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At least 235 records · Page 13

Mechanical and chemical effects of ion-texturing biomedical polymers

To determine whether sputter etching may provide substantial polymer surface texturing with insignificant changes in chemical and mechanical properties, an 8 cm beam diameter, electron bombardment, argon ion source was used to sputter etch (ion-texture process) nine biomedical polymers. The materials included silicone rubber, 32% carbon impregnated polyolefin, polyoxymethylene, polytetrafluoroethylene, ultrahigh molecular weight (UHMW) polyethylene, UHMW polyethylene with carbon fibers (10%), and several polyurethanes (bioelectric, segmented, and cross linked). Ion textured microtensile specimens of each material except UHMW polyethylene and UHMW polyethylene with 10% carbon fibers were used to determine the effect of ion texturing on tensile properties. Scanning electron microscopy was used to determine surface morphology changes, and electron spectroscopy for chemical analysis was used to analyze the near surface chemical changes that result from ion texturing. Ion energies of 500 eV with beam current densities ranging from 0.08 to 0.19 mA/sq cm were used to ion texture the various materials. Standard microtensile specimens of seven polymers were exposed to a saline environment for 24 hours prior to and during the tensile testing. The surface chemical changes resulting from sputter etching are minimal in spite of the often significant changes in the surface morphology.

Weigand, A. J.↗

Multifunctional polymer composite coatings and adhesives by incorporating cellulose nanomaterials

Regardless of their applications, polymers are still considered mechanically weak and functionally insufficient for certain demanding coating and adhesive uses. To address those issues, nanomaterials have been extensively studied as reinforcing fillers, which have been proven to effectively promote the performance of polymer coatings/adhesives. However, conventional nanofillers are expensive and non-biodegradable. Meanwhile, cellulose nanomaterials (CNMs), a class of nanomaterials produced from biomass feedstocks, can circumvent the drawbacks of conventional nanofillers. Here, this review paper first focuses on the multi-functionalities CNMs bring to polymer coatings, including mechanical reinforcement (wear resistance and hardness enhancement), gas barrier, flame resistance, corrosion resistance, self-healing (controlled-release), optical regulation, self-cleaning/antifouling, and antimicrobial characteristics. Then we discuss the benefits of CNM addition to polymer adhesives, such as mechanical enhancement, curing promotion, volatile organic compound (VOC) suppression, and electrical conductivity. Finally, we provide insights into future research efforts with CNMs. The goal of this paper is to promote the pilot-scale study and commercial use of CNMs as multifunctional additives in green and sustainable polymer composite coating and adhesive formulations.

36 MATERIALS SCIENCE↗

Improved interfacial li-ion transport in composite polymer electrolytes via surface modification of LLZO

Composite polymer electrolytes that incorporate ceramic fillers in a polymer matrix offer mechanical strength and flexibility as solid electrolytes for lithium metal batteries. However, fast Li + transport between polymer and Li + -conductive filler phases is not a simple achievement due to high barriers for Li + exchange across the interphase. This study demonstrates how modification of Li 7 La 3 Zr 2 O 12 (LLZO) nanofiller surfaces with silane chemistries influences Li + transport at local and global electrolyte scales. Anhydrous reactions covalently link amine-functionalized silanes [(3-aminopropyl)triethoxysilane (APTES)] to LLZO nanoparticles, which protects LLZO in air. APTES functionalization lowers the poly (ethylene oxide) (PEO)-LLZO interphase resistance to half that of unmodified LLZO and increases effective Li + transference number, while insulating Al 2 O 3 completely blocks ion exchange and lowers transference number and conductivity in PEO-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-LLZO composites. Modeling an inner resistive interphase between LLZO and PEO surrounded by an outer conductive interphase explains non-linear conductivity trends. Solid-state 7 Li & 6 Li nuclear magnetic resonance shows Li + only exchanges between PEO-LiTFSI and some LLZO interphase, with no appreciable Li + transport through bulk LLZO. Surface functionalization is a promising path toward lowering the polymer-ceramic interphase resistance. This work demonstrates that local changes in Li + transport affect macroscopic performance, highlighting the intricate relationships between all interfaces in inherently heterogeneous composite polymer electrolytes.

25 ENERGY STORAGE↗

The viscoelastic characterization of polymer materials exposed to the low-Earth orbit environment

Recent accomplishments in our research efforts have included the successful measurement of the thermal mechanical properties of polymer materials exposed to the low-earth orbit environment. In particular, viscoelastic properties were recorded using the Rheometrics Solids Analyzer (RSA 2). Dynamic moduli (E', the storage component of the elastic modulus, and E'', the loss component of the elastic modulus) were recorded over three decades of frequency (0.1 to 100 rad/sec) for temperatures ranging from -150 to 150 C. Although this temperature range extends beyond the typical use range of the materials, measurements in this region are necessary in the development of complete viscoelastic constitutive models. The experimental results were used to provide the stress relaxation and creep compliance performance characteristics through viscoelastic correspondence principles. Our results quantify the differences between exposed and control polymer specimens. The characterization is specifically designed to elucidate a constitutive model that accurately predicts the change in behavior of these materials due to exposure. The constitutive model for viscoelastic behavior reflects the level of strain, the rate of strain, and the history of strain as well as the thermal history of the material.

Strganac, Thomas↗

Li Morphology Evolution during Initial Cycles in a Gel Composite Polymer Electrolyte

Understanding and controlling lithium morphology evolution and lithium dendrite formation and growth during cycling is one of the key challenges for high-energy lithium metal batteries. This challenge applies to liquid electrolyte batteries as well as solid-state and semi-solid-state batteries. Our current knowledge about the evolution of the Li morphology is mostly obtained from liquid electrolyte-based studies in a Li–Li symmetrical cell configuration. The knowledge obtained in such conditions may not readily transfer into solid-state or semi-solid-state batteries. In this work, Li morphology evolution during initial cycling in a full cell configuration with the LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NMC 622) cathode and a semi-solid-state gel composite electrolyte is monitored via post-mortem photographs and scanning electron microscopy at multiple length scales. The gel composite electrolyte contains a cross-linked poly(ethylene oxide)-based polymer electrolyte, ceramic fillers, and a liquid plasticizer. The results show that severe surface pitting occurs as early as the second stripping cycle. Pit formation and continuous dissolution during the stripping process are the main cause of the Li surface roughening and dendrite growth mechanism in the model gel composite electrolyte. Comparing Li dendrite growth mechanisms in liquid, polymer, and ceramic solid electrolytes, the dendrite growth mechanism observed in this model electrolyte resembles that of the liquid electrolyte the most. This study suggests that strategies to control Li morphology and prevent dendrite growth in a gel composite electrolyte should be similar to strategies applicable to liquid electrolytes.

25 ENERGY STORAGE↗

Ion-Conducting Thermoresponsive Films Based on Polymer-Grafted Cellulose Nanocrystals

Mechanically robust, thermo-responsive, ion-conducting nanocomposite films are prepared from poly(2-phenylethyl methacrylate) grafted cellulose nanocrystals (MxG-CNC-g-PPMA). One-component nanocomposite films of the polymer grafted nanoparticle (PGN) MxG-CNC-g-PPMA are imbibed with 30 wt% imidazolium-based ionic liquid, to produce flexible ion-conducting films. These films with 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (MxG-CNC-g-PPMA/[H]) not only displays remarkable improvements in toughness (>25 times) and tensile strength (>70 times) relative to the corresponding nanocomposites consisting of the ionic liquid imbibed in the two component CNC/PPMA nanocomposite, but also shows higher ionic conductivity than the corresponding neat PPMA with the same wt.% of ionic liquid. Notably, the one-component film containing 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (MxG-CNC-g-PPMA/[E]) exhibits temperature responsive ionic conduction. The ionic conductivity decreases at around 60°C as a consequence of the lower critical solution temperature (LCST) phase transition of the grafted polymer in the ionic liquid, which leads to phase separation. Moreover, holding the MxG-CNC-g-PPMA/[E] film at room temperature for 24 hours returns the film to its original homogenous state. These materials exhibit properties relevant to thermal cutoff safety devices (e.g., thermal fuse) where a reduction in conductivity above a critical temperature is needed.

36 MATERIALS SCIENCE↗

Elastomer Mechanics of Cross-Linked Linear-Ring Polymer Blends

Cross-linking a blend of linear and ring polymers creates a new topology-based dual-network elastomer in which the two components differ significantly in their topology. We use molecular simulations and topological analysis to examine key mechanical properties as functions of ring polymer volume fraction Φ R . For Φ R < Φ R *, where the rings begin to overlap, the network shear modulus G and the maximum stretch ratio λ p are weakly dependent on Φ R . For Φ R > Φ R *, entanglements trapped in the network are diluted as the rings overlap, leading to a significant decrease in G and an increase in λ p with increasing Φ R . Here, the peak tensile stress, σ p , exhibits a maximum around Φ R *, indicating an enhancement of network strength due to the stronger cohesion from the entanglements between linear and ring polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer–Ceramic Composite Electrolytes for Lithium Batteries: A Comparison between the Single-Ion-Conducting Polymer Matrix and Its Counterpart

Single-ion-conducting polymer electrolytes are attractive to use in lithium batteries as the transference number of the lithium cation approaches unity. This helps prevent concentration gradients across the electrolyte, which can result in dendrite formation. The addition of ceramic particles to polymer electrolytes at high loadings can increase the mechanical strength of the polymer, which can also help suppress dendrite formation. Here, a single-ion-conducting polymer electrolyte is blended with lithium-conducting oxide ceramic particles to make a composite electrolyte. This electrolyte is studied in comparison to a composite electrolyte containing freely dissolved lithium salt. It is found that the addition of ceramic particles to the single-ion-conducting polymer can result in increased cation dissociation and consequent increased ionic conductivity. The electrolytes are cycled in lithium symmetrical cells, and it is found that the ceramic-containing electrolytes show increased interfacial stability with the lithium metal compared to the pristine polymer electrolytes. Our findings shed light on how to optimize the polymer host chemistry to form composite electrolytes that can meet the challenging requirements to stabilize the lithium metal anode.

25 ENERGY STORAGE↗

Recycling of Pretreated Polyolefin-Based Ocean-Bound Plastic Waste by Incorporating Clay and Rubber

Plastic waste found in oceans has become a major concern because of its impact on marine organisms and human health. There is significant global interest in recycling these materials, but their reclamation, sorting, cleaning, and reprocessing, along with the degradation that occurs in the natural environment, all make it difficult to achieve high quality recycled resins from ocean plastic waste. To mitigate these limitations, various additives including clay and rubber were explored. In this study, we compounded different types of ocean-bound (o-HDPE and o-PP) and virgin polymers (v-LDPE and v-PS) with various additives including a functionalized clay, styrene-multi-block-copolymer (SMB), and ethylene-propylene-based rubber (EPR). Physical observation showed that all blends containing PS were brittle due to the weak interfaces between the polyolefin regions and the PS domains within the polymer blend matrix. Blends containing clay showed rough surfaces and brittleness because of the non-uniform distribution of clay particles in the polymer matrix. To evaluate the properties and compatibility of the blends, characterizations using differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and small-amplitude oscillatory shear (SAOS) rheology were carried out. The polymer blend (v-LDPE, o-HDPE, o-PP) containing EPR showed improved elasticity. Incorporating additives such as rubber could improve the mechanical properties of polymer blends for recycling purposes.

42 ENGINEERING↗

Modeling the Nonlinear Rheology of Polymer Additive Manufacturing

This report summarizes molecular and continuum simulation studies focused on developing physics - based predictive models for the evolution of polymer molecular order during the nonlinear processing flows of additive manufacturing. Our molecular simulations of polymer elongation flows identified novel mechanisms of fluid dissipation for various polymer architectures that might be harnessed to enhance material processability. In order to predict the complex thermal and flow history of polymer realistic additive manufacturing processes, we have developed and deployed a high - performance mesh - free hydrodynamics module in Sandia's LAMMPS software. This module called RHEO – short for Reproducing Hydrodynamics and Elastic Objects – hybridizes an updated - Lagrange reproducing - kernel method for complex fluids with a bonded particle method (BPM) to capture solidification and solid objects in multiphase flows. In combination, our two methods allow rapid, multiscale characterization of the hydrodynamics and molecular evolution of polymers in realistic processing geometries.

36 MATERIALS SCIENCE↗

Electro-Active Polymer (EAP) Actuators for Planetary Applications

NASA is seeking to reduce the mass, size, consumed power, and cost of the instrumentation used in its future missions. An important element of many instruments and devices is the actuation mechanism and electroactive polymers (EAP) are offering an effective alternative to current actuators. In this study, two families of EAP materials were investigated, including bending ionomers and longitudinal electrostatically driven elastomers. These materials were demonstrated to effectively actuate manipulation devices and their performance is being enhanced in this on-going study. The recent observations are reported in this paper, include the operation of the bending-EAP at conditions that exceed the harsh environment on Mars, and identify the obstacles that its properties and characteristics are posing to using them as actuators. Analysis of the electrical characteristics of the ionomer EAP showed that it is a current driven material rather than voltage driven and the conductivity distribution on the surface of the material greatly influences the bending performance. An accurate equivalent circuit modeling of the ionomer EAP performance is essential for the design of effective drive electronics. The ionomer main limitations are the fact that it needs to be moist continuously and the process of electrolysis that takes place during activation. An effective coating technique using a sprayed polymer was developed extending its operation in air from a few minutes to about four months. The coating technique effectively forms the equivalent of a skin to protect the moisture content of the ionomer. In parallel to the development of the bending EAP, the development of computer control of actuated longitudinal EAP has been pursued. An EAP driven miniature robotic arm was constructed and it is controlled by a MATLAB code to drop and lift the arm and close and open EAP fingers of a 4-finger gripper. Keywords: Miniature Robotics, Electroactive Polymers, Electroactive Actuators, EAP Materials

Bar-Cohen, Y.↗

Simulations of Glass Transition and Mechanical Behavior of Off-Stoichiometric Crosslinked Polymers

Here, this work explores the influence of blend composition, network architecture, and hydrogen bonding on the material properties of crosslinked epoxy networks, focusing on the glass transition temperature (T g ) and Young’s modulus (Y). We used coarse-grained molecular dynamics simulations to simulate varying compositions of stiff and flexible components in epoxy monomer blends with varying excess of curative. We find that, without hydrogen bonding, networks of any composition show a monotonically increasing T g with decreasing excess curative, consistent with theory. In contrast, we find that when hydrogen bonding is introduced, the binary blend networks show significant enhancement in T g for lightly crosslinked systems. This result contributes to an explanation of the anomalous T g behavior observed experimentally in these systems. We further find that Y is generally enhanced by hydrogen bonds, especially below T g , demonstrating that hydrogen bonding has a significant influence on mechanical properties and can allow access to other desirable dynamic behavior, especially self-healing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Functional group effect of chemically modified microcrystalline methyl cellulose on thermoplastic polyurethane composites

Microcrystalline cellulose (MCC) is a promising bio-based filler for lightweight yet mechanically high-performance eco-polymer composites because of its low density and high biocompatibility. However, intermolecular hydrogen bonding among MCC is stronger than the polymer–filler interactions, which deteriorate the mechanical properties of the composites. Herein, we investigated the effects of functional groups on the mechanical properties of composites by scrutinizing chemically modified microcrystalline methyl cellulose (m-MMC) with three different substitution levels of hydroxyl group to hydroxypropyl (HP) group: no-, low-, and high-level substitution (HP-0, HP-low, and HP-high). The degree of HP substitution of m-MMC was quantitatively measured by CP/MAS NMR analysis. The relatively bulky HP groups interrupted the filler–filler intermolecular interactions and reduced the crystallinity and density of m-MMC, as evident from X-ray diffractometer and pycnometer data, respectively. For scalable production of the composites, the m-MMC were compounded with thermoplastic polyurethane (TPU) by a twin-screw extruder at concentrations between 0.5 and 10 wt%. Despite its low filler concentration, the toughness of m-MMC/TPU composites was remarkably enhanced, up to 28% (229.2 to 294.4 MJ/m 3 ) at 0.5 wt% loading of HP-low, owing to the enhanced polymer–filler interactions. In conclusion, the fundamental understanding on structure–property relationships will provide insights for designing of mechanically robust yet eco-friendly polymer composites.

composites↗

Polymer Retention Evaluation in a Heavy Oil Sand for a Polymer Flooding Application on Alaska’s North Slope

For a polymer flooding field trial in a heavy oil reservoir on Alaska’s North Slope, polymer retention is a key parameter. Because of the economic impact of retention, this parameter was extensively studied using field core material and conditions. Several important findings were noted. Polymer retention based on effluent viscosity measurements can be overestimated unless the correct (non-linear) relation between polymer concentration and viscosity is used. Polymer degradation (either mechanical or oxidative) can also lead viscosity-based measurements to overestimate retention. Inaccessible pore volume (IAPV) can be overestimated if insufficient brine is flushed through the sand between polymer banks. Around 100 pore volumes (PV) of brine may be needed to displace mobile polymer to approach a true residual resistance factor and properly measure IAPV. Even for a sand pack with kwsor = 20 mD, IAPV was zero for HPAM with molecular weight (Mw) of 18 million g/mol. Fine-grain particles (<20 μm) strongly impacted polymer retention values. Native NB#1 sand with a significant component of particles <20 μm exhibited 290 μg/g, while the same sand exhibited 28 μg/g after these small particles were removed. Polymer retention did not necessarily correlate with mineral composition. The NB#1, NB#3, and OA sands had similar elemental and clay compositions, but the NB#1 sand exhibited ~10 times higher retention than the NB#3 sand. Polymer retention did not necessarily correlate with permeability. NB#1 sand exhibited much higher retention than OA sand, even though NB#1 sand was twice as permeable as OA sand. No evidence of chromatographic separation of HPAM molecular weights was found in our experiments. Although retention tended to be greater without a residual oil saturation (than at Sor), the effect was not strong. Aging a core (with high oil saturation) at 60°C reduced HPAM retention by a factor of two. As expected, under similar conditions, polymer retention was greater for a higher Mw HPAM (18 million g/mol) than for a lower Mw HPAM (10-12 million g/mol). In many cases with high polymer retention values (e.g., 240 μg/g), polymer arrival at the end of the core was relatively quick, but achieving the injected concentration occurred gradually over many pore volumes. This effect was not due chromatographic separation of polymer molecular weights. Results from modeling of this behavior was consistent with concentrationdependent polymer retention. The form assumed for the retention function in a simulator can have an important impact on the timing and magnitude of the oil response from a polymer flood. Field-based observations can underestimate polymer retention, depending on when the tracer and polymer concentrations were measured and the assumptions made about reservoir heterogeneity.

Wang, Dongmei↗

Temperature Dependence of Structural Relaxation in Glass-Forming Liquids and Polymers

Understanding the microscopic mechanism of the transition of glass remains one of the most challenging topics in Condensed Matter Physics. What controls the sharp slowing down of molecular motion upon approaching the glass transition temperature T g , whether there is an underlying thermodynamic transition at some finite temperature below T g , what the role of cooperativity and heterogeneity are, and many other questions continue to be topics of active discussions. This review focuses on the mechanisms that control the steepness of the temperature dependence of structural relaxation (fragility) in glass-forming liquids. We present a brief overview of the basic theoretical models and their experimental tests, analyzing their predictions for fragility and emphasizing the successes and failures of the models. Special attention is focused on the connection of fast dynamics on picosecond time scales to the behavior of structural relaxation on much longer time scales. A separate section discusses the specific case of polymeric glass-forming liquids, which usually have extremely high fragility. We emphasize the apparent difference between the glass transitions in polymers and small molecules. We also discuss the possible role of quantum effects in the glass transition of light molecules and highlight the recent discovery of the unusually low fragility of water. At the end, we formulate the major challenges and questions remaining in this field.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Analogy between fluid cavitation and fracture mechanics

When the stresses imposed on a fluid are sufficiently large, rupture or cavitation can occur. Such conditions can exist in many two-phase flow applications, such as the choked flows, which can occur in seals and bearings. Nonspherical bubbles with large aspect ratios have been observed in fluids under rapid acceleration and high shear fields. These bubbles are geometrically similar to fracture surface patterns (Griffith crack model) existing in solids. Analogies between crack growth in solid and fluid cavitation are proposed and supported by analysis and observation (photographs). Healing phenomena (void condensation), well accepted in fluid mechanics, have been observed in some polymers and hypothesized in solid mechanics. By drawing on the strengths of the theories of solid mechanics and cavitation, a more complete unified theory can be developed.

Hendricks, R. C.↗

Polymer Crosslinked 3-D Assemblies of Nanoparticles: Mechanically Strong Lightweight Porous Materials

In analogy to supramolecular assemblies, which are pursued because of properties above and beyond those of the individual molecules, self-standing monolithic three-dimensional assemblies of nanoparticles also have unique properties attributed to their structure. For example, ultra low-density 3-D assemblies of silica nanoparticles, known as silica aerogels, are characterized by large internal void space, high surface area and very low thermal conductivity. Aerogels, however, are also extremely fragile materials, limiting their application to a few specialized environments, e.g., in nuclear reactors as Cerenkov radiation detectors, in space (refer to NASA's Stardust Program) and aboard certain planetary vehicles (thermal insulators on Mars Rovers in 1997 and 2004). The fragility problem is traced to well-defined weak points in the aerogel skeletal framework, the interparticle necks. Using the surface functionality of the nanoparticle building blocks as a focal point, we have directed attachment of a conformal polymer coating over the entire framework, rendering all necks wider. Thus, although the bulk density may increase only by 3x, the mesoporosity (pores in the range 2-50 nm) remains unchanged, while the strength of the material increases by up to 300... Having addressed the fragility problem, aerogels are now robust materials, and a variety of applications, ranging from thermal/acoustic insulators to catalyst supports, to platform for sensors, and dielectrics are all within reach. Our approach employs molecular science to manipulate nanoscopic matter for achieving useful macroscopic properties, and in our view it resides at the core of what defines nanotechnology. In that spirit, this technology is expandable in three directions. Thus, we have already crosslinked successfully amine-modified silica, and we anticipate that more rich chemistry will be realized by been creative with the nanoparticle surface modifiers. On the other hand, although we do not expect orders-of-magnitude increase in strength, nevertheless, by varying the polymer we expect to impart other properties such as hydrophobicity, thermal stability and perhaps electrical conductivity. Besides polymers, crosslinkers will include metals and ceramics (e.g., through POSS precursors). Finally, network morphology directs load dissipation, and of approximately 30 different crosslinked oxide aerogels, vanadia, whose structure is fibrous rather than particulate, yields a much stronger (by 4..) material than silica of the same density. It seems imperative to implement control of network morphology, even through templating.

Leventis, Nicholas↗

Thermo-Oxidation Analysis of Structural Adhesives: An Experimental Study

Abstract Cross-linked polymers play an important role in structural applications as adhesives. In this article, we performed an experimental study to understand the effects of high temperature i.e. thermo-oxidative aging on the mechanical behavior of polymers. Subsequently, the constitutive behavior, i.e. stress-strain relation of these adhesives before and after the accelerated aging tests were studied on samples aged at different temperature and different time durations at zero humidity. The aging conditions and periods selected for the tests have been specifically designed to simulate the effects of aging under the working conditions that the materials will be subjected to in their standard applications. The focus of this study is on the investigation of the effects of aging on the polymeric adhesives used in automotive applications. Consequently, four different polymeric adhesives (one silicone-based, two polyurethane-based, and one acrylic type), which are being used extensively in these applications, have been chosen. The quasi-static tensile loading was used on these four adhesives and the changes in the constitutive behavior were measured. The failure tensile tests as well as the cyclic tensile tests were performed in our lab using a Test-Resources tensile testing machine. The temperatures that were used in this work are 60, 80 and 95°C for varying aging periods of 24hrs, 240hrs, and 720hrs. Then, all the data was collected and consequently analyzed, and the resulting behavior was compared to that of the unaged material, showing varying results depending on the material, temperature, and aging period. Different behaviors have been observed after aging. The polymers’ behavior was expanding from no effect to significant damage caused by aging conditions. This work provides the core understanding required for modeling the material behavior during aging and lays down the groundwork for further data-infused model-free approaches.

Alazhary, Sharif↗