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At least 973 records · Page 54

Microscopic ergodicity breaking governs the emergence and evolution of elasticity in glass-forming nanoclay suspensions

We report a study combining x-ray photon correlation spectroscopy (XPCS) with in situ rheology to investigate the microscopic dynamics and mechanical properties of aqueous suspensions of the synthetic hectorite clay Laponite, which is composed of charged, nanometer-scale, disk-shaped particles. The suspensions, with particle concentrations ranging from 3.25 to 3.75 wt%, evolve over time from a fluid to a soft glass that displays aging behavior. The XPCS measurements characterize the localization of the particles during the formation and aging of the soft-glass state. The fraction of localized particles f 0 increases rapidly during the early formation stage and grows more slowly during subsequent aging, while the characteristic localization length r loc steadily de- creases. Despite the strongly varying rates of aging at different concentrations, both f 0 and r loc scale with the elastic shear modulus G' in a manner independent of concentration. During the later aging stage, the scaling between r loc and G' agrees quantitatively with a prediction of naive mode coupling theory. Breakdown of agreement with the theory during the early formation stage indi- cates the prevalence of dynamic heterogeneity, suggesting the soft solid forms through precursors of dynamically localized clusters.

36 MATERIALS SCIENCE↗

Random Close Packing as a Dynamical Phase Transition

Sphere packing is an ancient problem. The densest packing is known to be a face-centered cubic (FCC) crystal, with space-filling fraction Φ FCC = π / √ 18 ≈ 0.74 . The densest “random packing,” random close packing (RCP), is yet ill defined, although many experiments and simulations agree on a value Φ RCP ≈ 0.64 . We introduce a simple absorbing-state model, biased random organization (BRO), which exhibits a Manna class dynamical phase transition between absorbing and active states that has as its densest critical point Φ cmax ≈ 0.64 ≈ Φ RCP and, like other Manna class models, is hyperuniform at criticality. The configurations we obtain from BRO appear to be structurally identical to RCP configurations from other protocols. This leads us to conjecture that the highest-density absorbing state for an isotropic biased random organization model produces an ensemble of configurations that characterizes the state conventionally known as RCP.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Structural magnetic glassiness in the spin ice Dy 2 Ti 2 O 7

The origin and nature of glassy dynamics presents one of the central enigmas of condensed-matter physics across a broad range of systems ranging from window glass to spin glasses. The spin-ice compound Dy 2 Ti 2 O 7 , which is perhaps best known as hosting a three-dimensional Coulomb spin liquid with magnetically charged monopole excitations, also falls out of equilibrium at low temperature. How and why it does so remains an open question. Based on an analysis of low-temperature diffuse neutron-scattering experiments employing different cooling protocols alongside recent magnetic noise studies, combined with extensive numerical modeling, we argue that upon cooling, the spins freeze into what may be termed a “structural magnetic glass,” without an a priori need for chemical or structural disorder. Specifically, our model indicates the presence of frustration on two levels, first producing a near-degenerate constrained manifold inside which phase ordering kinetics is in turn frustrated. A remarkable feature is that monopoles act as sole annealers of the spin network and their pathways and history encode the development of glass dynamics, allowing the glass formation to be visualized. Our results suggest that spin ice Dy 2 Ti 2 O 7 provides one prototype of magnetic glass formation specifically and a setting for the study of kinetically constrained systems more generally.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Liquid fragility maximum in lithium borate glass‐forming melts related to the local structure

Abstract The structure of liquid lithium pyroborate, Li 4 B 2 O 5 ( J = Li/B = 2), has been measured over a wide temperature range by high‐energy X‐ray diffraction, and compared to that of its glass and borate liquids of other compositions. The results indicate a gradual increase in tetrahedral boron fraction from 3(1)% to 6(1)% during cooling from T = 1271(15) to 721(8) K, consistent with the larger N 4 = 10(1)% found for the glass, and literature 11 B nuclear magnetic resonance measurements. van't Hoff analysis based on a simple boron isomerization reaction BØ 3 O 2 – ⇌ BØO 2 2– yields Δ H = 13(1) kJ mol –1 and Δ S = 40(1) J mol –1 K –1 for the boron coordination change from 4 to 3, which are, respectively, smaller and larger than found for singly charged isomers for J ≤ 1. With these, we extend our model for N 4 ( J , T ), nonbridging oxygen fraction f nbr ( J , T ), configurational heat capacity , and entropy S conf ( J , T ) contributions up to J = 3. A maximum is revealed in at J = 1, and shown semi‐quantitatively to lead to a corresponding maximum in fragility contribution, akin to that observed in the total fragilities by temperature‐modulated differential scanning calorimetry. Lithium is bound to 4.6(2) oxygen in the pyroborate liquid, with 2.7(1) bonds centered around 1.946(8) Å and 1.9(1) around 2.42(1) Å. In the glass, n LiO = 5.4(4), the increase being due to an increase in the number of short Li–O bonds.

36 MATERIALS SCIENCE↗

Polymer Macrocycles: A novel topology to control dynamics of rubbery materials (Final Report)

We have successfully made synthetic polymer rings that are larger than previously reported having entanglement numbers as high as Z w ≈300 if the rings entangled as do linear chains. The synthesis was carried out using reversible radical recombination polymerization (R3P) of dithiols which produces a polymer with a very small persistence length. The reported results show surprising dilute solution behaviors due to the fact that polymeric rings expand more than their linear counterparts for polymer chains having a large number of persistence lengths, as developed in this study. The results strongly argue for a systematic investigation of the dilute solution properties of rings having different persistence lengths in different quality solvents, where the theta-condition should lead to results that are independent of the persistence length. For the rheological investigations related to chain entanglements, the polyDODT rings could be diluted so that the rheological data covered from less than one entanglement spacing relative to the linear counterpart to a value of Z w =300. Importantly, because we were able to dilute extremely high entanglement number polyDODT rings to a similar entanglement number as those reported for polystyrene rings that were highly purified using LCCC, we demonstrated that the dynamics of the polyDODT rings virtually overlaps with the dynamics of the polystyrene rings which is very strong evidence that these high molecular weight polyDODT rings are of high purity. Our results demonstrate that the onset of entanglement in rings, as evidenced by the appearance of a rubbery plateau G N 0 and by the onset of a strong power-law dependence of the viscosity on molecular weight (η~M w 5.8 ) or entanglement number (η~Z w 5.8 ), occurs at much higher molecular weights or polymer concentrations than is the case for linear chains. These results should serve as a benchmark for future investigations of the behavior of entangled, circular macromolecules.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Polymer Macrocycles: A novel topology to control dynamics of rubbery materials

We have successfully made synthetic polymer rings that are larger than previously reported having entanglement numbers as high as $Z_w$≈300 if the rings entangled as do linear chains. The synthesis was carried out using reversible radical recombination polymerization (R3P) of dithiols which produces a polymer with a very small persistence length. The reported results show surprising dilute solution behaviors due to the fact that polymeric rings expand more than their linear counterparts for polymer chains having a large number of persistence lengths, as developed in this study. The results strongly argue for a systematic investigation of the dilute solution properties of rings having different persistence lengths in different quality solvents, where the theta-condition should lead to results that are independent of the persistence length. For the rheological investigations related to chain entanglements, the polyDODT rings could be diluted so that the rheological data covered from less than one entanglement spacing relative to the linear counterpart to a value of $Z_w$=300. Importantly, because we were able to dilute extremely high entanglement number polyDODT rings to a similar entanglement number as those reported for polystyrene rings that were highly purified using LCCC, we demonstrated that the dynamics of the polyDODT rings virtually overlaps with the dynamics of the polystyrene rings which is very strong evidence that these high molecular weight polyDODT rings are of high purity. Our results demonstrate that the onset of entanglement in rings, as evidenced by the appearance of a rubbery plateau $G_N^0$ and by the onset of a strong power-law dependence of the viscosity on molecular weight (η~$M_w^{5.8}$) or entanglement number (η~$Z_w^{5.8}$), occurs at much higher molecular weights or polymer concentrations than is the case for linear chains. These results should serve as a benchmark for future investigations of the behavior of entangled, circular macromolecules.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Wavelength dispersive analysis with the synchrotron x ray fluorescence microprobe

A wavelength dispersive spectrometer (WDS) was tested on the synchrotron x ray fluorescence microprobe at Brookhaven National Laboratory. Compared to WDS spectra using an electron microprobe, the synchrotron WDS spectra have much better sensitivity and, due to the absence of bremsstrahlung radiation, lower backgrounds. The WDS spectrometer was successfully used to resolve REE L fluorescence spectra from standard glasses and transition metal K fluorescence spectra from kamacite.

Rivers, M. L.↗

The Effect of Heating on the Degradation of Ground Laboratory and Space Irradiated Teflon(r) FEP

The outer most layer of the multilayer insulation (MLI) blankets on the Hubble Space Telescope (HST) is back surface aluminized Teflon(R) FEP (fluorinated ethylene propylene). As seen by data collected after each of the three servicing missions and as observed during the second servicing mission (SM2), the FEP has become embrittled in the space environment, leading to degradation of the mechanical properties and severe on-orbit cracking of the FEP. During SM2, a sample of aluminized-FEP was retrieved from HST that had cracked and curled, exposing its aluminum backside to space. Because of the difference in optical properties between FEP and aluminum, this insulation piece reached 200 C on-orbit, which is significantly higher than the nominal MLI temperature extreme of 50 C. This piece was more brittle than other retrieved material from the first and third servicing missions (SM1 and SM3A, respectively). Due to this observation and the fact that Teflon thermal shields on the solar array bi-stems were heated on-orbit to 130 C, experiments have been conducted to determine the effect of heating on the degradation of FEP that has been irradiated in a ground laboratory facility or in space on HST. Teflon FEP samples were X-ray irradiated in a high vacuum facility in order to simulate the damage caused by radiation in the space environment. Samples of pristine FEP, X-ray irradiated FEP and FEP retrieved from the HST during SM3A were heat treated from 50 to 200 C at 25 intervals in a high vacuum facility and then tensile tested. In addition, samples were tested in a density gradient column to determine the effect of the radiation and heating on the density of FEP. Results indicate that although heating does not degrade the tensile properties of non-irradiated Teflon, there is a significant dependence of the percent elongation at failure of irradiated Teflon as a function of heating temperature. Irradiated Teflon was found to undergo increasing degradation in the elongation at failure as temperature was increased from room temperature to 200 C. Rate of degradation changes, which were consistent with the glass I transition temperatures for FEP, appeared to be present in both tensile and density data. The results indicate the significance of the on-orbit temperature of Teflon FEP with respect to its degradation in the low Earth orbital space environment.

deGroh, Kim K.↗

Surface Control of Cold Hibernated Elastic Memory Self-Deployable Structure

A new class of simple, reliable, lightweight, low packaging volume and cost, self-deployable structures has been developed for use in space and commercial applications. This technology called 'cold hibernated elastic memory' (CHEM) utilizes shape memory polymers (SMP)in open cellular (foam) structure or sandwich structures made of shape memory polymer foam cores and polymeric composite skins. Some of many potential CHEM space applications require a high precision deployment and surface accuracy during operation. However, a CHEM structure could be slightly distorted by the thermo-mechanical processing as well as by thermal space environment Therefore, the sensor system is desirable to monitor and correct the potential surface imperfection. During these studies, the surface control of CHEM smart structures was demonstrated using a Macro-Fiber Composite (MFC) actuator developed by the NASA LaRC and US Army ARL. The test results indicate that the MFC actuator performed well before and after processing cycles. It reduced some residue compressive strain that in turn corrected very small shape distortion after each processing cycle. The integrated precision strain gages were detecting only a small flat shape imperfection indicating a good recoverability of original shape of the CHEM test structure.

glass transition temperature Tg↗

Reliability of PWB Microvias for High Density Package Assembly

High density PWB (printed wiring board) with microvia technology is required for implementation of high density and high I/O area array packages (AAP). COTS (commercial off-the-shelf) AAP packaging technologies in high reliability versions with 1.27 mm pitch are now being considered for use in a number of NASA systems including Space Shuttle and Mars Rovers. NASA functional system designs are requiring more and more dense AAP packages and board space, which makes board microvia technology very attractive for effectively routing a large number of package inputs/outputs. However, the reliability of the fine feature microvias including via in pads is unknown for space applications. Understanding process and QA (quality assurance) indicators for reliability are important for low risk insertion of these newly available packages and PWBs. This paper presents literature search as well as test results for a high density board subjected to various thermal cycle and reflow profiles representative of tin-lead and lead-free solder reflow. Microvias sizes ranged from two to six mil with and without filling. Daisy chain microvias monitored during the test and PWBs were cross-sectioned to determine failure and locations. Optical and SEM photographs as well as resistance changes during cycling and Tg/Td (glass transition/decomposition temperature) characterisations are presented.

fill via↗

The Effect of Heating on the Degradation of Ground Laboratory and Space Irradiated Teflon® FEP

The outer most layer of the multilayer insulation (MLI) blankets on the Hubble Space Telescope (HST) is back surface aluminized Teflon® FEP (fluorinated ethylene propylene). As seen by data collected after each of the three servicing missions and as observed during the second servicing mission (SM2), the FEP has become embrittled in the space environment, leading to degradation of the mechanical properties and severe on-orbit cracking of the FEP. During SM2, a sample of aluminized-FEP was retrieved from HST that had cracked and curled, exposing its aluminum backside to space. Because of the difference in optical properties between FEP and aluminum, this insulation piece reached 200 C on-orbit, which is significantly higher than the nominal MLI temperature extreme of 50 C. This piece was more brittle than other retrieved material from the first and third servicing missions (SM1 and SM3A, respectively). Due to this observation and the fact that Teflon thermal shields on the solar array bi-stems were heated on-orbit to 130 C, experiments have been conducted to determine the effect of heating on the degradation of FEP that has been irradiated in a ground laboratory facility or in space on HST. Teflon FEP samples were x-ray irradiated in a high vacuum facility in order to simulate the damage caused by radiation in the space environment. Samples of pristine FEP, x-ray irradiated FEP and FEP retrieved from the HST during SM3A were heat treated from 50 to 200 C at 25intervals in a high vacuum facility and then tensile tested. In addition, samples were tested in a density gradient column to determine the effect of the radiation and heating on the density of FEP. Results indicate that although heating does not degrade the tensile properties of non-irradiated Teflon, there is a significant dependence of the percent elongation at failure of irradiated Teflon as a function of heating temperature. Irradiated Teflon was found to undergo increasing degradation in the elongation at failure as temperature was increased from room temperature to 200 C. Rate of degradation changes, which were consistent with the glass I transition temperatures for FEP, appeared to be present in both tensile and density data. The results indicate the significance of the on-orbit temperature of Teflon FEP with respect to its degradation in the low Earth orbital space environment.

Hubble Space Telescope↗

The Death of Airmanship: The Urgent Need to Understand Pilot Skills and Knowledge

Aviation awards a special name—airmanship—for the quality of being highly competent in foundational piloting skills, which seem to comprise primarily judgment, decision making, stick-and-rudder skills, and a bit of intuition. The term, which has a mystical quality, has historically resisted analysis; airmanship is acquired solely through experience. The graying of the Boomers and the extreme turbulence of the last few years in commercial aviation have led to a significant loss of those pilots who started out in simpler, round-dial airplanes and made a tortured transition to glass. Those pilots were comfortable disengaging the autopilot at any time, and more importantly, they continued to stay mentally engaged with flight and systems management even as automation continued to encroach on traditional pilot roles. As an industry, we need to prepare for the loss of these pilots by understanding the elements of airmanship and finding a way to replace the competency. The goal is to eliminate “airmanship” by understanding it...by demystifying it. Human factors/cognitive engineering offers tools and methods to develop a system interface that supports skilled performance from the human/technology team. In this presentation, I will talk about my efforts to understand the elements of skilled performance so that they can be trained, or supported by the interface in a seamless manner Specific topics will include the limits of SOP, monitoring for flight path management, alerting non-normals, and autoflight/mode confusion.

pilot skills↗

Quantifying a partial polyamorphic transition in a cerium-based metallic glass during cooling

Cerium-based metallic glasses are prototype polyamorphous systems with pressure-induced polyamorphic transitions extensively reported. Cooling typically has a similar effect on materials as compression with regard to reducing volume. However, previous studies show dramatically different behavior of Ce-based metallic glasses between cooling and compression, whose origin remains unclear. Here, using in situ low-temperature synchrotron high-energy x-ray diffraction, the structural evolution of a Ce68Al10Cu20Co2 metallic glass is accurately determined and analyzed by a structure factor and a reduced pair distribution function (PDF) during cooling from 298 to 83 K. An unusually large linear thermal expansion coefficient is revealed, which is associated with both continuous but inconsistent structural changes between the two subpeaks of the first atomic shell in terms of average bond lengths and coordination numbers. These phenomena are suggested to be attributed to a gradual 4f electron delocalization of only a minimal amount (∼2.6% at 83 K) of Ce atoms by quantitative analysis of the PDF data. However, a previously expected global polymorphic transition from a low-density amorphous state to a high-density amorphous state with an abrupt volume collapse is not observed. Moreover, electrical resistivity also shows a continuous increase during cooling without any sharp change. It is clarified that cryogenic temperatures could facilitate but are not powerful enough alone to trigger a global polymorphic transition in the Ce68Al10Cu20Co2 metallic glass, suggesting a wide distribution of its local atomic environment.

Chen, Zhi↗

Linear and nonlinear mechanical properties of a series of epoxy resins

The linear viscoelastic properties have been measured for a series of bisphenol-A-based epoxy resins cured with the diamine DDS. The linear viscoelastic master curves were constructed via time-temperature superposition of frequency dependent G-prime and G-double-prime isotherms. The G-double-prime master curves exhibited two sub-Tg transitions. Superposition of isotherms in the glass-to-rubber transition (i.e., alpha) and the beta transition at -60 C was achieved by simple horizontal shifts in the log frequency axis; however, in the region between alpha and beta, superposition could not be effected by simple horizontal shifts along the log frequency axis. The different temperature dependency of the alpha and beta relaxation mechanisms causes a complex response of G-double-prime in the so called alpha-prime region. A novel numerical procedure has been developed to extract the complete relaxation spectra and its temperature dependence from the G-prime and G-double-prime isothermal data in the alpha-prime region.

Curliss, D. B.↗