Silane functionalization of perfluoroether oligomers for reaction management and morphology control of two‐phase epoxy networks

Mixtures of an epoxy resin, hardener, and acid functionalized perfluoroether oligomers will readily undergo phase separation during curing. However, the conditions to bring about the growth of nuclei into microscopic particles have hitherto been found only for systems cured with anhydrides. In the present study perfluoroether oligomers were functionalized by established procedures to introduce both carboxylic acid groups and alkoxysilane groups in sites within the chain extended segments. The presence of alkoxysilane groups together with the prereaction step with an excess epoxy resin, prior to the addition of the aromatic amine hardener, induced phase separation by a nucleation‐and‐growth mechanism. The dual functionality in the perfluoroether oligomer was even more beneficial when the alkoxysilane groups were hydrolyzed prior to the addition of the amine hardener. Under such circumstances the precipitation of the perfluoroether oligomer occurred quantitatively, as indicated by the complete absence of any plasticization effects in the epoxy matrix. From electron microscopy examinations, thermal analysis, and measurements of mechanical properties it was possible to deduce a plausible mechanism for the formation of the typical core‐shell aggregates within the precipitated particles for these systems, which could also be applied to other systems, such as those using carboxylic‐acid‐terminated butadiene acrylonitrile oligomers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1036–1049, 2005     

MPaaS: Mobility prediction as a service in telecom cloud

Mobile applications and services relying on mobility prediction have recently spurred lots of interest. In this paper, we propose mobility prediction based on cellular traces as an infrastructural level service of telecom cloud. Mobility Prediction as a Service (MPaaS) embeds mobility mining and forecasting algorithms into a cloud-based user location tracking framework. By empowering MPaaS, the hosted 3rd-party and value-added services can benefit from online mobility prediction. Particularly we took Mobility-aware Personalization and Predictive Resource Allocation as key features to elaborate how MPaaS drives new fashion of mobile cloud applications. Due to the randomness of human mobility patterns, mobility predicting remains a very challenging task in MPaaS research. Our preliminary study observed collective behavioral patterns (CBP) in mobility of crowds, and proposed a CBP-based mobility predictor. MPaaS system equips a hybrid predictor fusing both CBP-based scheme and Markov-based predictor to provide telecom cloud with large-scale mobility prediction capacity.     

On detecting co-resident cloud instances using network flow watermarking techniques

Virtualization is the cornerstone of the developing third-party compute industry, allowing cloud providers to instantiate multiple virtual machines (VMs) on a single set of physical resources. Customers utilize cloud resources alongside unknown and untrusted parties, creating the co-resident threat—unless perfect isolation is provided by the virtual hypervisor, there exists the possibility for unauthorized access to sensitive customer information through the exploitation of covert side channels. This paper presents co-resident watermarking, a traffic analysis attack that allows a malicious co-resident VM to inject a watermark signature into the network flow of a target instance. This watermark can be used to exfiltrate and broadcast co-residency data from the physical machine, compromising isolation without reliance on internal side channels. As a result, our approach is difficult to defend against without costly underutilization of the physical machine. We evaluate co-resident watermarkingunder a large variety of conditions, system loads and hardware configurations, from a local laboratory environment to production cloud environments (Futuregrid and the University of Oregon’s ACISS). We demonstrate the ability to initiate a covert channel of 4 bits per second, and we can confirm co-residency with a target VM instance in $<$ 10 s. We also show that passive load measurement of the target and subsequent behavior profiling is possible with this attack. We go on to consider the detectability of co-resident watermarking, extending our scheme to create a subtler watermarking attack by imitating legitimate cloud customer behavior. Our investigation demonstrates the need for the careful design of hardware to be used in the cloud.     

Improved activity and thermostability of Candida antarctica lipase B by DNA family shuffling

DNA family shuffling was used to create chimeric lipase B proteins with improved activity toward the hydrolysis of diethyl 3-(3',4'-dichlorophenyl)glutarate (DDG). Three homologous lipases from Candida antarctica ATCC 32657, Hyphozyma sp. CBS 648.91 and Crytococcus tsukubaensis ATCC 24555 were cloned and shuffled to generate a diverse gene library. A high-throughput screening assay was developed and used successfully to identify chimeric lipase B proteins having a 20-fold higher activity toward DDG than lipase B from C.antarctica ATCC 32657 and a 13-fold higher activity than the most active parent derived from C.tsukubaensis ATCC 24555. In addition, the stability characteristics of several highly active chimeric proteins were also improved as a result of family shuffling. For example, the half-life at 45 degrees C and melting point (T(m)) of one chimera exceeded those of lipase B from C.antarctica ATCC 32657 by 11-fold and 6.4 degrees C, respectively, which closely approached the stability characteristics of the most thermostable parent derived from Hyphozyma sp. CBS 648.91.     

Ambient-pressure thermogravimetric characterization of four different coals and their chars

Ambient-pressure thermogravimetric characterization of four different coals and their chars was performed to obtain fundamental information on pyrolysis and coal and char reactivity for these materials. Using a Perkin-Elmer TGS-1 thermobalance, weight loss as a function of temperature was systematically determined for each coal heated in helium at 40 and 160 °C/min under various experimental conditions, and for its derived char heated in air over a temperature range of 20 to 1000 °C. The results indicate that the temperature of maximum rate of devolatilization increases with increasing heating rate for all four coals. However, heating rate does not have a significant effect on the ultimate yield of total volatiles upon heating in helium to 1000 °C; furthermore, coupled with previous data⁹ for identical coal samples, this conclusion extends over a wide range of heating rate from 0.7 to 1.5 × 10⁴ °C/s. Using the temperature of maximum rate of devolatilization as an indication of relative reactivity, the devolatilization reactivity differences among the four coals tested that were suggested by this criterion are not large. For combustion in air, the overall coal/char reactivity sequence as determined by comparison of sample ignition temperature is: N. Dakota lignite coal ≈ Montana lignite coal > North Dakota lignite char > III. No. 6 bituminous coal ≈ Pittsburgh Seam bituminous coal > Montana lignite char > III. No. 6 bituminous char > Pittsburgh Seam bituminous char. The reactivity differences are significantly larger than those for devolatilization. The reactivity results obtained suggest that coal type appears to be the most important determinant of coal and char reactivity in air. The weight loss data were fitted to a distributed-activation-energy model for coal pyrolysis; the kinetic parameters so computed are consistent with the view that coal pyrolysis involves numerous parallel first-order organic decomposition reactions.     

Viscoelastic effects on the scratch resistance of polymers: relationship between mechanical properties and scratch properties at various temperatures

Scratch durability of polymer surfaces and coatings is becoming critical for the increasing use of these materials in new applications, replacing other materials with harder surfaces.

Scratch resistance of polymers has been the subject of numerous studies, which have led to specific definitions for plastic deformation characterization and fracture resistance during scratch testing. Viscoelastic and viscoplastic behavior during a scratch process have been related to dynamic mechanical properties that can be measured via dynamic nano-indentation testing. Yet, the understanding of the origin of the fracture process of a polymer during scratch remains approximate. Parameters like tip shape and size, scratch velocity and loading rate, applied strain and strain rates, have been considered critical parameters for the fracture process, but no correlation has been clearly established.

The goal of this work is to define and analyze scratch parameters that relate to mechanical properties. The evolution of scratch resistance parameters as a function of temperature and strain rate, compared to the evolution of dynamic mechanical properties obtained from indentation and uniaxial tensile tests over a range of temperature for poly(methyl methacrylate) (PMMA) helped in identifying a correlation between the tensile stress–strain behavior and scratch fracture toughness.

This correlation brings a new understanding of the origin of the fracture mechanisms during a scratch process. In particular, it is demonstrated that the characteristic strain applied by the indenter is a most relevant parameter to describe the fracture resistance during a scratch process, independently of the indenter geometry.     

Contribution of the C-terminal amino acid to the stability of Bacillus subtilis neutral protease

The role of the C-terminal Leu300 in maintaining thermal stabilityof the neutral protease of Bacillus subtilis was investigated.From model building studies based on the three dimensional structureof thermolysin, the neutral protease of B.thermoproteolyticus,it was conduded that this residue is located in a hydrophobicpocket composed of residues located in the C-terminal and themiddle domain. To test the hypothesis that Leu300, by contributingto a stabilizing interaction between these domains, is importantfor enzyme stability, several neutral protease mutants wereconstructed and characterized. The thermostability of the enzymewas lowered by deleting Leu300 or by replacing this residueby a smaller (Ala), a polar (Asn) or a sterically unfavourable(He) amino acid. Thermostabiity was increased upon replacingLeu300 by Phe. These results are in agreement with model-buildingstudies. The effects on thermostability observed after mutatingthe corresponding Val318 in the thermostable neutral proteaseof B.stearothermophilus were less pronounced.     

Improvements in seismic event locations in a deep western U.S. coal mine using tomographic velocity models and an evolutionary search algorithm

Methods of improving seismic event locations were investigated as part of a research study aimed at reducing ground control safety hazards. Seismic event waveforms collected with a 23-station three-dimensional sensor array during longwall coal mining provide the data set used in the analyses. A spatially variable seismic velocity model is constructed using seismic event sources in a passive tomographic method. The resulting three-dimensional velocity model is used to relocate seismic event positions. An evolutionary optimization algorithm is implemented and used in both the velocity model development and in seeking improved event location solutions. Results obtained using the different velocity models are compared. The combination of the tomographic velocity model development and evolutionary search algorithm provides improvement to the event locations.     

Formation and Properties of Chalcogenide Glasses in the GeSe2–As2Se3–CdSe System

The glass-forming region in a GeSe₂–As₂Se₃–CdSe system and the dependence of properties on glass compositions as a formula of 70GeSe₂–(30− x )As₂Se₃– x CdSe ( x =0–25) were investigated. Measurements included density, micro-hardness, differential scanning calorimetry (DSC), X-ray diffraction, and IR transmission spectra. A large glass-forming region was shown while addition of Cd increases the crystallization trend of the system. Besides, the Cd content accommodated by the system to form glass is found to be lower in the As₂Se₃-rich region than in the GeSe₂-rich region. With the introduction of CdSe, density, micro-hardness, and T _g of glasses increase whereas an exothermal peak in the DSC curve appears and thermal stability (Δ T ) decreases. The activation energy of crystallization and the Avrami exponent were also obtained using the modified Ozawa equation.     

Kinetics and mechanism of ?-caprolactone and l,l-lactide polymerization coinitiated with zinc octoate or aluminum acetylacetonate: The next proofs for the general alkoxide mechanism and synthetic applications

Following our previous papers on mechanism of cyclic esters' polymerization coinitiated by tin(II) octoate [tin(II) bis-(2-ethylhexanoate), (Sn(Oct)₂)] in the presence of either the low molar mass coinitiator (an alcohol, hydroxy acid, or H₂O) or a macromolecule fitted with a hydroxy end group (ROH), the present work deals with ?-caprolactone (CL) and l,l-lactide (LA) polymerizations coinitiated with zinc octoate (Zn(Oct)₂) or aluminum acetylacetonate (Al(Acac)₃). A series of kinetic measurements revealed that similarly as in the Sn(Oct)₂ coinitiated process, these polymerizations proceed by simple monomer insertion into the …Mt-OR bond, reversibly formed in the reaction -Mt-L + ROH ? …-Mt-OR + LH (where Mt = Sn, Zn or Al; L = Oct or Acac), taking place throughout the whole polymerization process. MtL_n itself does not play an active role in the polymerization. Applicability of the commercially available Zn(Oct)₂ or Al(Acac)₃ for the aliphatic polyester (10³ ≤ M_n ≤ 4 × 10⁵) synthesis is also discussed.