Multiscale modeling of elastic properties of cortical bone

We model cortical bone as a composite material with hierarchical structure. At a nanostructural level, bone is composed of cross-linked collagen molecules, containing water and non-collagenous proteins in their gaps, reinforced with hydroxyapatite-like nanocrystals. Such a nanocomposite structure represents a mineralized collagen fibril, which serves as a primary building block of bone. At a sub-microstructural level (few microns), the mineralized collagen fibrils are embedded in an extrafibrillar hydroxyapatite matrix to form a single lamella, which also contains the lacunar cavities. At a microstructural level (hundreds of microns) one can distinguish two lamellar structures in the mature cortical bone: osteons, made of concentric layers of lamellae surrounding long hollow Haversian canals, and interstitial lamellae made of remnants of old osteons. At a mesostructural level (several millimeters), the cortical bone is represented by a random collection of osteons and resorption cavities in the interstitial lamellae. A macrostructural level is the whole bone level containing both the cortical (compact) and trabecular (spongy) bone types. In this paper, we predict analytically the effective elastic constants of cortical bone by modeling its elastic response at these different scales, spanning from the nanostructural to mesostructural levels, using micromechanics methods and composite materials laminate theories. The results obtained at a lower scale serve as inputs for the modeling at a higher scale. The predictions are in good agreement with the experimental data reported in literature.     

Modeling and Management of Firewall Policies

Firewalls are core elements in network security. However, managing firewall rules, especially for enterprise networks, has become complex and error-prone. Firewall filtering rules have to be carefully written and organized in order to correctly implement the security policy. In addition, inserting or modifying a filtering rule requires thorough analysis of the relationship between this rule and other rules in order to determine the proper order of this rule and commit the updates. In this paper we present a set of techniques and algorithms that provide automatic discovery of firewall policy anomalies to reveal rule conflicts and potential problems in legacy firewalls, and anomaly-free policy editing for rule insertion, removal, and modification. This is implemented in a user-friendly tool called ?Firewall Policy Advisor.? The Firewall Policy Advisor significantly simplifies the management of any generic firewall policy written as filtering rules, while minimizing network vulnerability due to firewall rule misconfiguration.     

Graphene nanoplatelets dispersion in poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactic acid): preparation method and its influence on electrical,crystallinity and thermomechanical properties

Poly(l-lactic acid) (PLLA)/graphene nanoplatelets (GnP) nanocomposites were prepared through solvent casting and coagulation methods. The better dispersion of graphene was achieved by ultrasounds and its effect on crystallinity, thermomechanical and electrical properties of PLLA were studied and compared in both methods. Differential scanning calorimetry (DSC) was used to investigate the crystallinity of PLLA and its composites. Field emission gun scanning electron microscope (FEG-SEM) and wide-angle X-ray scattering (WAXS) were employed to characterize the microstructure of PLLA crystallites. Dynamic mechanical thermal analysis (DMTA) was performed to study the thermomechanical properties of the nanocomposites. FEG-SEM images illustrated finer dispersion of GnP in samples obtained by coagulation method with respect to solvent casting method. Graphene imparted higher electrical conductivity to nanocomposites obtained by solvent casting under ultrasound due to better formation of graphene network. DSC thermograms and their resulting data showed positive effects of GnP on crystallization kinetics of PLLA in both methods enhanced by the nucleating effect of graphene particles. Meanwhile, the effect of GnP, as nucleating agent, was more prominent in samples produced by coagulation method without utilization of ultrasounds. WAXS patterns represented the same characteristic peaks of PLLA in nanocomposite specimens suggesting similar crystalline structure of PLLA in presence of graphene, and the intensified peaks of nanocomposites compared to neat PLLA confirmed the DSC results regarding its improved crystallinity. Graphene increased storage modulus in rubbery region and glass transition temperature of nanocomposites in the coagulation method due to restricted mobility of PLLA chains.     

A modified thermodynamic insight to deliquescence of a void‐containing nanocrystal confirmed by MD simulation

Existence of voids in crystalline structures can affect their physical and chemical properties considerably. When the size of the crystal reaches to nanoscale, experimental determination of its void fraction is difficult. In this work, a molecular dynamics approach is introduced to find equilibrium void fractions of a simple cubic (CsCl) and fcc (KCl) nanocrystals by determination of their deliquescence relative humidity (DRH) for different sizes and void fractions and extrapolation of the results to the bulk limit. To confirm the simulation results, the size dependency of DRH to the nanoparticle size was studied thermodynamically by inclusion of size‐dependent density of water nanodroplet which leads to a simple homographic equation. This method proposes the equilibrium void percents of CsCl and KCl nanoparticles to be 10 and 15%, respectively, which are obtained by extrapolation of the results to the bulk limit. The success of obtained Möbius function was also confirmed by fitting it to experimental data for deliquescence of NaCl nanoparticles which implies the importance of considering density of water nanodroplet as a size dependent quantity. Also, using the mentioned thermodynamic approach, void dependency of deliquescence for the nanoparticles was found to be as a quasi‐linear trend which is compatible with the simulation results. It is noticeable that the approach used this work for determination of equilibrium void fraction is only valid if the utilized force fields are accurate. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4066–4077, 2016     

Unveiling the presence of mixed oxidation states of Europium in Li7+δEuxLa3−δZr2−δO12−δ garnet and its impact on the Li-ion conductivity

Recently, lanthanides have been employed by researchers to examine their impact on the structure and properties of Li₇La₃Zr₂O₁₂ (LLZO) garnets. In this regard, we developed Europium oxide (Eu₂O₃) doped LLZO (Li_7+δEu_xLa_3−δZr_2−δO_12−δ) solid electrolyte which demonstrates a cubic phase with the symmetry of Iad (No.230) at room temperature. In this investigation, different concentrations of Eu ranging from 0.1 to 0.6 atoms per formula unit (pfu) were doped into Li₇La₃Zr₂O₁₂ to evaluate the impact of Eu on the stability of the cubic phase and thereby the ionic conductivity. The results unveiled that upon doping Eu³⁺ ions, the Eu²⁺ state is also formed and is then self-doped into the structure in which Rietveld refinement coupled with XPS, EPR, and solid-state NMR suggests that Eu³⁺ ions most probably partially occupy Zr⁴⁺ (16a) site, the Eu²⁺ ions occupy La³⁺ (24d) site, and the Li⁺ ions occupy two different sites (24d and 96h). It was further found that such a site preference induces distortion at LaO₈ polyhedrons opening up the neck for Li-ions diffusion, thereby enhancing the ionic conductivity. Moreover, it was revealed that Li-ions probably hop from 96h to 24d and then to 96h site to generate the Li-ion movement. Overall, by introducing Eu ions into the LLZO structure, an enhanced bulk ionic conductivity of 0.30 × 10⁻³ S/cm at 298 K with a minimum electronic conductivity of 2.547 × 10⁻⁹ S/cm at 298 K was achieved.     

Preparation of porous PLLA/PCL blend by a combination of PEO phase and NaCl particulate leaching in PLLA/PCL/PEO/NaCl blend

In this study, the ternary blends containing microporosity based on poly(l-lactic acid) (PLLA), poly(ε-caprolactone) (PCL) and polyethylene oxide (PEO) were prepared using an internal mixer via a polymer leaching technique. The particulate leaching is the most widely used technique to create porosity. To introduce macroporosity besides micropores, NaCl particulates were incorporated into the ternary blends at 40–80 wt % and macropores were formed by particulate leaching. Samples porosity were evaluated by calculating the ratio of porous scaffold density (ρ*) to the non-porous material density (ρ _s). The results showed that with an increase in NaCl particulate content, the amount of porosity increased and the distribution of pore size was gradually transformed from monomodal into bimodal form. The porosity plays a key role in governing the compression properties. Mechanical properties are presented by Gibson–Ashby model. Compressive modulus decreased with an increase in NaCl particulate concentration due to the increase in porosity and thinning of pore wall that caused rupture at these weaker spots. Blending and forming of the bio-scaffold can be made using conventional polymer processing equipment. This process seems promising for a large-scale production of porous bio-scaffold of many sizes through an economic method.     

Investigating Factors Affecting Water-In-Diesel Fuel Nanoemulsions

In this work, water-in-diesel fuel nanoemulsions were prepared with mixed nonionic surfactants. Several mixtures of sorbitan monooleate and polyoxyethylene (20) sorbitan monooleate, with different Hydrophilic–Lipophilic Balance (HLB) values (9.6, 9.8, 10, 10.2 and 10.4) were prepared to achieve the optimal HLB value. Three mixed surfactant concentrations were prepared at 6, 8 and 10 wt% to identify the optimum concentration. Five emulsions with different water contents: 5, 6, 7, 8 and 9 % (wt/wt) were prepared using a high energy method under the optimum conditions (HLB = 10 and mixed surfactant concentration = 10 %). The effect of the HLB value, mixed surfactant concentration and water content on the droplet size has been studied. The interfacial tension and thermodynamic properties of the individual and the blended emulsifiers were investigated. Droplet size of the prepared nanoemulsions was determined by dynamic light scattering and the nanoemulsion stability was assessed by measuring the variation of the droplet size as a function of time. From the results obtained, it was found that the mean droplet size was formed between 49.5 and 190 nm depending on the HLB value, surfactant concentration and water content of the blended emulsifiers.     

ADHESION OF ELASTOMERS: DWELL TIME EFFECTS

The strength of adhesion of elastomers to rigid substrates generally increases with time of contact. This effect has been studied for samples of butyl and chlorobutyl rubber adhering to some rigid substrates. The peel strength increased continuously over long periods of contact until in some cases failure became cohesive within the elastomer layer. At higher temperatures the strength increased more rapidly, consistent with the WLF relation governing molecular motions. It is postulated that slow molecular rearrangements occur at the interface and increase the bond strength. A criterion for the observed transition from interfacial to cohesive failure is suggested.     

Simultaneous multi-objective optimization of a new promoted ethylene dimerization catalyst using grey relational analysis and entropy measurement

A hybrid approach between the Taguchi method and grey relational analysis (GRA) with entropy measurement was applied to determine a single optimum setting for reaction factors of the proposed ethylene dimerization catalyst having overall selectivity to 1-butene (S_1-btn (%)) and turnover frequency (TOF (h^-1)) as multiple quality characteristics. Titanium tetrabutoxide (Ti(OC₄H₉)₄) catalyst precursor in combination with triethyl aluminum (TEA) activator, 1,4-dioxane as a suitable modifier, and ethylene dichloride (EDC) as a novel promoter were used in the catalysis. Control factors of temperature, pressure, Al/Ti, 1,4-dioxane/Ti, and EDC/Ti mol ratios were investigated on three levels and their main effects were discussed. The effect of the binary interaction between temperature, pressure, and Al/Ti mol ratio was also examined. Weight of the responses was determined using entropy. Analysis of variance (ANOVA) for data obtained from GRA indicated that EDC/Ti mol ratio with 27.64% contribution had the most profound effect on the multiple quality characteristics. Development of the weighted Grey-Taguchi method used the Taguchi method as its basic structure, adopted GRA to deal with multiple responses, and entropy to enhance the reasonability of the comprehensive index produced by GRA to make the results more objective and accurate. Overall, these combined mathematical techniques improved catalytic performance for 1-butene production.