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b) MW Averages c) Polydispersity Index d) Molecular Weight Determination Methods in Section 2 2) Chemical Composition a) Repeating Units b) Side Chains c) Crosslinking Groups d) End Groups e) Additives i) ii) iii) identity concentration localization
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The graphics in these notes indicated by Figure/Table/Equation/Etc., x.x in Stevens are taken from our lecture text: Polymer Chemistry: An Introduction - 3rd Edition Malcolm P. Stevens (Oxford University Press, New York,
Chemistry 5861 - Polymer Chemistry ii) iii) iv) some type of alternation blocks grafts
c) Linear or Branched i) ii) iii) branching topology amount of branching branch lengths
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Chemical Methods of Analysis A) Examples 1) Mostly of historical interest now 2) Head/Tail Structure of Vinyl Polymers a) Poly(vinyl alcohol) b) Oxidation by HIO4 or Pb(OAc)4 c) Head-Head links have 1,2-diols d) These are cleaved by these strong oxidizing agents (eventually to terminal carboxylic acids) e) reduced average MW f) reduced viscosity
1999).
Chemistry 5861 - Polymer Chemistry g) This experiment run in our Physical Chemistry Lab 3) Double Bond Location in Polydienes a) Ozonolysis i) ii) 1st O3, 2nd H2O cleaves olefin links to aldehyde and/or ketone groups
b) Polyisoprene i) ii) H(O)C-CH2-CH2-C(CH3)O as organic product was how polyisoprene structure determined
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B) Infrared Spectroscopy 1) Need change in dipole moment a) i.e., asymmetric vibration modes 2) FT-IR Databases 3) Analysis by comparison to Model
Chemistry 5861 - Polymer Chemistry 4) Spectral subtraction to observe minor species a) Figure 5.2 in Stevens b) e.g., spectrum of crystalline regions 5) Polymer Blends a) To look for new interactions b) From Polyblend spectrum
subtract that for the two homopolymers c) the difference spectrum is that for any new chemical or physical interactions
C) Raman Spectroscopy 1) Need change in polarizability a) i.e., symmetric vibration modes b) especially sensitive to vibrations with little or no change of dipole moments i) e.g., C-C vibrations cis-trans isomerism sulfur crosslinks in rubber 2) Problems/Limitations: a) Instruments relatively expensive b) Raman method harder to apply to colored materials
D) NMR Spectroscopy 1) Backbone & Side chain Structure 2) Tacticity Analysis in Solution a) Isotactic PMMA i) Figure 5.3 in Stevens
Chemistry 5861 - Polymer Chemistry ii) iii) Figure 5.5 in Stevens Cross Polarization transfer of polarization from 1H faster 13C relaxation iv) Magic Angle Spinning Magic Angle - 54.7 thousands of tens of thousands of Hz spin rate
E) Electron Spin Resonance, ESR, Spectroscopy 1) Requires Free Radical in Sample 2) Excellent for mechanistic studies a) synthesis b) degradation 3) Figure 5.6 in Stevens a) usually plotted in derivative mode
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X-ray, Electron, and Neutron Scattering A) Principles of Diffraction 1) Figure 5.7 in Stevens 2) WAXS a) Wide Angle X-Ray Scattering i) coherent
b) increased crystallinity sharper rings c) orientation of crystallites arcs & then spots d) single crystal studies 3) SAXS a) Small Angle X-Ray Scattering b) incoherent
B) Electron Diffraction 1) need conducting polymer (or coated polymer) 2) TEM, Transmission Electron Microscopy
C) Neutron Diffraction 1) especially sensitive to proton positions 2) require a cold neutron source!
Characterization & Analysis of Polymer Surfaces A) Surface Analysis 1) Table 5.2 in Stevens
Chemistry 5861 - Polymer Chemistry a) also called XPS i) X-ray Photoelectron Spectroscopy
b) uses soft X-rays to detach electrons from surfaces c) Binding Energy of Electron = h - Emitted electron energy d) valence electrons i) chemical information
D) Secondary-Ion Mass Spectrometry, SIMS, and Ion-Scattering Spectroscopy, ISS 1) Figure 5.12 in Stevens 2) Identification Species of Surface
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E) Atomic Force Microscopy 1) Figure 5.14 in Stevens 2) in physical contact with surface 3) surface does not need to be
conducting
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Thermal Analysis A) Differential Scanning Calorimetry, DSC, & Differential Thermal Analysis, DTA 1) DTA is older technique now generally replaced by DSC 2) Sample heated and heat flow watched a) typically in an inert atmosphere b) typically wrt. to a reference sample c) 0.5 to 10 mg samples sizes typical 3) DTA a) sample and reference heated by same source b) measure difference in temperature 4) DSC a) sample and reference heated separately b) different currents applied to keep same temperature c) differences in applied current reflect differences in thermal properties 5) Figure 5.15, 5.16, 5.17, & 5.18 in Stevens
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B) Thermomechanical Analysis, TMA, Dynamic Mechanical Analysis, DMA 1) A probe is in contact with the sample 2) Detects phase transitions by change in modulus or volume
Chemistry 5861 - Polymer Chemistry 1) Measures weight changes on heating a) depolymerization b) oxidation c) desolvation d) additive loss e) etc. 2) Figure 5.19 in Stevens 3) Often hyphenated technique a) TGA-MS i) Figure 5.20 in Stevens
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A) Evaluation 1) Predictable from chemical reasoning when wetting, pores, etc., taken into account 2) tested by immersion
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