point? Crystallinity? Degradation/durability? Chemical resistance? Moisture absorption? Reactivity? Density? .

– Usually the molecular weight of a polymer is characterized by average molecular weight and a range of distribution – The molecular weights of polymers are much larger than the molecules usually encountered in organic chemistry – Molecular weight and its distribution affects the properties significantly . It has a range. n can vary from zero to Infinity – Single polymer contains number of molecules with varying weights.Molecular Weight and Distribution Molecular weight: – Polymer = (mer)n – n is not a single numebr. Theoretically.

Molecular Weight Distribution in Polymer .

The weighted mean can be taken with the weight fraction.Average Molecular Weights • Different average values can be defined depending on the statistical method that is applied. the mole fraction or the volume fraction: – – – – Weight average molar mass or Mw Number average molar mass or Mn Viscosity average molar mass or Mv Z average molar mass or Mz .

– DP based on average molecular weight – DP based on number average molecular weight .Average Molecular Weights • Average Molecular weight based on Degree of Polymerization(DP) – DP is the number. n. of repeating units in the polymer chain. – The molecular weight of a particular polymer molecule is a product of the degree of polymerization and the molecular weight of the repeating unit.

representing the total weight of the molecules present divided by the total number of molecules. • Ni: number of molecules with mass Mi • Pi: number average probablity of Ni .Number Average Molecular Weight Number-Average Molecular Weight • The number average is the simple arithmetic mean.

Weight Average Molecular Weight • Weight-average emphasizes the mass of the molecules so that the heavier molecules are more important. • Pi : weight average probability of molecule Ni with mass Mi .

The viscosity-average molecular weight lies somewhere between the number average and the weight average a is constant that depends on the polymer-solvent pair and on temperature .Viscosity Average Molecular Weight • One of the oldest methods of measuring the average molecular weight of polymers is by solution viscosity.

Z Average Molecular Weight .

Comparison of Average Molecular Weights Mn < Mv < Mw < Mz .

MWD: Polydispersity Index • Molecular weight distribution also plays important role in determining the properties along with the average molecular weight • The weight-average molecular weight is larger than or equal to the number-average molecular weight. • The ratio of the weight-average and number-average molecular weights. is a measure of the polydispersity of a polymer mixture .

• A ratio that is around 1. a high ratio indicates that the range is wide. With rare exceptions.MWD: Polydispersity Index • Polydispersity Index indicates how widely distributed the range of molecular weights are in the mixture. all synthetic polymers are polydisperse .0 indicates that the range of molecular weights in the mixture is narrow.

Polydispersity Index

Ni

Mi

Number Average Molecular Weight:
Example
Example :
Size exclusion chromatographic data of a new polymer shows the
following molecular weight distribution.
Number of Molecules
Mass of each molecule
5
10,000
3
30,000
2
60,000
Calculate the number average (Mn) and the weight average (Mw)
molecular weights of this polymer.

Number Average Molecular Weight:
Example
Multiply the weight of the polymer molecule by the number of
polymer molecules of that weight



ΣNiMi would be: 5(1000) + 3(30,000)+ 2(60,000) = 260,000
ΣNi would be: 5+3+2 = 10
Therefore, Number Average Molecular Weight Mn
= 260,000 / 10 = 26,000

Number Average Molecular Weight:
Example

ΣNiMi = 260,000
Weight Average Molecular Weight is ΣWiMi = 39,960

Experimental Methods For Molecular Weight Determination .

– Calculate average Molecular weight of PE with DP of 1000 .

Number Average Molecular Weight: Experimental Measurement Technique The number average molecular weight may be determined by colligative property measurements: – – – – Osmometry Vapor pressure change Freezing point depression (rare) Boiling point elevation (rare) .

MW/MWD • The weight average molecular weight may be determined experimentally by – Scattering measurements • Light • X-rays • Neutrons – Sedimentation equilibrium (ultracentrifuge) .

Molecular Weight and Properties • MW ----> Viscosity ----> Processing hardness ---->Part property • Performance properties of finished product and processing parameters affected by MW • • • • • • • • • • Tensile strength Impact strength Toughness Creep resistance Stress-crack resistance Elongation to break Reversible elasticity Melting temperature Melt viscosity Difficulty of processing .

polymer does not exhibit its properties for a particular application • Threshold MW depends on the Application.Threshold and Working Molecular Weight • Below a certain molecular weight. known as threshold molecular weight. – For adhesive. Threshold MW is quite high • With MW strength and other properties increases but Viscosity increases due to chain entanglement • High viscosities create processing problems • Working is defined as the MW optimized for processing and properties . threshold MW is relatively low – For high strength shaped plastic products.

Molecular Weight and Properties .

Number of molecules Molecular weight 50 1000 45 2000 30 3000 40 5000 80 6000 25 7000 30 8000 20 9000 10 10000 . Calculate number average molecular weight.Assignment: 6. weight average molecular weight and polydispersity index from the following size exclusion chromatography data.

What is pendant group? Name and write the formula of two polymers which has the pendant group identifying pendant groups. 2.Assignment 3: Molecular characterization and molecular weight 1. Write the formula for number average molecular weight. 3. . Why polymer characterization is so important for a polymer engineer? List characterization parameters. weight average molecular weight and polydispersity index.

000 10 600.000 8 350.000 5 700.000 3 250.Calculate number average.000 3 750.000 13 550.000 20 500.000 5 300.000 .000 10 400.000 1 200.000 13 450.000 8 650. and polydispersity index Number of Molecules Mass of each Molecule 1 800. weight average.

800.000 20 500.500.000 3 250.000 750.000 1.000 Number average Molecular weight=5.000 4.000 200.000.000 7.000 3 750.000 8 650.000 Ni = 100 NiMi = 50.000 13 550.Number Average Molecular Weight Number of Molecules.500.000 10.000 6.000 5 300.000 2. NiMi 1 800.000.000 1 200.000.000 .000 5.000 800.150.000 10 400.250.000 13 450.00. Mi Total Mass of Each Type of Molecule. Ni Mass of Each Molecule.850.000 5 700.000 10 600.000 2.200.000 5.000 8 350.000 3.000.

000 6.600 PDI=531600/500000=1.000 2.000 0.000 10.000 4.000 8 350.Weight Average MW & PDI Number of Molecules Mass of Each Molecule Total Mass of Each Type of Molecule Weight Fraction Type of Molecule (Ni) (Mi) (NiMi) NiMi) (WiMi) 1 800.080 32.016 12.000.000 7.000 13 550.104 67.500.250.070 49.063 .000 0.000 0.000 0.000 2.800 3 750.600 10 600.800.000 800.000 13 450.000 0.600 5 300.000 0.000 1.000 750.000.120 72.000 5.045 33.000 5.004 800 WiMi = 531.750 5 700.000 0.143 78.000 0.000 0.000 200.000 8 650.500.850.000 3 250.650 10 400.000 0.000 0.650 20 500.000.200.056 19.150.000 0.117 52.750 1 200.015 3.000 0.000 3.030 9.200 100.

6 • Molecular weight data for some polymer are tabulated here. which one of the polymers listed in Table 4. Compute (a) the number-average molecular weight.Problem Statement 4. and (b) the weight-average molecular weight. (c) If it is known that this material’s number-average degree of polymerization is 477.3 is this polymer? Why? (d) What is this material’s weight-average degree of polymerization? .

000-92.000 0.000 0.16 80.10 0.000 0.18 0.08 32.000-56.000-32.23 68.000 0.000-80.29 56.21 0.05 .Problem Statement 4.17 44.000 0.000-20.000-44.03 0.000 0.000-68.28 0.000 0.05 0.02 20.6 Molecular Weight Range (g/mol) xi wi 8.15 0.

. • wi – the weight fraction – The mass of polymer chains that fall within a certain molecular weight range divided by the total mass.xi versus wi • xi – the number fraction – The number of polymer chains that fall within a certain molecular weight range divided by the total number of polymer chains.

(a) Number-average molecular weight.28 14000 62. Mi (g/mol) xi xi*Mi (g/mol) 14.05 700 26.000 0.000 0.21 7980 50.10 7400 86.000 0.15 3900 38.03 2580 Mn=ΣxiMi =47720 g/mol .18 11160 74.000 0.000 0.000 0.000 0.

000 0.17 6460 50.000 0.000 0.16 11840 86.000 0.(b) Weight-average molecular weight Mi (g/mol) wi wi*Mi (g/mol) 14.000 0.08 2080 38.000 0.23 14260 74.000 0.29 14500 62.02 280 26.05 4300 Mw=ΣwiMi =53720 g/mol .

042 g/mol . therefore m = 100. where m is the molecular weight of a mer unit – nn = 477 and Mn = 47720 g/mol.(c) Identify polymer using number-average degree of polymerization • nn = number-average degree of polymerization – Average number of mer units per polymer chain – nn = Mn / m.

(c) Identify polymer using number-average degree of polymerization • Molecular weight of each mer unit can be found by summing molecular weights of constituent atoms • In this case we’ll ignore the molecular weight contributions of the terminal groups .

152 g/mol PMMA 8H+5C+2O 100.17 g/mol Nylon 6.104 g/mol PET 8H+10C+4O 192.014 g/mol PP 5H+2C 29.499 g/mol PTFE 4F+2C 100.17 g/mol Polycarbonate 14H+16C+3O 254.285 g/mol .6 6H+4C+2O+2N 114.062 g/mol PS 8H+8C 104.054 g/mol PVC 3H+2C+Cl 62.Mer Unit Molecular Weights Polymer Atoms in Mer Mer Unit MW PE 4H+2C 28.117 g/mol Bakelite 9H+9C+1O 133.

(c) Identify polymer using number-average degree of polymerization • Most likely PTFE (Teflon) or PMMA (Plexiglass) • Differentiate by color – Teflon – white – PMMA – clear • Unlikely to use this procedure to identify a polymer in real life .

(d) Weight-average degree of polymerization

nw = weight-average degree of polymerization
– Average number of mer units per polymer chain
– nw = Mw / m, where m is the molecular weight of a mer unit
– m = 100.042 g/mol and Mw = 53720 g/mol, therefore nw = 537

Different from nn because calculated using different average
molecular weight, Mw vs Mn

Topology
• Molecular topology is a description of
molecules which includes their stereo-chemical
arrangement, branching, formation of helices
and network/looping/entanglement
characteristics
• Physical properties of chain depends on interactions
between its chains.
• Interactions between chains depend on the shape of the
chain making up the backbone

Topology

Topology

Such polymers are said to be nonlinear – Polymers with pendant groups. reducing their density . such as low density polyethylene (LDPE). such as the methyl group in polypropylene. have branches of different sizes irregularly spaced along the chain. are considered to be linear – The branches prevent the nonlinear molecules from packing as closely as the linear.Topology • Linear Polymers: – Can form close packed structure • Nonlinear (Branched) Polymers – Some polymers.

Topology
• Cross linked and Network Polymers
– Some polymers have cross-links between polymer chains creating
three-dimensional networks
– A high density of cross-linking restricts the motion of the chains and
leads to a rigid material
• Different structure give rise to very different properties
• linear polyethylene has a melting point 20C higher than branched
polyethylene. Unlike linear and branched polymers, network polymers do
not melt and will not dissolve in solvents.
• The effect of structure on polymer properties is called the “StructureProperty Relationship“.

Isomerism



Regularity of polymer chains decides the morphology
Highly irregular chains form amorphous polymer
Highly regular structure promotes crystalline growth
Some isomeric forms of polymer chains decrease the
regularity of chains reducing the probability of forming
crystalline structure

Isomerism
• Isomers are molecules
– with same molecular formula
– Different arrangement of the atoms in space

• Different arrangements which are simply due to the molecule rotating as a
whole, or rotating about particular bonds is not considered as isomers
• Three forms of isomerism in polymers
– Monomer orientation
• Head-to-tail
• Head-to-head
– Geometric
• Cis isomerism
• trans isomerism
– Stereoisomerism or tacticity
• Isotactic
• Syndiotactic
• Atactic

Monomer Orientation
• Monomers with pendant groups can attach in two ways.
– head-to-tail
– head-to-head

• The usual arrangement is head-to-tail with the pendant
groups on every other carbon atom in the chain

Head to tail

Head to head

When a monomer with two conjugated double bonds. such as isoprene.Geometric Isomerism • Double bonds in the polymer chain can show cis.or trans-isomerism. . undergoes chain polymerization one double bond can remain in the chain.

Stereoisomerism • Three different form – Atactic (Random configuration) – Isotactic (Same configuration) – Syndiotactic (Alternating configuration) .

Stereoisomerism .

.Stereoisomerism • The physical properties of a polymer can have a strong dependence on tacticity. • Atactic has lower melting temp (< 0° C). It is also more soluble in most solvents. • Isotactic and syndiotactic polypropylene have regular structures. and can be molded. rubbery. which allow favorable polymer-polymer packing • Atactic polyprop. is soft. has an irregular structure and poor packing • Isotactic and syndiotactic forms have higher melting temperatures (~165° and 130° C) and are poorly soluble in many solvents.

branched. crosslinked – Molecular Weight • Phases of polymer – Crystalline phase – Amorphous phase .Morphology • Polymer morphology is the overall description of polymer structure including Phases • Morphology is determened by – Topology • Linear.

These polymers are said to be amorphous • Amorphous polymers are – Softer – have lower melting points – penetrated more by solvents .Amorphous Phase • Polymer chains with branches or irregular pendant groups cannot pack together regularly enough to form crystals.

less affected by solvent penetration strong but with low impact resistance • Polymer Molecules form lamella . These polymers are called crystalline polymers • Polymers are semi crystalline • Highly crystalline polymers – – – – rigid high melting.Crystalline Phase • Polymer chains without branches or bulkier pendant groups can pack together regularly enough to form crystals.

Crystalline Phase • Regular polymers forms plate like structure called lamellar • Usual thickness of the lamella is about 10 to 20 nm .

chain entanglements are extremely important.Semi-Crystalline Polymers • • • Semi-crystalline polymers have both crystalline and amorphous regions When crystals are formed from the melt. the amorphous portion is outside the lamella . Polymer chains meandering in and out of ordered crystalline portions The crystalline portion is in the lamellae.

The percent crystallinity has an important influence on the properties of the polymer.Semi-Crystalline Polymers • Ppercentage of the polymer that is crystalline is called the percent crystallinity. .

Spherulites • • • When a molten crystallizable polymer cools. the crystals grow from individual nuclei and radiate out like the spokes of a bicycle wheel The crystalline portions actually radiate out in in three dimensions. forming spheres that are called spherulites In a sample of a crystalline polymer there are billions of spherulites .

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Spherulite .

Factors Affecting Crystallinity • • • • • Structural Regularity Degree of Polymerization Intermolecular Forces Pendant Groups Processing – Rate of Cooling – Orientation .

Structural Regularity • Structural Regularity promotes crystallization • Crystallization is favoured by – Linear structure – High degree of symmetry • Syndiotactic and or isotactic isomers • Limited crystallization can take place if a small number of branches are present. .

because the long chains tend to be more tangled.Degree of Polymerization • Relatively short polymer chains form crystals more readily than long chains. • High crystallinity generally means a stronger material. . so the polymer chains can slide by each other and cause a break in the material. but low molecular weight polymers usually are weaker in strength even if they are highly crystalline • Low molecular weight polymers have a low degree of chain entanglement.

Dipole-dipole forces between the polar groups hold the PET molecules in strong crystals.Intermolecular Forces • Crystallinity is favoured by strong inter backbone forces • The presence of polar and hydrogen bonding groups favours crystallinity because they make possible dipoledipole and hydrogen bonding intermolecular forces • Polyethylene terepthalate. contains polar ester groups. .

bulky pendant groups • Poly vinyl alcohol (PVA) is made by the hydrolysis of poly vinyl acetate ) (PVAc). PVA crystallizes more readily than PVAc because of the bulky acetate groups in PVAc. The -OH groups in PVA also form strong hydrogen bonds.Pendant Groups • Regular polymers with small pendant groups crystallize more readily than do polymers with large. PVAc PVA .

. polymers often are cooled rapidly from the melt. crystallization is controlled by kinetics rather than thermodynamics There may not be time for the chains. which are entangled in the melt.Processing : Cooling Rate • • • • • Major difference between small molecules and polymers is that the morphology of a polymer is dependent on its thermal history The crystallinity of a polymer can be changed by cooling the polymer melt slowly or quickly. to separate enough to form crystals. In this situation. so the amorphous nature of the melt is "frozen into" the solid A polymer is more likely to have a higher percent crystallinity if it is cooled slowly from the melt. and by "pulling" the bulk material either during its synthesis or during its processing When they are processed industrially.

Processing: Orientation • Crystallinity can be enhanced by stretching the bulk material either when it is synthesized or during its processing • Induced crystallization due to orientation is common for both films and fibers • When a film is formed the small crystallites tend to be randomly oriented relative to each other. . Drawing (stretching) the film pulls the individual chains into a roughly parallel organization • Films can either be uniaxially oriented (oriented in only one direction) or biaxially oriented (oriented in two directions).

Unstretched nylon fibers are brittle. .Processing: Orientation • Fibers normally are drawn so that they are oriented in one direction. When the fibers are stretched the oriented fibers are strong and tough. for example..

Effect of Crystallinity on Properties .

3: Polymer Properties .Module 1: Fundamentals of Polymer Section 1.

Polymer Properties • Thermal Properties – Melting point – Glass transition – Thermal Stability • Mechanical Properties – – – – – – – Strength Modulus Elongation Toughness Impact Creep Stress Relaxation .

Shear rate – Shrinkage/cooling – Polymer swelling/memory effect • Other – Electrical properties .Polymer Properties Chemical Properties – – – – – – Oxidation Thermooxidative stability Degradability Chemical resistance Flammability/flame resistance UV resistance • Melt properties – Polymer Rheology • Flow Characteristics • Viscosity vs.

Tm Molten State . Tg Glassy State Crystalline Polymer Heat.Thermal Properties Amorphous Polymer Heat.

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Tg Glassy State .Thermal Properties Semicrystalline polymer Heat. Tm Molten polymer Heat.

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polymers are glassy • Rubbery behavior due to polymers ability to change its conformation at high temperature • Glassy behaviour due to lack of ability to change conformation at low temperature .Glass Transition temperature • Above Tg polymers are rubbery whereas below Tg.

Change in modulus with Tg

Factors Affecting Tg

– Polarizing group
• Polar groups increases Tg
– Cross linking
• Tg in creases with cross link density
– Plasticizer
• Plasticizer decreases Tg

Factors Affecting Tg

– Polarizing group
• Polar groups increases Tg
– Cross linking
• Tg in creases with cross link density
– Plasticizer
• Plasticizer decreases Tg

Tg and Molecular Weight

Backbone Flexibility .

Pendant Group .

Pendant Group .

Pendant Group .

Pendant Group .

Pendant Group .

Polar Molecules Polar Molecules .

Cross Linking .

Effect of Plasticizer .

Effect of Stereochemistry .

Factors Affecting Melting point • Melting temperature depends on % Crystallinity • Chemical composition • Chain entanglement .

Melting Temperature and chemical composition .

Melting Temperature and Crystallinity .

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Mechanical Properties • The mechanical properties of a polymer involve its behavior under stress How strong is the polymer? How much can you stretch it before it breaks? How stiff is it? How much does it bend when you push on it? Is it brittle? Does it break easily if you hit it hard? Is it hard or soft? Does it hold up well under repeated stress? .

Mechanical Properties • • • • Tensile strength:Resistance to stretching Compressive strength:Resistance to compression Flexural strength:Resistance to bending(flexing) Impact strength:Resistance to sudden stress. flexural. like a hammer blow • Fatigue:Resistance to repeated applications of tensile. or compressive stress • Creep:Increase in strain when a polymer sample is subjected to a constant (typical Viscoelastic Properties): time dependent • Stress relaxation:Decrease in stress when a sample is elongated rapidly to constant strain (typical Viscoelastic Properties): time dependent .

Strain=elongation=L/L0 Youngs Modulus = Stress/Strain .

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Effect of T on E .

Factors affecting stiffness .

Factors affecting stiffness .

Typical Stress Strain Curve for Plastic C B A A: Linear elastic region B: Yield Point C: Failure point .

Toughness .

Comparison of toughness .

Creep and Stress Relaxation .

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Chemical Properties .

Chemical Properties • • • • • • Oxidation Thermal stability Chemical resistance UV resistance Flammability/flame resistance Degradability .

Resistance to Oxidation and Thermal Degradation • Oxygen in the atmosphere and high heat can cause the can polymer degradation • Tertiary carbon atoms are more vulnerable for this type of degradation • Usually Antioxidants(polymer additives) are added to improve the oxidaive properties of polymers .

Resistance to Oxidation and Thermal Degradation Polymer degrades at high temperature. Two things happen when polymer is heated to a very high temperature: Processing temperature is well below than the degradation temperature .

Resistance to Oxidation and Thermal Degradation Thermo-oxidative Stability .

Chemical Resistance • Chemicals can break the bond • Can extract additives and antioxidants • Can fill up of void and cause for swelling. Swelling reduces mechanical strength • Chemical resistance varies among polymers • Chemical resistance of polymers can be increased by modifying the polymers • Crystalline polymers are more resistant than Amorphous polymers • Crosslinking increases chemical resistance • Most of the polymers are better chemical resistant than metals .

Resistance to UV Light UV light can cause the degradation of Polymer .

Resistance to UV Light .

Resistance to UV Light •UV stabilizer can be added to improve the UV resistance of polymer •Carbon Black is an excellent UV stabilizer .

Ozonolysis • ozone in atmosphere can cause the degradation of polymers by breaking the bond .

Resistance to Burning – Polymer mostly being carbon and hydrogen is flamable – Additives can be added to improve the flame retardant properties of polymer – Halogens are excellent flame retardants. Most of the flame retardant additives are halogen based – European countries does not allow halogen because of the toxicity of the aloen based additives – Aluminium trihydroxide (ATH) and Magnesium di hydroxides (MDH) are non alogeneted flame retardant additives .

Resistance to Burning .

Resistance to Burning .

Retarding Combustion Process .

Char Formation .

Decomposing Material .

moisture and mechanical tension .Durability • How long polymer will last in service condition? • Durability usually is determined by the combined effect of environments and chemicals • To predict the service lifetime usually accelerated aging test is conducted in a simulated service condition such as heat. chemicals.

Flow/Melt Properties • • • • To process the polymer. polymer needs to be melted Viscosity of molten polymer is an important parameter for processing Polymer is highly non Newtonian fluid and polymer rheology is very complex Thermal history and memory effect also very important for process engineers and to determine how the polymer will respond to processing condition .

Material Selection-Design Requirements • Structural/load constraints – – – – Load Frequency Worst case scenarios During manufacturing/shipping/use • Environmental constraints – – – – Temperature Humidity Chemical Radiation .

Material Selection-Design Requirements • Regulation/standards constraints – – – – • Trade groups Governmental Need to identify all Range from materials to design Marketing constraints – Costs – Esthetic – Use models • Durability .

Additives • The reason to add additives. reinforcements. and fillers – – – – – – – – – To improve process ability To reduce costs To reduce shrinkage To improve surface finish To change thermal & electrical properties To prevent degradation To provide desirable color To improve mechanical properties To lower the coefficient of friction .

Additives • Increase properties of plastics – – – – – – – – Strength Glass fibers Graphite fibers Kevlar fibers Wood fibers Impact strength Particles Talc .

Additives • Increase properties of plastics – Flame retardants – Stability (UV and chemical) – Mold release • Antioxidants – Oxidation of plastics – breaking of bonds in polymers – Effects on plastics: chain scission – How to overcome: Add antioxidants • Primary antioxidant: stop oxidative reactions • Secondary antioxidant: neutralize reactive materials • Examples: – Plastics: PP &PE – Primary: Phenolic. Thioesters . Amine – Secondary: Phosphite.

Plastisizers • Increase flexibility • Reduce melt temperature • Lower viscosity – – – – Water Mild solvents Commercial Dioctyl phthalate .

– 2-hydrocybenzophenone .UV stabalizers (Carbon black) • UV can C-C backbone and many side groups • Brittle • Weaken • Other additives.

Flame retardant • • • • Ammonium phosphate Chlorinated hydrocarbons Chemicals of bromine.antimony Effects: – Emit fire-extinguishing gas (CO2 +N2) – Form an insulation barrier against heat and flame. . chlorine.

releasing gases – Chemical: -release gases due to a chemical reaction • Uses: – Polyurethane pads – seats for cars.Foaming Agents • Foaming agents – Physical: -decompose at specific temperatures.trucks – sofas .

3. No-sticking to the mold. 2. • Examples: – Waxes – Metallic soaps .Internal Lubricants • Lubricants 1. Prevent products from adhering to each other. Lower external and internal friction.

Antistatic Agents • Attract moisture from the air making the • surface more conductive and then dissipating static charges • Examples: – Amines Quaternary ammonium compounds – Organic phosphates Polyethylene glycol – esters .