Polymer Synthesis

The Macromolecular Nanomaterials laboratories include a wide range of polymer synthesis capabilities, with extensive fume hoods (including walk-in hoods for large scale apparatus) and glove boxes for handling sensitive materials.

Polymerization Techniques

  • Ionic Polymerizations: World-class expertise in the preparation of well-defined, narrow molecular distribution polymers and copolymers including complex polymer architectures (i.e. block, star, comb, graft and hyperbranched polymers) by anionic and cationic polymerizations.
  • Controlled Radical Polymerization: Extensive expertise in free radical and controlled radical (ATRP, NMP, RAFT) polymerizations.
  • Ring Opening Polymerization: Expertise in the controlled ring-opening polymerization of lactones and lactides and N-carboxyanhydrides (NCA) for the synthesis of bio-inspired materials.
  • Metal-catalyzed Cross-Coupling: Growing expertise in the synthesis of conjugated polymers by GRIM, Suzuki, and other polymerization mechanisms.
  • Deuterated Polymers: Selective deuteration of polymers, enabled by our expertise in deuteration of small molecules, for the study of polymer morphololgy, dynamics and structure with neutron techniques.

Small Molecule Synthesis

  • Synthesis of novel monomers and small molecule building blocks: Expertise in small molecule organic synthesis and characterization.
  • Deuterated Monomers & other building blocks: Unique expertise in synthesis of deuterated monomers for neutron studies.

Macromolecular Characterization

The synthetic capabilities are complemented by extensive analytical resources for rigorous characterization of materials produced by CNMS staff and our user community. Additional capabilities applicable to polymeric materials (scanning probes, electron microscopy, Raman spectroscopy, etc.) are available in other groups within the CNMS or as shared resources at ORNL.

Molecular Weight Characterization

  • Size Exclusion Chromatography (SEC)
    Multiple SEC systems are available for molecular weight characterization in a variety of media (organic, aqueous) and temperatures. All systems are equipped with multidetector systems that include light scattering for absolute molecular weight determination.
  • Temperature Gradient Interaction Chromatography (TGIC)
    Unique chromatography technique for high resolution separation of polymers based on degree of polymerization rather than size. TGIC is particularly useful for the characterization of polymers with complex architectures.
  • Vapor Phase & Membrane Osmometry
    For measurement of absolute molecular weights from 100 to 1,000,000 g/mol.
  • Matrix Assisted Laser Desorption Ionization Time-of-Flight Mass Spectrometer (MALDI-TOF MS)
    The Bruker Autoflex II is used for the determination of molecular weight of polymers and copolymers, end-group and compositional analysis, and protein identification and sequencing.

Solution Properties

  • Multi-angle Laser Light Scattering (18 angles) (MALLS)
    Wyatt Heleos with Quasi-Elastic Light Scattering is capable of measuring molecular weight, hydrodynamic radii, and conformation of macromolecules in solution.
  • Simultaneous Static and Dynamic Light Scattering
    ALV Goniometer system based on a rotary disk allowing for precise angular steps. Four detection angles separated by 34° in angular space and temperature can be controlled from -10 to 140°C for simultaneous measurements of static and dynamic light scattering. Instrument contains prisms for depolarized detecting to obtain rotational diffusion coefficient.
  • Absolute and differential refractive index detector
    Wyatt Technology Optilab Rex capable of measuring absolute refractive index and refractive index increment (dn/dc) of solutions at various temperatures and wavelengths.

Mechanical and Thermal Properties

  • Rheology
    TA Instruments ARES AR-G2 is capable of characterization of both the structure and flow properties of simple and structured fluids over a temperature range of -160 – 600°C. Cone and plate, parallel plates, and concentric cylinder geometries are available.
  • Dynamic Mechanical Analysis
    TA Instruments 800 DMA with various operating modes and test probes available with temperature range from -160 – 600°C. Three point bending, fiber, film, and cantilever geometries are available.
  • Thermogravimetric Analysis
    TA Instruments Q5000IR capable of measuring weight loss (0.1 mg sensitivity) at heating rates up to 1200°C under a variety of purge gases.
  • Differential Scanning Calorimeter
    TA Instruments Q1000 with temperature range from -180 to 550°C.

Spectroscopic Techniques

  • Nuclear Magnetic Resonance Spectroscopy (NMR)
    500 MHz multinuclear solution NMR Spectroscopy.
  • GC-MS
    Hewlett-Packard 7890 GC with a 5975 mass spectrometer with EI and CI ionization capabilities.
  • UV-Visible-NIR
    Varian Cary 5000 absorption spectrometer with liquid/solid sample holder, polarizers, diffuse reflectance, and specular reflectance accessory to probe the optical properties of solid, liquids, and solutions.
  • Fourier Transform Infrared Spectrometer (FTIR)
    Mid and far IR vacuum spectrometer with a variety of sample configurations including transmission, diffuse reflectance, ATR, as well as an IR microscope. Instrument has capabilities for vibrational circular and IR reflectance absorbance spectroscopy.
  • In Situ Fourier Transform Infrared Spectrometer (In-situ IR)
    Bruker IRCube with various probes for in-situ monitoring of chemical reactions in progress. Temperature range from cryogenic to 250°C, spectral range 7500-750 cm-1.

Thin Film Characterization

  • Spectroscopic Ellipsometer
    JA Woollam M-2000U for analysis of the thickness and refractive index of multi-layered structures.
  • Phase Modulated Ellipsometer
    Beaglhole Instruments Picometer Ellipsometer uses a photoelastic birefringence modulator to analyze the ellipticity of the reflected beam with a 1 ms response time and a detection limit of 1x 10 m. The Picometer Ellipsometer operates at a fixed wavelength of 632 nm.
  • Contact Angle Goniometer
    The KRÜSS DSA 30 contact angle goniometer is equipped with a CCD camera and automated liquid handling controls allowing for precise measurements.
  • Optical Microscope
    The Leica DM4500P is an intelligent function research polarized microscope with one-button access to bright field transmission or reflected (incident), dark field transmission, as well as polarized (transmission or reflected) microscopy and auto tracking of calibration for spatial quantitation. Samples are examined on slides as well as a thermal stage.
  • Quartz Crystal Microbalance
    QCM with dissipation can be used to determine film thickness in a liquid environment (such as the thickness of an adsorbed protein layer) or the amount of material attached to a substrate (e.g., gold or silicon) and can be used to further investigate properties of the sample such as the viscoelasticity of the layer.

Soft Matter Transmission Electron Microscopy (TEM)

A Zeiss LIBRA 120 TEM capable of operating between 60 keV and 120 keV is available for soft matter imaging (e.g., polymers and their nanocomposites). The instrument can be used to acquire electron energy loss spectra for quantitative chemical and electronic structure analysis and is suitable for generating high angular resolution nano-diffraction patterns from regions as small as a few hundred nanometers.


Capabilities provided by other CNMS groups