Macromolecular Nanomaterials

Macromolecular Nanomaterials

The Macromolecular Nanomaterials laboratories include a wide range of polymer synthesis capabilities with special emphasis on selective deuteration and ionic polymerization. 

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. (David Uhrig, Kunlun Hong)
  • Controlled Radical Polymerization: Extensive expertise in free radical and controlled radical (ATRP, NMP, RAFT) polymerizations. (Brad Lokitz, Kunlun Hong)
  • Ring Opening Polymerization: Expertise in the controlled ring-opening polymerization for the synthesis of well-defined polymeric materials. (Kunlun Hong)
  • Metal-catalyzed Cross-Coupling: Growing expertise in the synthesis of conjugated polymers by KCTP, Suzuki coupling, and other polymerization mechanisms. (Peter Bonnesen, Kunlun Hong)
  • 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. (Peter Bonnesen, Kunlun Hong)

Small Molecule Synthesis

  • Synthesis of novel monomers and small molecule building blocks: Expertise in small organic molecule synthesis and characterization. (Peter BonnesenKunlun Hong)
  • Deuterated monomers, polymers, and specialty molecules: Unique expertise in synthesis of deuterated monomers and building blocks for neutron studies. (Peter BonnesenKunlun Hong)

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.

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 (DLS)
    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 Discovery Hybrid Rheometer (HR2) is capable of characterization of rheological properties of simple and complex fluids, gels, and elastomers over a wide temperature range of -160 - 600°C. Cone and plate, parallel plates (with solvent trap option), concentric cylindrical geometries, as well as the SER3 universal testing platform for extensional rheology are available.
    -Ubbelohde capillary viscometers of various sizes, capable of accurate measurement of low viscosity liquids from 0 - 150°C.
  • Dynamic Mechanical Analysis (DMA)
    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 (TGA)
    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 (DSC)
    -TA Instruments Q2000 with temperature range from -180 to 550°C.
    -Nano DSC capable of characterization of the thermal stability and heat capacity of proteins and other macromolecules in dilute solutions. 

Spectroscopic Techniques

  • Matrix Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF-MS)
    Bruker MALDI-TOF Autoflex LRF instrument with imaging capabilities (5 micron spatial resolution) and capabilities for collisionally induced dissociation (CID) of any species. This system is equipped with the latest FlashDetector technology, enabling the instrument outstanding resolution (R > 26,000) and mass accuracy (≤  2 ppm) in reflection mode for addressing the complexity of co-polymer samples. With its real on-axis detector design (in linear mode), the system is capable of detecting extremely large molecules > 500 kDa.
  • Novocontrol broadband dielectric/impedance spectrometer
    Turnkey broadband dielectric spectrometer with temperature control and data acquisition system. Broad frequency range and high measurement accuracy based on high-resolution ALPHA-A analyzer. Frequency range: 3×10-5 – 4×107 Hz; Capacity: 10-15 – 1 F; Impedance: 0.01 – 1014 W; Loss factor accuracy < 3×10-5, resolution 10-5. QUATRO Cryosystem: -160°C to 400°C, with temperature stability 0.01°C. A few different sample cells are available, including plate electrodes of different sizes, liquid sample cells, and devices for ultrathin film measurements. The Alpha-A Modular Measurement System from Novocontrol for dielectric, conductivity and electrochemical impedance spectroscopy is developed especially for materials research. A wide range of topics can be addressed by the dielectric technique, including molecular dynamics in confining space, collective dynamics of liquid crystals, molecular dynamics in thin polymer films, and dielectric properties of semiconducting materials.
  • ​Rheo-dielectric capability
    TA Instruments HR2 hybrid rheometer coupled with Keysight E4980 Precision LCR Meter, capable of performing simultaneous rheological and dielectric measurements, in the temperature range -160°C to 350°C. The voltage range is between 0.005 to 20 V with a frequency range of 20 Hz to 2 MHz. Disposable plates are available for curing system.
  • 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) 
    Bruker Vertex70 spectrometer with a variety of sample configurations including transmission, diffuse reflectance, variable angle ATR, and temperature controlled ATR. Instrument has capabilities for vibrational circular and IR reflectance absorbance spectroscopy.
  • Fourier Transform Infrared Spectrometer (FTIR)  Microscope
    Bruker LUMOS is a fully automated stand-alone FTIR microscope with an 8x objective and can be used in transmission, reflection and ATR mode. The measurement results in a single file including visible images, spectral data and sample information. For evaluation and visualization of the microscopic data the software provides powerful and intuitive Chemical Imaging functionality.
  • 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. Temperature controlled and liquid sample environments available.
  • 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.