Slide-Set-3-Chain-Structure-L8

Slide-Set-3-Chain-Structure-L8 - Chain Structure and...

Info iconThis preview shows page 1. Sign up to view the full content.

View Full Document Right Arrow Icon
This is the end of the preview. Sign up to access the rest of the document.

Unformatted text preview: Chain Structure and Configuration: Configuration: Lecture Slide Set #3 Lecture 8 Dr. Anthony Brennan University of Florida Tel: 352.392.6281 Email: abrennan@mse.ufl.edu EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 1 Slide Set #3 – Chain Structure and Slide Configuration Configuration • Learning Objectives: – Understand correlation between chemistry, Understand structure and energy structure • • • • Bond structure Bond rotation PE Distinguish Conformation and Configuration Balance of three energies – Method Specific Properties • Chemical – XPS, FTIR, WAXD, EDAX, Contact Angle, Chemical Radionucleotide, Derivatization Radionucleotide, • Physical – AFM, SEM, TEM, Ellipsometry, DTMA EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 2 Polymer Structure -Property Behavior Polymer Chain Dimensions • Conformation (model) – – spatial arrangement changes with rotation around bonds • configuration – bonding arrangement – changes only through bond breakage • aspect ratio (L/D) for PE (100kg/mol) – 60,000 EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 3 Isomerism Isomerism H H3C CH3 H H H3C H H3C H H H H H H CH3 H CH2 H3C H H H H H H CH3 H CH2 H3C H2C CH3 CH2 CH3 EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 4 Chain architecture "Branched" or "graft" Blend A A B Block or triblock Network or Crosslinked EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 5 Balance of Three Energies Balance • Intramolecular – – – PE vs Nylon 6 Nylon 6 vs Kevlar Kevlar vs Nomex • Intermolecular – Nylon vs PE • Thermal – kT per repeat unit • Bond rotation – Nylon 6 : 10 to 20 Nylon kcal/mol (Tm: 220°C) kcal/mol – Kevlar: >20 kcal/mol • Secondary Bonding – H-Bonds, Dipole, Ionic, H-Bonds, van der Waals van – 2 to 11 kcal/mol • Low energy – ~0.6 kcal/mol EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 6 Importance of Chemistry Importance P o ly e th y le n e H o m o p o ly m e r L in e a r H ig h D e n s ity C o p o ly m e r Low D e n s ity L in e a r L o w D e n s ity Low D e n s ity 7 EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 CH3 CH3 CH3 CH3 CH3 CH3 Si Si Si Si Si Si O H3C H3C O H3C O H3C O H3C O H3C O n Tg = -123C, Tm = -60C H H H H H C H H n C C H H H C C H H H C C H H C C H H C H H C H H C H H H Tg = -120C; Tm = 140C EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 8 CH3 CH3 CH3 CH3 CH3 CH3 Si Si Si Si Si Si O H3C H3C O H3C O H3C O H3C O H3C O n Tg = -123C, Tm = -60C H H H H H C H H n C C H H H C C H H H C C H H C C H H C H H C H H C H H H Tg = -120C; Tm = 140C EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 9 H H H H H C H H H H n C C H H C C H H C C H H C C H H C H H C H C H H H H Tg = -120C; Tm = 140C H H N H H H H H C C C C C C H H H H H H H H N C O H H H C C C C H H H H Tg = 55C; Tm = 265C Tg EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA O C n 10 H H N H H H H H C C C C C C H H H H H H H H N C O H H H C C C C H H H H O C Tg = 55C; Tm = 265C n H H N N O C C O n Tg > Td EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 11 EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 12 Importance of Chemistry Importance B io p o ly m e r s P o ly s a c c h a r id e s P r o te in s G e n e tic C o d in g S tru c tu ra l e g . C o lla g e n S tru c tu ra l e g . C e llu lo s e , C o tto n C a ta ly s is eg. enzym es P o ly n u c le o tid e s eg. D N A, R N A 13 EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 Importance of Chemistry Importance Protein Tertiary Structure Conformational Structure HEAT HEAT COOL COOL HEAT COOL EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 14 Chain Dimensions Chain Rotational Isomers Rotational Ref: Chem Draw Pro – ethane_conformers Ref: • Staggered conformation – Erot~ 0 kJ/mol, Φ = kJ/mol, 60, 180, 300 deg. 60, • Eclipsed - Erot~ 12 kJ/mol, Φ = 0/360, 120, 240 Eclipsed 12 deg. deg. • Staggered 0 kJ/mol < Erot < 0 kJ/mol, Staggered kJ/mol EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 15 Chain Dimensions Chain Ethanes Rotational Isomer Energies States Ethanes EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 16 Chain Dimensions Chain n-Butane Conformational States n-Butane Ref: Chem Draw Pro file – butane conformers EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 17 Chain Dimensions Chain Local Steric Repulsion Local EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 18 Summary • Chain Chemistry defines structure. • Chain bond rotational potential Chain energies dictate properties energies • Balance of three energies defined by Balance structure/processing structure/processing • Characteristic dimensions defined by Characteristic structure and environment structure EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 19 References • Introduction to Physical Polymer Science, 4th Edition, Lesley H. Sperling, Wiley Interscience (2006) ISBN 13 978-0-471-70606-9 ISBN • Principles of Polymer Chemistry, P.J. Flory (1953) Principles Cornell University Press, Inc., New York. Cornell • The Physics of Polymers, Gert Strobl (1996) The Springer-Verlag, New York. Springer-Verlag, • Figures were reproduced from Polymer Physics, Figures (1996) Ulf Gedde, Chapman & Hall, New York. (1996) EMA 4161C Phys Prop Poly - University of Florida Copyright 2009 EMA 20 ...
View Full Document

Ask a homework question - tutors are online