It is generally believed that the strength of the polymer–nanoparticle interaction controls the modification of near-interface segmental mobility in polymer nanocomposites (PNCs). However, little is ...known about the effect of covalent bonding on the segmental dynamics and glass transition of matrix-free polymer-grafted nanoparticles (PGNs), especially when compared to PNCs. In this article, we directly compare the static and dynamic properties of poly(2-vinylpyridine)/silica-based nanocomposites with polymer chains either physically adsorbed (PNCs) or covalently bonded (PGNs) to identical silica nanoparticles (R NP = 12.5 nm) for three different molecular weight (MW) systems. Interestingly, when the MW of the matrix is as low as 6 kg/mol (R NP/R g = 5.4) or as high as 140 kg/mol (R NP/R g= 1.13), both small-angle X-ray scattering and broadband dielectric spectroscopy show similar static and dynamic properties for PNCs and PGNs. However, for the intermediate MW of 18 kg/mol (R NP/R g = 3.16), the difference between physical adsorption and covalent bonding can be clearly identified in the static and dynamic properties of the interfacial layer. We ascribe the differences in the interfacial properties of PNCs and PGNs to changes in chain stretching, as quantified by self-consistent field theory calculations. These results demonstrate that the dynamic suppression at the interface is affected by the chain stretching; that is, it depends on the anisotropy of the segmental conformations, more so than the strength of the interaction, which suggests that the interfacial dynamics can be effectively tuned by the degree of stretchinga parameter accessible from the MW or grafting density.
The mechanical reinforcement of polymer nanocomposites (PNCs) above the glass transition temperature, T g, has been extensively studied. However, not much is known about the origin of this effect ...below T g. In this Letter, we unravel the mechanism of PNC reinforcement within the glassy state by directly probing nanoscale mechanical properties with atomic force microscopy and macroscopic properties with Brillouin light scattering. Our results unambiguously show that the “glassy” Young’s modulus in the interfacial polymer layer of PNCs is two-times higher than in the bulk polymer, which results in significant reinforcement below T g. We ascribe this phenomenon to a high stretching of the chains within the interfacial layer. Since the interfacial chain packing is essentially temperature independent, these findings provide a new insight into the mechanical reinforcement of PNCs also above T g.
The structure and polymer–nanoparticle interactions among physically adsorbed poly(2-vinylpyridine) chains on the surface of silica nanoparticles (NPs) were systematically studied as a function of ...molecular weight (MW) by sum frequency generation (SFG) and X-ray photoelectron (XPS) spectroscopies. Analysis of XPS data identified hydrogen bonds between the polymer and NPs, while SFG evaluated the change in the number of free OH sites on the NP’s surface. Our data revealed that the hydrogen bonds and amount of the free −OH sites have a significant dependence on the polymer’s MW. These results provide clear experimental evidence that the interaction of physically adsorbed chains with nanoparticles is strongly MW dependent and aids in unraveling the microscopic mechanism responsible for the strong MW dependence of dynamics of the interfacial layer in polymer nanocomposites.
An ultrathin aluminum oxide (Al2O3) coating improves significantly the stability of plasmonic structures used in tip enhanced Raman spectroscopy (TERS). The coating does not alter the favorable ...optical properties of metallic structures yet improves wear resistance and inhibits degradation, so that signal enhancement remains constant over 40 days for structures with a 3 nm thick protective coating. Most unprotected structures show substantial losses in enhancement over periods as short as 10 days when stored and used in ambient conditions.
The high luminosity upgrade of the Large Hadron Collider, foreseen for 2027, requires the replacement of the ATLAS Inner Detector with a new all-silicon Inner Tracker (ITk). The expected total ...integrated luminosity of 4000 fb−1 means that the strip part of the ITk detector will be exposed to a large radiation fluence of up to Φeq = 1.6 × 1015 1 MeV neq/cm and an ionizing dose of 0.66 MGy, including a safety factor of 1.5. Radiation-hard n+-in-p micro-strip sensors for use in the ITk have been developed by the ATLAS ITk Strip Sensor collaboration and produced by Hamamatsu Photonics K.K. In this paper, the results obtained from the electrical characterization of the latest barrel ATLAS17LS sensor prototype, before and after irradiation, are shown.
Surface properties of the long-strip barrel, full-sized and miniature sensors have been studied before and after proton, neutron and gamma irradiation up to the maximal fluences and radiation doses specified for the ITk Strip tracker. Sensors have been irradiated by protons at CYRIC, Tohoku University (Japan), the Proton Irradiation Facility at CERN, Karlsruhe Inst. Tech. (Germany) and at the University of Birmingham (UK), by neutrons from the Ljubljana TRIGA reactor (Slovenia) and by gamma rays from the 60Co source in UJP Praha (Czech Republic).
It has been verified that the surface radiation damage does not influence the sensor functionality. The breakdown voltage is well above the maximum operational voltage. All the tested surface parameters, such as the inter-strip resistance and capacitance, coupling capacitance and bias resistance satisfy the ATLAS ITk specifications for strip sensors.
The inner tracker of the ATLAS detector is scheduled to be replaced by a completely new silicon-based inner tracker (ITk) for the Phase-II of the CERN LHC (HL-LHC). The silicon strip detector covers ...the volume 40<R<100 cm in the radial and |z|<300 cm in the longitudinal directions. The silicon sensors for the detector will be fabricated using the n+-on-p 6-inch wafer technology, for a total of 22,000 wafers. Intensive studies were carried out on the final prototype sensors ATLAS17LS fabricated by Hamamatsu Photonics (HPK). The charge collection properties were examined using penetrating 90Sr β-rays and the ALIBAVA fast readout system for the miniature sensors of 1 cm ×1 cm in area. The samples were irradiated by protons in the 27 MeV Birmingham Cyclotron, the 70 MeV CYRIC at Tohoku University, and the 24 GeV CERN-PS, and by neutrons at Ljubljana TRIGA reactor for fluence values up to 2 × 1015 neq/cm2. The change in the charge collection with fluence was found to be similar to the previous prototype ATLAS12, and acceptable for the ITk. Sensors with two active thicknesses, 300μm (standard) and 240μm (thin), were compared and the difference in the charge collection was observed to be small for bias voltages up to 500 V. Some samples were also irradiated with gamma radiation up to 2 MGy, and the full depletion voltage was found to decrease with the dose. This was caused by the Compton electrons due to the 60Co gamma radiation. To summarize, the design of the ATLAS17LS and technology for its fabrication have been verified for implementation in the ITk. We are in the stage of sensor pre-production with the first sensors already delivered in January of 2020.
Two boron-containing, ortho-icosahedral carborane lipophilic antifolates were synthesized, and the crystal structures of their ternary complexes with human dihydrofolate reductase (DHFR) and ...dihydronicotinamide adenine dinucleotide phosphate were determined. The compounds were screened for activity against DHFR from six sources (human, rat liver, Pneumocystis carinii, Toxoplasma gondii, Mycobacterium avium, and Lactobacillus casei) and showed good to modest activity against these enzymes. The compounds were also tested for antibacterial activity against L. casei, M. tuberculosis H37Ra, and three M. avium strains and for cytotoxic activity against seven different human tumor cell lines. Antibacterial and cytotoxic activity was modest, with one sample, the closo-carborane 4, showing about 10-fold greater activity. The less toxic nido-carborane 2 was also tested as a candidate for boron neutron capture therapy, but showed poor tumor retention and low selectivity ratios for boron distribution in tumor tissue versus normal tissue.
PDF
