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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Processing and mechanical characterization of short carbon fiber-reinforced epoxy composites for material extrusion additive manufacturing

Fiber-reinforced polymer composites have been extensively utilized in recent years as feedstock materials for material extrusion additive manufacturing (AM) processes to improve strength, stiffness, and functionality of printed parts over unfilled printed polymers. However, the widespread adoption of AM of fiber-reinforced polymer composites requires a deeper understanding of the process-structure-property relationships in printed components, and such relationships are not well understood yet. Fiber length is critically important to the mechanical performance of short fiber composites, but very few studies to-date have focused on how the fiber length distribution (FLD) evolves during processing of composite feedstocks and how this evolution affects printing behavior and mechanical properties in 3D-printed composites. Here, FLD is measured for carbon fiber reinforced epoxy composites over a wide range of ink compositions and shear mixing times, and the distributions are fit with a Weibull-type distribution function. The effects of FLD on the tradeoff between ink processability, ink rheology, printing behavior and mechanical properties are investigated. Furthermore, the effects of printing parameters (nozzle size and print speed) on mechanical anisotropy and fiber orientation distribution (FOD) in printed composites are explored. Mechanical properties of printed composites are characterized via 3 pt-flexural testing, and microstructure is investigated using optical and scanning electron microscopy (SEM), and x-ray computed tomography. Finally, the fitted Weibull parameters are fed into a composite model that incorporates FLD and FOD, and model predictions are found to be in excellent agreement with experimental observations.

3D printing↗
DOE OSTI2022

Designing Stress-Adaptive Dense Suspensions Using Dynamic Covalent Chemistry

The non-Newtonian behaviors of dense suspensions are central to their use in technological and industrial applications and arise from a network of particle–particle contacts that dynamically adapt to imposed shear. Reported herein are studies aimed at exploring how dynamic covalent chemistry between particles and the polymeric solvent can be used to tailor such stress-adaptive contact networks, leading to their unusual rheological behaviors. Specifically, a room temperature dynamic thia-Michael bond is employed to rationally tune the equilibrium constant (K eq ) of the polymeric solvent to the particle interface. It is demonstrated that low Keq leads to shear thinning, while high K eq produces antithixotropy, a rare phenomenon where the viscosity increases with shearing time. It is proposed that an increase in K eq increases the polymer graft density at the particle surface and that antithixotropy primarily arises from partial debonding of the polymeric graft/solvent from the particle surface and the formation of polymer bridges between particles. Thus, the implementation of dynamic covalent chemistry provides a new molecular handle with which to tailor the macroscopic rheology of suspensions by introducing programmable time dependence. These studies open the door to energy-absorbing materials that not only sense mechanical inputs and adjust their dissipation as a function of time or shear rate but also can switch between these two modalities on demand.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Antielectrophoretic Response-Driven Bending–Tilting Deformation of Cationic Polyelectrolyte Brushes Drives Nonlinear Electroosmotic Transport in Brush-Grafted Nanochannels

In this paper, we use all-atom molecular dynamics (MD) simulations to describe a non-linearly enhanced electroosmotic (EOS) flow, where, in a nanochannel grafted with cationic PMETAC ([Poly(2-(Methacryloyloxy)Ethyl) Trimethylammonium Chloride]) brushes, a two-fold increase in the electric field strength leads to a several-fold (more than two-fold) increase in the EOS flow strength and volume flow rate. The electric field enforces the PMETAC brushes to undergo a bending-tilting driven deformation with a significant portion of the brush layer becoming parallel to the grafting surface. In response, a substantial fraction of the counterions leave the brush layer (hence become more mobile), but instead of going into the bulk, accumulate at the brush-bulk interface, i.e., stay in proximity of the brush segments aligned parallel to the grafting surface. This creates an interesting situation, where the counterions are not completely within the brush layer, yet they fully screen the brush charges. Such “freer” conditions enable the counterions to achieve very high velocity, thereby ensuring that the water solvating the counterions themselves move very fast triggering the significantly augmented EOS transport. Probing deeper we can identify that the bending-tilting driven brush deformation, enforcing the brushes to align parallel to the substrate, results from the anti-electrophoretic behavior of the brushes, where despite being positively charged, the brushes move against the electric field direction. Such an anti-electrophoretic behavior of the PE brushes, which has not been reported before, can be associated with the very fast velocities of the negatively charged counterions and the electrostatic and hydrodynamic coupling of the counterions with the positive functional groups of the brushes. Here, we anticipate that the findings of this paper will shed light on strategies for nanochannel flow, the anti-electrophoretic response of charged polymer chains, and the significance of capturing the detailed chemical architecture of polyelectrolytes in nanoscale science and engineering.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Wood-reinforced composites by stereolithography with the stress whitening behavior

In this study, poplar wood flour at various concentrations (1–10 wt%) is incorporated into a methacrylate-based resin via solution blending to fabricate wood-reinforced composites using stereolithography apparatus (SLA) 3D printing. Differential scanning calorimetry (DSC) along with Fourier transform infrared spectroscopy (FTIR) analysis shows the presence of a small amount of residual monomer in the printed samples. For the printed composites, the glass transition temperature (T g ) from dynamic mechanical analysis (DMA) decreases as more wood flour is incorporated, which indicates an increase in free volume occupied by polymer chains. The tensile strength is improved up to 17.3% from 21.1 MPa (no wood flour) to 24.7 MPa (1.0 wt% wood flour). The highest Young’s modulus reaches 323.8 MPa (2.0 wt% wood flour), which is 1.9-fold of that of the sample without wood flour. Moreover, the composites show “stress whitening” with the addition of wood flour during the uniaxial drawing. Morphology analysis of the tested samples show that the formation of microcraze and microvoids likely causing the stress whitening. This is the first study that demonstrates wood flour can be utilized in SLA 3D printed wood plastic composites (WPC) which can reinforce the printed products with a modest loading amount.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Sub-5 Ångstrom Porosity Tuning in Calixarene-Derived Porous Liquids via Supramolecular Complexation Construction

Sub-Ångstrom-level porosity engineering, which is appealing in gas separations, has been demonstrated in solid carbon, polymer, and framework materials but rarely achieved in the liquid phase. In this work, a gas molecular sieving effect in the liquid phase at sub-5 Ångstrom scale is created via sophisticated porosity tuning in calixarene-derived porous liquids (PLs). Type II PLs are constructed via supramolecular complexation between the sodium salts of calixarene derivatives and crown ether solvents. The chemical structure variation and assembly behavior of the porous host upon PL construction are monitored by spectroscopy-, X-ray-, and neutron-scattering techniques. The presence of permanent porosity in calixarene-derived PLs is verified by pressure swing gas uptake, altered CO 2 physisorption behavior, and molecular simulations. Sub-5 Ångstrom porosity tuning within the PL phase is achieved by introducing bulky substituted groups on the benzene ring of the calixarene host, which then greatly affects the dynamic motion and transport behavior of CO 2 molecules and the Xe uptake performance. Further, the approach being demonstrated in this work represents a promising pathway to tune and leverage the porosity effect for enhanced gas uptake capacity and selectivity in liquid sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Carboxylic Group Rotation and Lattice Expansion in a Co 2 (Pyrazine-2,3-Dicarboxylate) 2 (4,4'-Bipyridine) Porous Coordination Polymer Induced by CO 2 Adsorption at Ambient Temperature

Here, a Co 2 (pzdc) 2 (bpy)(H 2 O) m (pzdc: pyrazine-2,3dicarboxylate; bpy: 4,4'-bipyridine) porous coordination polymer (PCP) was studied for CO 2 uptake and concomitant structural changes at ambient temperature. Extended structural characterization included evaluation of lattice parameter changes upon CO 2 adsorption and in situ synchrotron X-ray powder diffraction data. The PCP effective pore size increased by ~2% with gas uptake over the pressure range of 1-50 atm, allowing the adsorption capacity to double. Furthermore, the hysteretic behaviors seen during CO 2 adsorption at moderate pressures are commensurate with the structural changes from synchrotron data. The adsorption and hysteresis occur with rotation of the linking carboxylate groups, and yet only minor changes in unit cell volume (ΔV ≈ 6 Å 3 ) are observed. This contrasts the findings for [Cu 2 (pzdc) 2 (bpy)] n , where a combination of pillar bpy rotations and significant lattice expansion (ΔV ≈ 68 Å(3)) takes place upon hysteretic adsorption of CO 2 . In situ high-temperature X-ray diffraction revealed that the Co(II)-based material has good thermal stability up to ca. 200° C. Finally, the CO 2 uptake also appears to be at a physisorption level, with adsorbent-adsorbate interactions that are ca. 30% stronger than what has been reported for CO 2 adsorption onto [Cu 2 (pzdc) 2 (bpy)] n .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Electroresponse of weak polyelectrolyte brushes

Abstract End-tethered polyelectrolytes are widely used to modify substrate properties, particularly for lubrication or wetting. External stimuli, such as pH, salt concentration, or an electric field, can induce profound structural responses in weak polyelectrolyte brushes, which can be utilized to further tune substrate properties. We study the structure and electroresponsiveness of weak polyacid brushes using an inhomogeneous theory that incorporates both electrostatic and chain connectivity correlations at the Debye–Hückel level. Our calculation shows that a weak polyacid brush swells under the application of a negative applied potential, in agreement with recent experimental observation. We rationalize this behavior using a scaling argument that accounts for the effect of the surface charge. We also show that the swelling behavior has a direct influence on the differential capacitance, which can be modulated by the solvent quality, pH, and salt concentration. Graphical Abstract

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2001

General Multimechanism Reversible-Irreversible Time-Dependent Constitutive Deformation Model Being Developed

Since most advanced material systems (for example metallic-, polymer-, and ceramic-based systems) being currently researched and evaluated are for high-temperature airframe and propulsion system applications, the required constitutive models must account for both reversible and irreversible time-dependent deformations. Furthermore, since an integral part of continuum-based computational methodologies (be they microscale- or macroscale-based) is an accurate and computationally efficient constitutive model to describe the deformation behavior of the materials of interest, extensive research efforts have been made over the years on the phenomenological representations of constitutive material behavior in the inelastic analysis of structures. From a more recent and comprehensive perspective, the NASA Glenn Research Center in conjunction with the University of Akron has emphasized concurrently addressing three important and related areas: that is, 1) Mathematical formulation; 2) Algorithmic developments for updating (integrating) the external (e.g., stress) and internal state variables; 3) Parameter estimation for characterizing the model. This concurrent perspective to constitutive modeling has enabled the overcoming of the two major obstacles to fully utilizing these sophisticated time-dependent (hereditary) constitutive models in practical engineering analysis. These obstacles are: 1) Lack of efficient and robust integration algorithms; 2) Difficulties associated with characterizing the large number of required material parameters, particularly when many of these parameters lack obvious or direct physical interpretations.

Saleeb, A. F.↗
DOE OSTI2020

Composite Structured Surfaces for Durable Dropwise Condensation

Dropwise condensation of steam on hydrophobic substrates has a 10X higher heat transfer coefficient compared to filmwise condensation. To promote dropwise condensation, low surface energy hydrophobic coatings (polymers) are typically utilized. The low intrinsic thermal conductivity (k < 1 W/(m · K)) of polymers, coupled with high heat transfer coefficient of dropwise condensation (100 kW/(m 2 · K)), necessitates that the coating be thin (< 1µm) in order to avoid reducing the overall heat exchanger conductance. However, thin polymeric films easily degrade. The two opposing requirements result in the need for optimization between the durability (thick coating) and the heat transfer (thin coating). To enable high thermal conductivity in thicker coatings, we develop metal-polymer structured surfaces. By using porous structures as inter-connected heat-conducting backbones that are filled with hydrophobic materials, we enable tuning of the coating effective thermal conductivity and surface energy. Three metal structures were studied; micro/nanowires, inverse opals, and sintered spheres. Heat transfer performance was calculated using three-dimensional finite element method simulations with two distinct boundary conditions; convection at the walls and isothermal walls. Interestingly, the overall conductance shows up to 40% difference depending on the boundary condition used in calculating the composite coating effective thermal conductivity. We use our model to predict the heat transfer performance as a function of metal fraction by volume and by surface area for condensation. By coupling our thermal simulations with a previously verified analytical model for predicting wetting behavior on heterogeneous surfaces, we propose a regime map to predict dropwise-to-filmwise transition. Furthermore, our work not only forms a starting point for the development of durable dropwise condensing surfaces, it identifies important considerations needed for computing effective thermal conductivity of composites.

42 ENGINEERING↗
NASA NTRS1989

Non linear viscoelasticity applied for the study of durability of polymer matrix composites

A methodology is described for the durability analysis of polymer matrix composites, based on nonlinear viscoelasticity theory. The durability analysis is performed on the basis of a certain number of tests carried out on limited and, if possible, short time scale by the use of accelerating factors. The method was applied to thermomatrix composites under uniaxial and biaxial loadings, showing satisfactory agreement between the life-time predictions and the published data on real-time behavior.

Cardon, A.↗
DOE OSTI2022

Hydroporphyrin-Doped Near-Infrared-Emitting Polymer Dots for Cellular Fluorescence Imaging

We report Near-infrared (NIR) fluorescent semiconductor polymer dots (Pdots) have shown great potential for fluorescence imaging due to their exceptional chemical and photophysical properties. This paper describes the synthesis of NIR emitting Pdots with great control and tunability of emission peak wavelength. The Pdots were prepared by doping poly [(9,9-dioctylfluorenyl-2,7-diyl)-altco-(1,4-benzo-(2,1’,3)-thiadiazole)] (PFBT), a semiconducting polymer commonly used as a host polymer in luminescent Pdots, with a series of chlorins and bacteriochlorins with varying functional groups. Chlorins and bacteriochlorins are ideal dopants due to their high hydrophobicity, which precludes their use as molecular probes in aqueous biological media but on the other hand prevents their leakage when doped into Pdots. Additionally, chlorins and bacteriochlorins have narrow deep-red to NIR emission bands and the wide array of synthetic modifications available for modifying their molecular structure enables tuning their emission predictably and systematically. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements show the chlorin and bacteriochlorin-doped Pdots to be nearly spherical with an average diameter of 46±12 nm. Efficient energy transfer between PFBT and the doped chlorins or bacteriochlorins decreases the PFBT donor emission to near baseline level and increases the emission of the doped dyes that serve as acceptors. The chlorin and bacteriochlorindoped Pdots show narrow emission bands ranging from 640 nm to 820 nm depending on the doped dye. The paper demonstrates the utility of the systematic chlorin and bacteriochlorin synthesis approach by preparing Pdots of varying emission peak wavelength, utilizing them to visualize multiple targets using wide field fluorescence microscopy, binding them to secondary antibodies, and determining the binding of secondary antibody-conjugated Pdots to primary antibody-labeled receptors in plant cells. Additionally, the chlorin and bacteriochlorin doped Pdots show a blinking behavior that could enable their use in super resolution imaging methods like STORM.

13C-NMR↗
DOE OSTI2020

Impact of wet-dry cycling on the phase behavior and compartmentalization properties of complex coacervates

Abstract Wet-dry cycling on the early Earth is thought to have facilitated production of molecular building blocks of life, but its impact on self-assembly and compartmentalization remains largely unexplored. Here, we investigate dehydration/rehydration of complex coacervates, which are membraneless compartments formed by phase separation of polyelectrolyte solutions. Solution compositions are identified for which tenfold water loss results in maintenance, disappearance, or appearance of coacervate droplets. Systems maintaining coacervates throughout the dehydration process are further evaluated to understand how their compartmentalization properties change with drying. Although added total RNA concentrations increase tenfold, RNA concentration within coacervates remains steady. Exterior RNA concentrations rise, and exchange rates for encapsulated versus free RNAs increase with dehydration. We explain these results in light of the phase diagram, with dehydration-driven ionic strength increase being particularly important in determining coacervate properties. This work shows that wet-dry cycling can alter the phase behavior and protocell-relevant functions of complex coacervates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

High-speed x-ray phase contrast imaging and digital image correlation analysis of microscale shock response of an additively manufactured energetic material simulant

The performance of energetic materials subjected to dynamic loading significantly depends on their micro- and meso-scale structural morphology. The geometric versatility offered by additive manufacturing opens new pathways to tailor the performance of these materials. Additively manufactured energetic materials (AMEMs) have a wide range of structural characteristics with a hierarchy of length scales and process-inherent heterogeneities, which are hitherto difficult to precisely control. It is important to understand how these features affect AMEMs’ response under dynamic/shock loading. Therefore, temporally and spatially resolved measurements of both macroscopic behavior and micro- and meso-level processes influencing macroscopic behavior are required. In this paper, we analyze the shock compression response of an AMEM simulant loaded under several impact conditions and orientations. Furthermore, x-ray phase contrast imaging (PCI) is used to track features across the observed shock front and determine the linear shock velocity vs particle velocity equation of state, as well as to quantify the interior deformation fields via digital image correlation (DIC) analyses. Photon Doppler velocimetry is simultaneously used to measure the particle velocities of the specimens, which are consistent with those obtained from x-ray PCI. The DIC analyses provide an assessment of the average strain fields inside the material, showing that the average axial strain depends on the loading intensity and reaches as high as 0.23 for impact velocities up to 1.5 km/s. The overall results demonstrate the utility of x-ray PCI for probing “in-material” equation of state and interior strains associated with dynamic shock compression behavior of the AMEM simulant.

3D printing↗
DOE OSTI2022

Guiding Self-Assembly of Active Colloids by Temporal Modulation of Activity

Self-organization phenomena in ensembles of self-propelled particles open pathways to the synthesis of new dynamic states not accessible by traditional equilibrium processes. The challenge is to develop a set of principles that facilitate the control and manipulation of emergent active states. In this study, we report that dielectric rolling colloids energized by a pulsating electric field self-organize into alternating square lattices with a lattice constant controlled by the parameters of the field. We combine experiments and simulations to examine spatiotemporal properties of the emergent collective patterns and investigate the underlying dynamics of the self-organization.We reveal the resistance of the dynamic lattices to compression and expansion stresses leading to a hysteretic behavior of the lattice constant. The general mechanism of pattern synthesis and control in active ensembles via temporal modulation of activity can be applied to other active colloidal systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Electrochemical Behavior of Copper Ion Complexed with Nanoparticle Organic Hybrid Materials

Nanoscale Organic Hybrid Materials (NOHMs) have unique properties that show potential for their use as novel electrolytes that can interact with redox active species. In this work, we probe the effects of adding poly(ethyleneimine)-based NOHMs (NOHM-I-PEI) on copper ion electrochemical reactions. As NOHM-I-PEI is added to a solution containing Cu(II), the voltammetric peak current decreases. This is likely caused by strong complex formation between the PEI nitrogen and the copper, similar to complexation observed in solutions of the polymer with copper. Upon copper addition to a NOHM-I-PEI solution, the pH decreases from 10.1, plateauing at pH = 5.3 at ~3:1 N:Cu ratio indicating that Cu(II) displaces protons. The UV–visible spectra exhibit a Cu-PEI peak, the intensity of which levels off at ~2.8 N:Cu. Acid titration of the N-moieties of the PEI reveals three inflections corresponding to N-environments in the PEI. Upon controlling the pH of the solution by buffering, the "sequestration" of Cu(II) is found to occur when there are unprotonated nitrogens present in the NOHM-I-PEI system; this phenomenon is also supported by UV-vis results. Furthermore, this work highlights the potential of and the design of NOHMs to carry charged electroactive species in solutions along with key factors to control for optimal function.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2007

Micromechanics of Spray-On Foam Insulation

Understanding the thermo-mechanical response of the Space Shuttle External Tank spray-on foam insulation (SOFI) material is critical, to NASA's Return to Flight effort. This closed-cell rigid polymeric foam is used to insulate the metallic Space Shuttle External Tank, which is at cryogenic temperatures immediately prior to and during lift off. The shedding of the SOFI during ascent led to the loss of the Columbia, and eliminating/minimizing foam lass from the tank has become a priority for NASA as it seeks to resume scheduled space shuttle missions. Determining the nature of the SOFI material behavior in response to both thermal and mechanical loading plays an important role as any structural modeling of the shedding phenomenon k predicated on knowledge of the constitutive behavior of the foam. In this paper, the SOFI material has been analyzed using the High-Fidelity Generalized Method of Cells (HFGMC) micromechanics model, which has recently been extended to admit a triply-periodic 3-D repeating unit cell (RUC). Additional theoretical extensions that mere made in order to enable modeling of the closed-cell-foam material include the ability to represent internal boundaries within the RUC (to simulated internal pores) and the ability to impose an internal pressure within the simulated pores. This latter extension is crucial as two sources contribute to significant internal pressure changes within the SOFI pores. First, gas trapped in the pores during the spray process will expand or contract due to temperature changes. Second, the pore pressure will increase due to outgassing of water and other species present in the foam skeleton polymer material. With HFGMC's new pore pressure modeling capabilities, a nonlinear pressure change within the simulated pore can be imposed that accounts for both of these sources, in addition to stmdar&-thermal and mechanical loading; The triply-periodic HFGMC micromechanics model described above was implemented within NASA GRC's MAC/GMC software package, giving the model access to a range of nonlinear constitutive models for the polymeric foam skeleton material. A repeating unit cell architecture was constructed that, while relatively simple, still accounts for the geometric anisotropy of the porous foam microstructure and its thin walls and thicker edges. With the lack of reliable polymeric foam skeleton materia1 properties, many simulations were executed aimed at backing out these material properties. Then, using these properties, predictions of the thermo-mechanical behavior of the foam, including calculated internal applied pressure profiles, were performed and compared with appropriate experimental data.

Bednarcyk, Brett A.↗
DOE OSTI2020

Rheological behavior of neat and carbon fiber-reinforced poly(ether ketone ketone) for extrusion deposition additive manufacturing

To develop new materials for extrusion additive manufacturing (AM) systems, a fundamental understanding of rheological properties is essential to correlate the effect of processing on material structure and its properties. In this work, the rheological properties of five different grades of neat and carbon fiber (CF)-reinforced poly(ether ketone ketone) are reported. Rheological properties are essential to understand the effect of reinforcing fibers and AM process parameters such as time, temperature, environment, and shear rate on flow behavior during processing. Small-amplitude oscillatory shear tests and steady shear tests indicated neat grades to exhibit less increase in viscosity over time when processed in air than the CF-filled grades. The filled grades showed greater shear thinning and lower sensitivity to temperature. Altogether, this rheological analysis provides a broad framework for determining appropriate processing conditions for extrusion deposition AM of such high-temperature polymer systems.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Ethylene Polymerizations Catalyzed by Fluorinated “Sandwich” Diimine-Nickel and Palladium Complexes

Nickel and palladium complexes bearing “sandwich” diimine ligands with perfluorinated aryl caps have been synthesized, characterized, and explored in ethylene polymerization reactions. The X-ray crystallographic analysis of the precatalysts 16 and 6b show differences from their non-fluorinated analogues 17 and 19, with the perfluorinated aryl caps centered precisely over the nickel and palladium centers which results in higher buried volumes of the metal centers relative to the non-fluorinated analogs. The sandwich diimine palladium complexes 5a and 5b containing perfluorinated aryl caps polymerize ethylene in a controlled fashion with activities that are substantially increased compared with their non-fluorinated analogues. Migratory insertion rates in relevant methyl ethylene complexes agree with activities exhibited in bulk polymerization experiments. DFT studies suggest that facility of ethylene rotation from its preferred orientation perpendicular to the Pd-alkyl bond into a parallel in-plane conformation contributes to the higher polymerization activity for 5b relative to 18a. For these palladium systems polymer molecular weights can be controlled via hydrogen addition (hydrogenolysis) which is unusual for late transition metal-catalyzed olefin polymerizations with no catalyst deactivation occurring. Sandwich diimine nickel complexes 6a and 6b with perfluorinated aryl caps show ethylene polymerization activities that are about half that of classical tetraisopropyl-substituted catalyst 2 but again are more active than the analogous nonfluorinated sandwich complexes. Ethylene polymerizations exhibit living behavior and branched ultra-high molecular weight polyethylenes (UHMWPEs) with very low molecular weight distributions (less than 1.1) are obtained. The activated nickel catalysts are stable in the absence of monomer and show good long-term stability at 25 °C.

36 MATERIALS SCIENCE↗