IIT Jodhpur Structure & Property for Polymers 2024-2025 PDF

Department of Chemical Engineering @ IIT Jodhpur AY2024-25: SemI Structure & Property for Polymers CHL7490 (3-0-0) Deepak Arora  SPP (CHL7490) – First Class Handout...

Department of Chemical Engineering @ IIT Jodhpur AY2024-25: SemI Structure & Property for Polymers CHL7490 (3-0-0) Deepak Arora  SPP (CHL7490) – First Class Handout The course and timings- Course CHL7490 and Structure & Property for Polymers Number and Title Lectures Days Slot J/ Tues, Thurs, Fri Time 4 – 4:50 PM Venue PH104 Tutorials Days none Time NA Venue NA Laboratory Days none Time NA Venue NA 2  SPP (CHL7490) – First Class Handout Instructor(s)- Name Email Departm Contact Office Address ent Number Course Coordinator Deepak deepakarora Chemical 02192801705 334, Dept of Chemical Arora @iitj.ac.in Engineer Engineering, Anantharaman ing Building Co-Instructor Tutors Office Timings during the week: 9:30 AM – 6 PM (Preferred time to meet 12 Noon – 1 PM) 3  SPP (CHL7490) – First Class Handout Contact details of Teaching Assistants (TAs): Please contact the TAs for any query related to the course or attendance. Name of the TA Contact details None 4  SPP Course Details Title Structure & Property for Polymers Number CHL7490 Departme Chemical Engineering L-T-P [C] 3-0-0 nt Offered BTech, MTech, PhD Type PE for Prerequisit An introductory course on polymers for e BTech, None for MTech Objectives To Learn various structures in polymers and its relation with the mechanical and thermal properties Learning Outcomes The students are expected to gain: 1. Understanding of structure-property for various polymeric systems 2. Understanding of thermal transition in polymers 3. Understanding of viscoelasticity and mechanical models 5  SPP Course Details: AY2024-25 - SemI Contents Introduction: Outline of the course, review of basics of polymers, polymerization reactions and classification [2 lectures] Amorphous and Semicrystalline Polymers: Glass transition, free-volume theory, factors affecting glass transition temperature, solution grown single crystals and chain-folding mechanism, melt crystallization, spherulites, degree of crystallinity, Bragg’s law, crystal thickness and chain extension, flow-induced crystallization, dimensionless numbers in crystallization, factors affecting melting, relationship between melting and glass transition [11 lectures] Multicomponent Polymeric Systems: Polymer blends, block copolymers, thermoplastic elastomers, examples, phase diagram, glass transition, compatibilization, morphology diagram [6 lectures] Deformation in Polymers: Elastic deformation, stress-strain relationship, polymer chain deformation, crystal moduli, elastic deformation in semicrystalline polymers, yield and crazing – necking and it’s mathematical treatment, yield criteria, mechanisms, plastic deformation [9 lectures] Viscoelasticity: Introduction, examples, Mechanical models, Boltzmann superposition principle, dynamic mechanical testing, transitions and polymer structure, t-T superposition, entanglements [9 lectures] Polymer Composites: Matrix and fillers, composition, elastic deformation, fracture, packing, experiments, nanocomposites [5 lectures] 6  Resources Textbook – 2011, Introduction to Polymers, 3rd Edition, Robert J Young and Peter A Lovell Reference Books 1. Chanda M. (2006) Introduction to Polymer Science & Chemistry, CRC Press Online Course Material 1. Adhikari B, Science & Technology of Polymers, NPTEL Course Material, Department of Metallurgy & Material Science, Indian Institute of Technology Kharagpur, https://nptel.ac.in/courses/113105028/ 7  Evaluation policy for the course No.IITJ/OAA/Circular/2024-25/52/683, Jul 8, 2024 Components Weightage (%) Date and Timings Remarks Assignments 10 – 20 % After first 5-10 1-2 take home sessions assignments Quizzes 20- 30 % After first 5-10 20 – 45 mis, 1-6 sessions written quizzes Minor 20 – 30 % Mid of the 2 hrs, Written semester Examination (Academic calendar) Major 40 – 60 % after all the 3 hrs, Closed Book, lectures (Academic Written Calendar) examination, Scientific calculators are permitted Projects …… …... 8 Note: Assignments + Quizzes + Minor will have a contribution of a maximum of 60 %. Guidelines for Examination: Attendance Policy: As per institute policy No. IITJ/OAA/ Circular/ 2024-25/51/682 , Jul 8, 2024 Any other relevant information: 9  Teaching Methodology & Evaluation Evaluation (offline + online) % (Academic Regulations 4.2) Lecture break-up Continuous evaluation + Minor (60 - 40 %): Recap – Assignments Content Class notes Summary & address Surprise quizzes questions Quizzes Flipped classroom Discussion board Case studies Paper reviews Projects – Classroom participation – In class problem solving – Guest lectures – In class demos (Lab 206 for more !) 10 Major examination (40 – 60 %)  Communication Board! Class schedule and location – start date Aug 13th , 2024 Slot J - Tues, Thurs, Fri : 4 – 4:50 PM; location PH104 Evaluation (offline + online) % Introduction of TAs – In Google Classroom (Academic Regulations 4.2) Student count/ background – 8/ CH, PH Continuous evaluation + Minor (60 - 40 %): Extra class/ buffer days – Assignments Last day of classes/ attendance submission – Nov 18th , 2024 Class notes / Monday Surprise quizzes Quizzes Examination dates and modalities Flipped classroom – Minor – Sep 19th-21st, 2024 Discussion board – Major: Nov 20th -26th, 2024 Case studies Paper reviews Attendance Projects Make class notes – Classroom participation – In class problem solving Last day for add/ drop – Aug 9th, 2024 – Guest lectures Institute day-off : Aug 15th,Aug 19th, 2024 – In class demos (Lab 206 for Substitution days more !) Major examination (40 – 60 %) Recognize Class performance – performers ! Feedback Continuous evaluation 11  Introduction Polymer → Poly stands for many. Polymers are the macromolecules made up of monomers. Polymers in nature: Polymers in nature: DNA Wood - Cellulose RNA Pectin Proteins Silk Polysaccharides Cotton Shellac Natural Rubber (polyisoprene) - trees Terpene resin Skin Bone ? History: 1820 - Thomas Hancock – Observed that natural rubber (polyisoprene) becomes more fluid when subjected to the repeated high shear forces. This process is called mastication. Blending of other additives in rubber becomes easier due to mastication process. Mastication process also eases the moulding process for rubber and rubber-based polymer composites. Why is it that the rubber becomes more fluid upon mastication? Process → Structure → Property for Polymers 1839 – Charles Goodyear – Found that the elastic properties of natural rubber can be improved and it’s tackiness can be eliminated by heating the natural rubber with sulfur. → Vulcanization , until this finding, usage of polyisoprene was limited to low temp applications. What’s the cause for reduced tackiness of rubber after vulcanization with sulfur? 12  Communication Board! Class schedule and location – start date Aug 13th , 2024 Slot J - Tues, Thurs, Fri : 4 – 4:50 PM; location Evaluation (offline + online) % (Academic Regulations 4.2) PH104 Continuous evaluation + Minor (60 - 40 Introduction of TAs – In Google Classroom %): – Assignments Student count/ background – 9/ CH, PH Class notes Extra class/ buffer days – Tues 3 : 3:50 PM ? Surprise quizzes Last day of classes/ attendance submission – Quizzes Nov 18th , 2024 / Monday Flipped classroom Discussion board Examination dates and modalities Case studies – Minor – Sep 19th-21st, 2024 Paper reviews – Major: Nov 20th -26th, 2024 Projects – Classroom participation Attendance - correlation – In class problem solving Make class notes – Guest lectures Institute day-off : Aug 15th,Aug 19th, 2024 – In class demos (Lab 206 for more !) Substitution days – Sep 4th, 2024 (Wed) → Major examination (40 – 60 %) Friday’s timetable Recognize Class performance – performers ! Feedback Continuous evaluation 13  History 1846 – Christian Schonbem – synthesized Gun Cotton (cellulose nitrate/ nitro cellulose). It’s an explosive. It’s a hard elastic material and is soluble. It is moldable by application of heat and pressure. 1850s – sap from gutta percha tree –> trans-isomer of polyisoprene 1851 – Nelson Goodyear – came up with hard rubber (ebonite or vulcanite) via increased amount of sulfur Why does increased amount of sulfur lead to increased hardness of rubber? 1869 – Celluloid was patented, John Wesley Hyatt, an American inventor 1892 – Charles Cross, Edward Beven and Clayton Beadle discovered Cellophane film. “Semi-synthetic polymers” 14  History Cis-isomer of polyisoprene is amorphous → sensitive to temperature changes Trans-isomer → Gutta percha → crystallizable → useful solid properties above room temperature Both have same Tg → below room temp Gutta percha → insulating material for underwater telegraph wires Both Cis and trans polyisoprene are non-polar Cis polyisoprene even in crosslinked form → poor chemical resistance to salt water as compared to gutta percha → improved chemical resistance due to crystallinity Gutta percha -- > coating on wires as electrical insulator (Invention of extruder !) 1910 – production of first fully synthetic polymer, Bakelite, started. Bakelite → Phenol formaldehyde resins – Leo Baekeland. Until 1920’s, it was believed that polymers consist of physical aggregates of small molecules (monomers). Example: physical aggregate of small 15 molecules 16  History 1910 – production of first fully synthetic polymer, Bakelite, started. Bakelite → Phenol formaldehyde resins – Leo Baekeland. Until 1920’s, it was believed that polymers consist of physical aggregates of small molecules (monomers). History: Macromolecule – term was coined by Hermann Staudinger to describe polymers. Polymers consist of macromolecules that are made up of monomers which are small molecules. Small molecules → Macromolecules → Polymers He demonstrated that macromolecules are large molecules with sequence of small molecules connected together via covalent bonds. Staudinger synthesized polyoxymethylene (PoM) and polystyrene (PS) to demonstrate the macromolecule aspect of polymers. Wallace Carothers – polyamides and polyesters – Father of condensation polymers 1953 – Hermann Staudinger was awarded Nobel Prize. 1974 – Paul Flory was awarded with the Nobel Prize for Chemistry for his contributions to Polymer Science. 17 18  Synthetic Polymers A few of the popular synthetic polymers are: Polystyrene (PS) Polyethylene (PE) Nylon 6,6 Polyvinylchloride (PVC) Styrene-butadiene rubber (SBR) Silicones Teflon (PTFE – polytetrafluoroethylene) Hip replacement device – Polymethylmethacrylate (PMMA) stainless steel and Polyurethane UHMPE (Ack: Wiki) Latest trends in design and development of polymers: Biomedical Electronics Space and defense Green polymers Ack: polymerinnovationblog.com 19  iPhone SE 2016 Fig 1:iPhone SE Fig 2:Overall Size & Weight of iPhone SE Fig 3: iPhone SE used in Lab for dismantle Source : https://gadgets.ndtv.com/apple-iphone-se-3393  Disassembly of iPhone SE Camera module Sensor housing (light and proximity sensors) Logic board or main board Graphite sheet for cooling Metallic heat shield for the screen Speaker Home button with fingerprint sensor Fig 4: Dismantle of iPhone SE Source : https://www.anandtech.com/show/9686/the-apple-iphone-6s-and-iphone-6s-plus-review/3  A9 Processor Fig 20 : A9 Processor of iPhone SE Source: https://www.fdocuments.in_apple-a9-series-application-processor Front Side A9 Processor 4 Fig 12: PCB – 5 3 1 2 Front side A9 Processor: heating at 320 °C to detach the overmold 1. Manufacturers: TSMC or Samsung 2. Type of Processor: 64-bit ARM 3 based, system-in-package 3. Minimum feature size: 16 nm (TSMC) or 14 nm (Samsung) 3 4. Transistor type: FinFET (lower power consumption than MOSFETs) Fig 15: Dismantle of A9 Processor (a) Over mold top down (b) Die package on PCB (a) (b) I/O’s  A9 Processor – Feature Size Apple A9 Apple A9 APL0898/339S00114 APL1022/339S00129 SAMSUNG 14 nm FinFET TSMC 16 nm FinFET process process Size: 104. 5 mm2 Size: 96 mm2 Fig 22: A9 Processor – Feature Size Source: Smith R. & Ho J., The Apple iPhone 6s and iPhone 6s Plus Review, AnandTech, Nov. 2, 2015, http://www.anandtech.com/show/9686/the-apple-iphone-6s-and-iphone-6s-plus-review.  PCB- Cross-section image iPhone SE (2016) PCB Fig 14: PCB – Cross-sectional Image Source: https://www.researchgate.net/publication/320906509_Positioning_Techniques_with_Smartphone_Technology_Performances_a nd_Methodologies_in_Outdoor_and_Indoor_Scenarios Microsystems Integration, Aug. 28-Sept. 2 2014,  Application of Polymers IT HAPPENED! Elon Musk Went Public With Tesla Home – Boxabl Uses no wood, rather EPS - expanded PS for walls etc http://www.youtube.com/watch?v=5iXUnAGvRjc https://www.motortrend.com/cars/t esla/cybertruck/ https://www.boxabl.com/how-to-get-elon- 26 musks-50k-boxabl-home-for-yourself/  Basic Terminologies & Definitions Polymer Macromolecules Monomer - ethylene / Macromer Monomer Polymerization Polymerization Repeat unit Macromolecules - Polyethylene Polymer - Polyethylene It is the long chain nature of the polymers that gives rise to their unique properties as compared to the monomers (small molecules). 27  Classification of Polymers Criteria for classification Origin Skeletal structure Repeat unit/ structural unit Thermal processing behavior Molecular arrangement 28  Skeletal Structure Skeletal structure Linear polymers (Polyethyleneterephthlate / PET) Non-linear polymers Cyclic/ ring polymers (cyclic silicones, condensation of diamines and dicarboxylic acids to cyclic polyamides) Branched polymers Chain ends (branched polyethylene) Network polymers (epoxys) 29  Branched Polymers Branch / junction points branches Low high branching branching Examples: branched PE, branched PP Branch Vs side group ? 30 Branched Polymers Within branched polymers: Dendrimers Hyperbranched polymers These are branched polymers with controlled/ defined branching. Branching can be used to tune level of voids and channels within the molecules. Branching also offers a way to vary the end groups that can be functionalized for applications such as targeted drug delivery. 31  Network Polymers Crosslinks Crosslink density or degree of crosslinking (number of crosslink points per unit volume) Closed loops Junction/ network/ crosslink points Examples: epoxy resins, Urea-formaldehyde polymers, melamine formaldehyde resins , unsaturated polyester resins 32  Branched and Network Polymers Branched and network polymers are formed by : Polymerization of monomers (Ex- epoxy) Linking of macromolecules (Ex- vulcanization of rubber) Polymerization of monomers (Ex- epoxy) Closed loop Ack: www.pslc.ws/macrog/kidsmac/epoxy.htm 33  Branched and Network Polymers Branched and network polymers are formed by : Polymerization of monomers (Ex- epoxy) Linking of macromolecules (Ex- vulcanization of rubber) Isoprene (monomer) Polyisoprene (polymer, various isomer) Ack: Wiki 34