Waters Corporation · NYSE:WAT

Waters — Postnova Analytics — Technical Presentation (September 2016)

27 slides from Waters's technical presentation, September 2016

  1. Slide 1: Comprehensive Characterization of Natural Rubber Samples using Thermal Field-Flow-Fractionation

    Comprehensive Characterization of Natural Rubber Samples using Thermal Field-Flow-Fractionation coupled with MALS and Triple Detection Dr. Gerhard Heinzmann, Postnova Analytics GmbH, Germany International Symposium on GPC/SEC and Related Techniques, Amsterdam, The Netherlands, September 26th-29th, 2

  2. Slide 2: Agenda

    • FFF Separation Platform • Thermal FFF (TF3) • TF3-MALS and TF3-Triple/Tetra/Penta Detection • Application Examples www.postnova.com . © Postnova 2016 2

  3. Slide 3: Separation and Detection Platform

    Separation and Detection Platform Size Separation Malvern Light Scattering Zetasizer Detector PN3621 MALS CF2000 Centri FFF AF2000 Flow FFF TF2000 Thermal FFF SC2000 GPC Concentration Viscometer detector PN3310 UV detector PN3211 DAD detector PN3241 RI detector PN3150 Fluori detector PN3411 Agilent

  4. Slide 4: FFF Separation Principle

    FFF Separation Principle Separation Mechanism • Separation in a narrow ribbon-like channel • Laminar flow inside the channel • External field perpendicular to the solvent flow www.postnova.com . © Postnova 2016 4

  5. Slide 5: Thermal FFF – Principle

    Thermal FFF – Principle TF2000: Separation Thermal Diffusion Coeffcient -> Depends on Applications VE ~ DTΔT/D chemical composition • Rubbers Polymers • Gels / Latexes • Cross-linked Polymers • Thermal gradient up to Δ120°C • Separation kDa up to several MDa • Analysis time, 10 – 120min (no upper li

  6. Slide 6: Thermal FFF vs. GPC/SEC

    Thermal FFF vs. GPC/SEC Advantages of Thermal FFF compared to GPC/SEC: No filtration of gel material, no clogging of No shear degradation in columns porous columns / frits No interaction Excellent separation for with stationary high MW extended phase ´Exclusion Limit´ www.postnova.com . © Postnova 2

  7. Slide 7: FFF – Triple Detection

    FFF – Triple Detection - MALS - Viscometer - Concentration Detector(s) www.postnova.com . © Postnova 2016 7

  8. Slide 8: Thermal FFF

    Thermal FFF Setup of TF2000 Thermal FFF with Triple Detection (Penta Detection) MALS / Viscometer / 3x Concentration Detector Detector Setup: UV => MALS => Visc => RI => ELSD Conditions: Solvent = THF, Flow rate = 0.3 mL/min Alternative Setup: UV => MALS => Split: Visc => Waste and RI => ELSD => Was

  9. Slide 9: Determination of Mw, Rg, IV and Structure

    Determination of Mw, Rg, IV and Structure LS signal = KLS * (dn/dc)2 * Conc * Mw RI signal = KRI * (dn/dc) * Conc UV signal = KUV * Ɛ * Conc Visco signal = KVisco * [ƞ] * Conc • MW from MALS + RI • Rg from MALS • IV from Viscometer + RI • Rh from Viscometer + RI + MALS • Mark-Houwink plot (log IV vs

  10. Slide 10: Results

    Results www.postnova.com . © Postnova 2016 10

  11. Slide 11: TFFF Applications – PS

    TFFF Applications – PS Separation of PS standards System • TF2000 FFF System • PN3150 RI Detector Conditions • Injection Volume: 20 µL • Concentration: 2 mg/mL • Temp. grad. T = 90°K to 0°K www.postnova.com . © Postnova 2016 11

  12. Slide 12: TFFF Applications – PS with Pentadetection

    TFFF Applications – PS with Pentadetection DOW PS 1683 / MW = 250 kDa, PD = 2.5 System • TF2000 FFF System • PN3621 MALS • PN3310 Viscometer • PN3211 UV • PN3150 RI • PN3510 ELSD Conditions • Injection Volume: 50 µL • Concentration: 5 mg/mL • Temp. grad. T = 90°K to 0°K www.postnova.com . © Postnov

  13. Slide 13: TFFF Applications – PS with Pentadetection

    TFFF Applications – PS with Pentadetection System DOW PS 1683 / MW = 250 kDa, PD = 2.5 • TF2000 FFF System • PN3621 MALS • PN3310 Viscometer • PN3211 UV • PN3150 RI • PN3510 ELSD Conditions • Injection Volume: 50 µL • Concentration: 5 mg/mL • Temp. grad. T = 90°K to 0°K www.postnova.com . © Postnov

  14. Slide 14: TFFF – Separation by Chemical Composition

    TFFF - Separation by Chemical Composition Separation of PS and PMMA-Standards with same Rh SEC vs. Thermal FFF (TF3) TF3 enables separation of molecules with the same hydrodynamic volume according to their chemical composition! www.postnova.com . © Postnova 2016 14

  15. Slide 15: TFFF Applications – SBR Rubber with Pentadetection

    TFFF Applications – SBR Rubber with Pentadetection MALS Viscometer RI ELSD UV www.postnova.com . © Postnova 2016 15

  16. Slide 16: Application Example: Natural Rubber

    Application Example: Natural Rubber www.postnova.com . © Postnova 2016 16

  17. Slide 17: TFFF Applications - Natural Rubber

    TFFF Applications - Natural Rubber Molar Mass Radius of Gyration • Nanoscale impurities with same size separated according to different chemical composition www.postnova.com . © Postnova 2016 17

  18. Slide 18: TFFF Applications – Natural Rubber with Pentadetection

    TFFF Applications – Natural Rubber with Pentadetection Natural Rubber Sample (Polyisoprene) System • TF2000 FFF System • PN3621 MALS • PN3310 Viscometer • PN3211 UV • PN3150 RI • PN3510 ELSD Conditions • Injection Volume: 50 µL a = 0.98 • Concentration: 5 mg/mL • Temp. grad. T = 90°K to 0°K Stiff c

  19. Slide 19: TFFF Applications – Natural Rubber with Pentadetection

    TFFF Applications – Natural Rubber with Pentadetection Natural Rubber Sample System • TF2000 FFF System • PN3621 MALS • PN3310 Viscometer • PN3211 UV • PN3150 RI a = 0.49 • PN3510 ELSD Conditions • Injection Volume: 50 µL • Concentration: 5 mg/mL • Temp. grad. T = 90°K to 0°K a = 0.98 More compact

  20. Slide 20: TFFF Applications - Natural Rubber: Raw Data Fractogram

    TFFF Applications - Natural Rubber Raw Data Fractogram of TF3 - MALS and ELSD __ LS 92° __ ELSD System 0.225 • PN5300 Auto Injector 0.21 • TF2000 Thermal FFF LS Detector Signal [V] ELSD Detector Signal [V] • ELSD • PN3621 MALS (92° SLS) 0.125 0.206 Conditions • Injection Volume: 100 µL • Concentrati

  21. Slide 21: Natural Rubber: Overlay Molar Mass and LS Signal

    TFFF Applications - Natural Rubber Overlay: Molar Mass and LS Signal • The molar mass was calculated from MALS and ELSD data • Literature value for dn/dc = 0.124 mL/g • In the 1st peak the sample contains rubber material with a molar mass of appr. 4.7 x 105 g/mol (w- average) and in the 2nd peak of

  22. Slide 22: Natural Rubber: Overlay Radius of Gyration and LS Signal

    TFFF Applications - Natural Rubber Overlay: Radius of Gyration and LS Signal • The Radius of Gyration was calculated from MALS angular data • The main/1st peak shows a Radius of Gyration of 42 nm (z-average) and the 2nd peak a Radius of Gyration of 218 nm. Radius / LS 92° Conditions 1,000 0.008 • Ra

  23. Slide 23: Natural Rubber: Molar Mass Distribution

    TFFF Applications - Natural Rubber Molar Mass Distribution Zoom in Molar Mass Distribution Molar Mass Molar Mass 0.1 1.0 1.0 1.0 0.09 0.08 0.07 0.06 Differential Cumulative Cumulative 0.05 0.04 0.03 0.02 0.01 0.0 0.0 0.0 0.0 1e+4 1e+5 1e+6 1e+7 1e+8 1e+9 1e+10 1e+4 1e+5 1e+6 1e+7 1e+8 1e+9 1e+10 Mol

  24. Slide 24: TFFF Applications - Natural Rubber: Fractal Dimension

    TFFF Applications - Natural Rubber Fractal Dimension 1.0E+01 System 9.0E+00 • PN5300 Auto Injector • AF2000 FFF System 8.0E+00 • PN3621 MALS Detector • PN3150 RI Detector log M 7.0E+00 • PN3510 ELSD 6.0E+00 Conditions 5.0E+00 • Injection Volume: 20 µL 4.0E+00 • Concentration: 2 mg/mL 2 log r www.pos

  25. Slide 25: TFFF Applications - Natural Rubber: Fractal Dimension

    TFFF Applications - Natural Rubber Fractal Dimension 17.5 - 44.6 min Fractal Dimension 51.6 – 54.8 min Fractal Dimension=1.78 Fractal Dimension=2.92 7.0E+00 1.0E+01 6.0E+00 9.0E+00 log M log M 5.0E+00 8.0E+00 1.2 1.25 1.3 1.35 1.4 1.45 1.5 1.55 1.6 1.65 1.7 1.75 1.8 1.95 2 2.05 2.1 2.15 2.2 2.25 2.3

  26. Slide 26: Summary

    Summary Thermal FFF is a Powerful Method for Polymer and Biopolymer Characterization • Increased resolution for high molar mass species • Huge flexibility in choice of fractionation power (gradient) • No interaction with stationary phase / no artifacts • No degradation due to shear stress during the

  27. Slide 27: Thank you for your Attention

    Thank you for your Attention www.postnova.com . © Postnova 2016 27

Postnova Analytics — Technical Presentation (September 2016) on 6ix