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At least 19 records

Temperature-dependent self-assembly and rheological behavior of a thermoreversible pmma-P n BA-PMMA triblock copolymer gel

Self-assembly and mechanical properties of triblock copolymers in a mid-block selective solvent are of interest in many applications. Herein, we report physical assembly of an ABA triblock copolymer, [PMMA–PnBA–PMMA] in two different mid-block selective solvents, n-butanol and 2-ethyl-1-hexanol. Gel formation resulting from end-block associations and the corresponding changes in mechanical properties have been investigated over a temperature range of -80 °C to 60 °C, from near the solvent melting points to above the gelation temperature. Shear-rheometry, thermal analysis, and small-angle neutron scattering data reveal formation and transition of structure in these systems from a liquid state to a gel state to a percolated cluster network with decrease in temperature. The aggregated PMMA end-blocks display a glass transition temperature. Our results provide new understanding into the structural changes of a self-assembled triblock copolymer gel over a large length scale and wide temperature range.

36 MATERIALS SCIENCE↗

On a physics-based model equation for shock-position evolution in PMMA

A governing differential equation for shock position in PMMA was derived from momentum conservation and an experimentally determined decay law for shock pressure. A new multi-diagnostic characterization method for measuring detonator pressure and wave shape output in PMMA witness blocks provided temporally resolved, 1-D, shock-position data that was iteratively fit by solutions to the governing equation via a unique genetic algorithm solver. The goal was to calculate a solution that describes the temporal evolution of shock pressure in PMMA starting at the detonator interface. The empirical decay law was investigated using experimental data, where different regimes were considered for the decay coefficients. A successful solution provides extensive performance information that is directly relevant to the understanding and characterization of detonator function.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

An end of service life assessment of PMMA lenses from veteran concentrator photovoltaic systems

The optical performance of poly(methyl methacrylate) lenses from veteran concentrator photovoltaic modules was examined after the end of their service life. Lenses from the Martin-Marietta and Intersol module designs were examined from the 'Solar Village' site near Riyadh, Saudi Arabia, as well as the Phoenix Sky Harbor airport, followed by the Arizona Public Service Solar Test and Research (APS-STaR) center in Tempe, Arizona. The various lens specimens were deployed for 20, 27, and 22 years, respectively. Optical characterizations included lens efficiency (Solar Simulator instrument), material transmittance and haze (of coupons cut from veteran lenses, then measured again after their faceted back surface was polished, and then measured again after the incident front surface was polished), and direct transmittance (as a function of detector's acceptance angle, using the Very Low Angular Beam Spread ('VLABS') instrument). Lens efficiency measurements compared the central region to the entire lens, also using hot and cold mirror measurements to diagnose differences in performance. A series of subsequent characterizations was performed because a decrease in performance of greater than 10% was observed for some of the veteran lenses. The optimal focal distance of the lenses was quantified using the Solar Simulator, and then correlated to lens curvature using a recently developed measurement technique. Surface roughness was examined using atomic force microscopy and scanning electron microscopy. Facet geometry (tip and valley radius) was quantified on cross-sectioned specimens. As a result, molecular weight was compared between the incident and faceted surfaces of the lenses.

14 SOLAR ENERGY↗

Understanding the Mechanism of Solvent-Mediated Adhesion of Vacuum Deposited Au and Pt Thin Films onto PMMA Substrates

The adhesion of 100 nm thick electron-beam deposited Au and Pt and magnetron sputtered Au thin films onto poly(methyl methacrylate) (PMMA) substrates can be significantly enhanced to over 90% adhesion by either spin-casting or vapor-exposure to hydrohalocarbon solvents prior to metal deposition compared to samples that are either cleaned in isopropyl alcohol or pre-treated with a remote O2 plasma. X-ray photoelectron spectroscopy (XPS) and evolved gas Fourier transform infrared spectroscopy (EGA-FTIR) reveal the presence of residual halogenated solvent molecules at the PMMA surface which chemically activates the surface to produce a stable chemical interaction between the noble metal film and the PMMA. Density functional theory (DFT) calculations show that the halogenated solvent molecules preferentially form a Lewis acid-base adduct with the oxygen atoms in the ester group in PMMA which is consistent with the measured enthalpy of desorption of chloroform (CHCl3) on PMMA determined by EGA-FTIR to be 36 kJ mol-1. The DFT model also supports the experimentally observed change in the high resolution XPS O 1s peak at 533.77 eV after metallization attributed to a change in the local bonding environment of the bridging O in the PMMA ester group. DFT also predicts that the deposited metal atom (M) inserts into the C-X bond where X is the halogen atom on either CHCl3 or bromoform (CHBr3) to form a O M X interaction that is observed by a M-X bond in the high resolution XPS Cl 2p3/2 peak at 198.03 eV and Br 3p3/2 peak at 182.06 eV. A range of solvents with differing polarities for PMMA pre-treatment have been used and it is proposed that non-complexing solvents result in significant metal adhesion improvement. The Gutmann acceptor number can be used to predict the effectiveness of solvent treatment for noble metal adhesion. A model is proposed in which the bond energy of the C-X bond of the solvent must be sufficiently low so that the C-X bond can be cleaved to form the M-X bond. Supporting this model, a negative control of vapor phase exposure to fluoroform (CHF3) is shown to have no effect on noble metal adhesion due to the higher bond dissociation energy of the C-F bond compared to the C-Cl and C-Br bond energy. The surface activation of vapor-phase exposed PMMA surfaces is technologically significant for the fabrication of polymer microdevices requiring Au or Pt metallization.

Mo, Alan K↗

Influence of amine-grafted multi-walled carbon nanotubes on physical and rheological properties of PMMA-based nanocomposites

In this work, poly(methyl methacrylate) (PMMA) was grafted onto amine treated multi-walled carbon nanotubes (NH-MWNTs) and the physical and rheological properties of the NH-MWNTs-g-PMMA nanocomposites were investigated. The graft reaction of NH-MWNTs and the PMMA matrix was confirmed from the change of the N{sub 1S} peaks, including those of amine oxygen and amide oxygen, by X-ray photoelectron spectroscopy (XPS). The thermal and mechanical properties of the NH-MWNT-g-PMMA nanocomposites were enhanced by the graft reaction between NH-MWNTs and PMMA matrix. In addition, the viscosity of the nanocomposites was increased with the addition of NH-MWNTs. Storage (G') and loss modulus (G'') were significantly increased by increase in the NH-MWNT content compared to acid-treated MWNTs/PMMA nanocomposites. This increase was attributed to the strong interaction by the grafting reaction between NH-MWNTs and the PMMA matrix. - Graphical abstract: This describes the increase of mechanical properties in NH-MWNTs-g-PMMA hybrid composites with different NH-MWNT contents. Highlights: > Aminized carbon nanotubes are used as reinforcement for poly(methylmethacrylate). > Poly(methylmethacrylate) is grafted on aminized carbon nanotubes by thermal reaction. > Grafting of carbon nanotubes and polymer provide enhanced physical properties. > It was due to the strong interaction between carbon nanotubes and polymer matrix.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shock Response of Polymethyl Methacrylate (PMMA) Under Explosive Loading

Abstract The dynamic response of polymethyl methacrylate (PMMA) is well understood for one-dimensional planar impact shocks, but limited research has been performed on the response of PMMA under spherical shock loading. In this work, the shock decay of an explosively-driven shock wave into PMMA was experimentally measured. PMMA cubes of various geometries were explosively loaded with an RP-80 detonator to produce the explosive shock wave. High-speed schlieren imaging was implemented to measure the explosively-driven shock wave velocity throughout the PMMA cubes. Photon Doppler velocimetry (PDV) was used to measure the particle velocity imparted by the shock wave at the surface of the cubes. The material shock response was studied at distances from 21.91 to 133.3 mm from the explosive source. The particle velocity history measured by PDV was compared to the wave profile visualized in the high-speed images. The shock wave pulse amplitude decreased with increased distance from the source. The conducted experiments extend the PMMA shock Hugoniot relating to the lower shock and particle velocity regime.

Torres, S. M. (ORCID:0009000287177206)↗

Effect of Electric Field Alignment of MWCNT in PMMA Matrix for Hydrogen Gas Purification

The composite membranes of multi-walled carbon nanotube (MWCNT) and polymethylmethacrylate (PMMA) were prepared by solution cast method. The MWCNT was dispersing a very low concentration (0.1 wt %) in PMMA matrix. Alignment of MWCNT in PMMA matrix has been performed by inducing a DC electric field at different voltage parameter varying from 350 V/cm to 1250 V/cm. The MWCNT/PMMA composites were characterized by gas permeation and electrical measurement before and after electric field alignment. The effect of electric field alignment has been studied on gas permeation measurements for gas purification applications. These measurements indicate the enhancement in gas permeability due to the aligned of MWCNT in PMMA matix as compare to randomly dispersed MWCNT. I-V characteristics measurement also indicates that aligned MWCNT/PMMA composite membrane exhibits electron tunneling conductivity.

36 MATERIALS SCIENCE↗

Ag{sup +12} ion induced modifications of structural and optical properties of ZnO-PMMA nanocomposite films

The influence of swift heavy ion (SHI) irradiation on structural and photoluminescence (PL) properties of ZnO-PMMA nanocomposite films, prepared by solution casting method, was studied. The ZnO-PMMA nanocomposite films were irradiated using 120 MeV Ag{sup +12} ions at different fluences varying from 1 Multiplication-Sign 10{sup 11} to 1 Multiplication-Sign 10{sup 13} ions/cm{sup 2}. The intensity of the X-ray diffraction peaks is increased at the high fluence, without evolution of any new peak. A shift in absorption edge (i.e. shift in optical band gap) towards higher wavelength was observed after irradiation and PL from ZnO-PMMA nanocomposite films is found to increase up to a critical fluence and then found to be suppressed for higher fluence (1 Multiplication-Sign 10{sup 12} ion/cm{sup 2}). The change in photoluminescence after irradiation can be attributed to the change in microstructure of PMMA matrix as well as the agglomeration of ZnO nanoparticles.

36 MATERIALS SCIENCE↗

Qualification of a multi-diagnostic detonator-output characterization procedure utilizing PMMA witness blocks

In this study, experiments were conducted to qualify a multi-diagnostic characterization procedure for the performance output of a detonator when fired into a poly(methyl methacrylate) (PMMA) witness block. A suite of optical diagnostics were utilized in combination to both bound the shock wave interaction state at the detonator/PMMA interface and characterize the nature of the shock wave decay in PMMA. The diagnostics included the Shock Wave Image Framing Technique (SWIFT), a photocathode tube streak camera, and photonic Doppler velocimetry (PDV). High-precision, optically clear witness blocks permitted dynamic flow visualization of the shock wave in PMMA via focused shadowgraphy. SWIFT-and streak-imaging diagnostics captured the spatiotemporally evolving shock wave, providing a two-dimensional temporally discrete image set and a one-dimensional temporally continuous image, respectively. PDV provided the temporal velocity history of the detonator output along the detonator axis. Lastly, through combination of the results obtained, a bound was able to be placed on the interface condition and a more-physical profile representing the shock wave decay in PMMA for an exploding-bridgewire detonator was achieved.

47 OTHER INSTRUMENTATION↗

Mechanisms for hyperthermal polyatomic hydrocarbon modification of PMMA surfaces from molecular dynamics simulations

Classical molecular dynamics simulations are performed to determine the mechanisms by which hyperthermal hydrocarbon polyatomics, which are present in low-energy plasmas, chemically modify polymer surfaces. In particular, C 2 H, CH 3 , and C 3 H 5 are deposited on an amorphous poly (methyl methacrylate) (PMMA) substrate with kinetic energies of 4, 10, 25, and 50 eV and compared to the deposition of H at the same energies. The short-range forces on the atoms are determined using the second generation reactive empirical many-body potential, while the long-range forces are determined using a Lennard-Jones potential. The simulations predict that at all these incident energies, the chemical modification of the PMMA is limited to within a nanometer of the surface. Atoms, fragments, and incident polyatomics are further predicted to chemically attach to specific sites on the PMMA monomers at low energies and to attach to a wider range of sites at higher energies. However, no appreciable cross-linking between polymer chains is predicted to occur. Variation in the penetration depth of the deposited polyatomics or H is correlated to differences in their size and bond saturation. The greatest extent of chemical modification of the PMMA surface slab is achieved for C 2 H deposition with 50 eV of kinetic energy.

36 MATERIALS SCIENCE↗

Properties of electrospun CdS and CdSe filled poly(methyl methacrylate) (PMMA) nanofibres

Graphical abstract: SEM images of CdS/PMMA showing coiling as loading of CdS nanoparticles is increased. Thermal stability is increased with increase in %loading of both CdS and CdSe nanoparticles. Research highlights: {yields} TOPO-capped CdS and HDA-capped CdSe nanoparticles were synthesized and fully characterized. {yields} The nanoparticles were mixed with the polymer, PMMA using electrospinning technique using 2, 5 and 10% weight loadings. {yields} The mixture was spun to produce fibres with optical and thermal properties showing significant change and also the increase in loading causing bending or spiraling. {yields} Both TEM images for nanoparticles and SEM for fibres shows the morphology and sizes of the particles. -- Abstract: Electrospinning technique was used to fabricate poly(methyl methacrylate) (PMMA) fibres incorporating CdS and CdSe quantum dots (nanoparticles). Different nanoparticle loadings (2, 5 and 10 wt% with respect to PMMA) were used and the effect of the quantum dots on the properties of the fibres was studied. The optical properties of the hybrid composite fibres were investigated by photoluminescence and UV-vis spectrophotometry. Scanning electron microscopy (SEM), X-ray diffraction and FTIR spectrophotometry were also used to investigate the morphology and structure of the fibres. The optical studies showed that the size-tunable optical properties can be achieved in the polymer fibres by addition of quantum dots. SEM images showed that the morphologies of the fibres were dependent on the added amounts of quantum dots. A spiral type of morphology was observed with an increase in the concentration of CdS and CdSe nanoparticles. Less beaded structures and bigger diameter fibres were obtained at higher quantum dot concentrations. X-ray diffractometry detected the amorphous peaks of the polymer and even after the quantum dots were added and the FTIR analysis shows that there was no considerable interaction between the quantum dots and the polymer fibres at low concentration of quantum dots however at higher concentrations some interactions were observed which shows that QDs were present on the surfaces of the fibres.

36 MATERIALS SCIENCE↗

Influence of dopant concentration on the electrical properties of the CdSe-PMMA nanocomposite

This paper reports the synthesis and electrical characterization of CdSe-PMMA nanocomposite. CdSe-PMMA nanocomposite has been prepared by ex-situ technique through chemical route. The influence of three different Ag doping concentrations on the electrical properties has been studied in the temperature range ∼ 303-353 K. Transmission electron micrograph reveals the spherical morphology of the CdSe nanoparticles and their proper dispersion in the PMMA matrix. The electrical conduction of the polymer nanocomposites is through thermally activated process with single activation energy. With Ag doping, initially the activation energy increases upto 0.2 % Ag doping concentration but with further increase in Ag concentration, it decreases. This behavior has been discussed on the basis of randomly oriented grain boundaries and defect states. Thus, the results indicate that the transport properties of the polymer nanocomposites can be tailored by controlled doping concentration.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Reshock analysis for PMMA driven above the threshold for chemical decomposition

Polymethyl methacrylate (PMMA) is a transparent thermoplastic often used in shock compression science. Previous proceedings (AIP Conf. Proc. 845, 131 (2006)) described plate impact experiments in which PMMA was reshocked to pressures of up to ~130 GPa, well above that at which it decomposes on its principal Hugoniot. Because some of the conclusions of the original analysis were surprising, the results were reanalyzed in a later proceeding (ibid. 1426, 771 (2012)). In addition to our own reanalysis of the data, we performed hydrodynamic simulations of the experiments based on a new equation of state for PMMA shocked above its threshold for decomposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Melt Self-Assembly of PS-PMMA-PLA Triblock Bottlebrush Copolymers

Polystyrene–poly(methyl methacrylate)–polylactide (PS–PMMA–PLA) triblock bottlebrush copolymer with nearly symmetric volume fractions was synthesized by grafting from a symmetrical triblock backbone and the resulting melt was characterized by scanning electron microscopy and small-angle X-ray scattering. The copolymer backbone was prepared by sequential reversible addition–fragmentation chain transfer (RAFT) polymerization of solketal methacrylate (SM), 2-(bromoisobutyryl)ethyl methacrylate (BIEM), and 5-(trimethylsilyl)-4-pentyn-1-ol methacrylate (TPYM). PMMA branches were grafted by atom transfer radical polymerization from the poly(BIEM) segment, PS branches were grafted by RAFT polymerization from the poly(TPYM) block after installment of the RAFT agents, while PLA side chains were grafted from the deprotected poly(SM) block. The resulting copolymer was found to exhibit a lamellae morphology with a domain spacing of 79 nm. Differential scanning calorimetry analysis indicated that PMMA was preferentially mixing with PS while phase separating from PLA domains.

Bolton, Justin↗

Shock compression of poly(methyl methacrylate) PMMA in the 1000 GPa regime: Z machine experiments

Hydrocarbon polymers are used in a wide variety of practical applications. In the field of dynamic compression at extreme pressures, these polymers are used at several high energy density (HED) experimental facilities. One of the most common polymers is poly(methyl methacrylate) or PMMA, also called Plexiglass® or Lucite®. Here, we present high-fidelity, hundreds of GPa range experimental shock compression data measured on Sandia’s Z machine. We extend the principal shock Hugoniot for PMMA to more than threefold compression up to 650 GPa and re-shock Hugoniot states up to 1020 GPa in an off-Hugoniot regime, where experimental data are even sparser. These data can be used to put additional constraints on tabular equation of state (EOS) models. The present results provide clear evidence for the need to re-examine the existing tabular EOS models for PMMA above ~120 GPa as well as perhaps revisit EOSs of similar hydrocarbon polymers commonly used in HED experiments investigating dynamic compression, hydrodynamics, or inertial confinement fusion.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗