Search results for: bias-enhanced nucleation and growth

Authors: Meriem Hamla, Mohamed Benaicha, Sabrine Derbal

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In the present work, several materials such as M/glass (M = Pt, Mo) were investigated to test their suitability for studying the early nucleation stages and growth of copper-tin clusters. It was found that most of these materials stand as good substrates to be used in the study of the nucleation and growth of electrodeposited Cu-Sn alloys from aqueous solution containing CuCl2, SnCl2 as electroactive species and Na3C6H5O7 as complexing agent. Among these substrates, Pt shows instantaneous models followed by 3D diffusion-limited growth. On the other hand, the electrodeposited copper-tin thin films onto Mo substrate followed progressive nucleation. The deposition mechanism of the Cu-Sn films has been studied using stationary electrochemical techniques (cyclic voltammetery (CV) and chronoamperometry (CA). The structural, morphological and compositional of characterization have been studied using X-ray diffraction (XRD), scanning electron microscopy (SEM) and EDAX techniques respectively.

Keywords: electrodeposition, CuSn, nucleation, mechanism

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Authors: V. Nikkhah Rashidabad, M. Manteghian, M. Masoumi, S. Mousavian

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In this research, the changes in bubbles diameter and number that may occur due to the change in heat flux of pure water during pool boiling process. For this purpose, test equipment was designed and developed to collect test data. The bubbles were graded using Caliper Screen software. To calculate the growth and nucleation rates of bubbles under different fluxes, population balance model was employed. The results show that the increase in heat flux from q=20 kw/m2 to q=102 kw/m2 raised the growth and nucleation rates of bubbles.

Keywords: heat flux, bubble growth, bubble nucleation, population balance model

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Authors: Charine Faith H. Lagrimas, Rommel N. Galvan, Rizalinda L. de Leon

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An ongoing study, methyl laurate to be used as a refrigerant in an HVAC system, requires the crystallization kinetics of the said substance. Step-wise and normal forms of Avrami model parameters were used to describe the isothermal crystallization kinetics of methyl laurate at different temperatures from Differential Scanning Calorimetry (DSC) measurements. At 3 °C, parameters showed that methyl laurate exhibits a secondary crystallization. The primary crystallization occurred with instantaneous nuclei and spherulitic growth; followed by a secondary instantaneous nucleation with a lower growth of dimensionality, rod-like. At 4 °C to 6 °C, the exotherms from DSC implied that the system was under the isokinetic range. The kinetics behavior is the same which is instantaneous nucleation with one-dimensional growth. The differences for the isokinetic range temperatures are the activation energies (directly proportional to T) and nucleation rates (inversely proportional to T). From the images obtained during the crystallization of methyl laurate using an optical microscope, it is confirmed that the nucleation and crystal growth modes obtained from the optical microscope are consistent with the parameters from Avrami model.

Keywords: Avrami model, isothermal crystallization, lipids kinetics, methyl laurate

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Authors: Mei Yuin Joanne Wee, Rosli Md. Illias

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Cell surface display is the expression of a protein with an anchoring motif on the surface of the cell. This approach offers advantages when used in bioconversion in terms of easier purification steps and more efficient enzymatic reaction. A surface display system using ice nucleation protein (InaA) from Erwina ananas as an anchoring motif has been constructed to display xylanase (xyl) on the surface of Escherischia coli. The InaA was truncated so that it is made up of the N- and C-terminal domain (INPANC-xyl) and it has successfully directed xylanase to the surface of the cell. A study was also done on xylanase fused to two other ice nucleation proteins, InaK (INPKNC-xyl) and InaZ (INPZNC-xyl) from Pseudomonas syringae KCTC 1832 and Pseudomonas syringae S203 respectively. Surface localization of the fusion protein was verified using SDS-PAGE and Western blot on the cell fractions and all anchoring motifs were successfully displayed on the outer membrane of E. coli. Upon comparison, whole-cell activity of INPANC-xyl was more than six and five times higher than INPKNC-xyl and INPZNC-xyl respectively. Furthermore, the expression of INPANC-xyl on the surface of E. coli did not inhibit the growth of the cell. This is the first report of surface display system using ice nucleation protein, InaA from E. ananas. From this study, this anchoring motif offers an attractive alternative to the current surface display systems.

Keywords: cell surface display, Escherischia coli, ice nucleation protein, xylanase

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Authors: M. M. Moharam, E. M. Elsayed, M. M. Rashad

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Single phase Cu₂O films have been prepared via an electrodeposition technique onto ITO glass substrates at room temperature. Likewise, Cu₂O films were deposited using a potentiostatic process from an alkaline electrolyte containing copper (II) nitrate and 1M sodium citrate. Single phase Cu₂O films were electrodeposited at a cathodic deposition potential of 500mV for a reaction period of 90 min, and pH of 12 to yield a film thickness of 0.49 µm. The mechanism for nucleation of Cu₂O films was found to vary with deposition potential. Applying the Scharifker and Hills model at -500 and -600 mV to describe the mechanism of nucleation for the electrochemical reaction, the nucleation mechanism consisted of a mix between instantaneous and progressive growth mechanisms at -500 mV, while above -600 mV the growth mechanism was instantaneous. Using deposition times from 30 to 90 min at -500 mV deposition potential, pure Cu2O films with different microstructures were electrodeposited. Changing the deposition time from 30 to 90 min varied the microstructure from cubic to more complex polyhedra. The transmittance of electrodeposited Cu₂O films ranged from 20-70% in visible range, and samples exhibited a 2.4 eV band gap. The electrical resistivity for electrodeposited Cu₂O films was found to decrease with increasing deposition time from 0.854 x 105 Ω-cm at 30 min to 0.221 x 105 Ω-cm at 90 min without any thermal treatment following the electrodeposition process.

Keywords: Cu₂O, electrodeposition, film thickness, characterization, optical properties

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Authors: Sheraz Ahmad, Li Yiming, Li XiangFang, Xia Wei, Zeen Chen

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Holding CO₂ at massive scale in the enclathrated solid matter called hydrate can be perceived as one of the most reliable methods for CO₂ sequestration to take greenhouse gases emission control measures and global warming preventive actions. In this study, a dynamically coupled mass and heat transfer mathematical model is developed which elaborates the unsteady behavior of CO₂ flowing into a porous medium and converting itself into hydrates. The combined numerical model solution by implicit finite difference method is explained and through coupling the mass, momentum and heat conservation relations, an integrated model can be established to analyze the CO₂ hydrate growth within P-T equilibrium conditions. CO₂ phase transition, effect of hydrate nucleation by exothermic heat release and variations of thermo-physical properties has been studied during hydrate nucleation. The results illustrate that formation pressure distribution becomes stable at the early stage of hydrate nucleation process and always remains stable afterward, but formation temperature is unable to keep stable and varies during CO₂ injection and hydrate nucleation process. Initially, the temperature drops due to cold high-pressure CO₂ injection since when the massive hydrate growth triggers and temperature increases under the influence of exothermic heat evolution. Intermittently, it surpasses the initial formation temperature before CO₂ injection initiates. The hydrate growth rate increases by increasing injection pressure in the long formation and it also expands overall hydrate covered length in the same induction period. The results also show that the injection pressure conditions and hydrate growth rate affect other parameters like CO₂ velocity, CO₂ permeability, CO₂ density, CO₂ and H₂O saturation inside the porous medium. In order to enhance the hydrate growth rate and expand hydrate covered length, the injection temperature is reduced, but it did not give satisfactory outcomes. Hence, CO₂ injection in vacated natural gas hydrate porous sediment may form hydrate under low temperature and high-pressure conditions, but it seems very challenging on a huge scale in lengthy formations.

Keywords: CO₂ hydrates, CO₂ injection, CO₂ Phase transition, CO₂ sequestration

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Authors: Pixiang Wang, Shaoyang Liu, Yucheng Peng

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Polypropylene (PP) is an essential material of numerous applications in different industrial sectors, including packaging, construction, and automotive. Because the application of homopolypropylene (HPP) is limited by its relatively low impact strength and high embrittlement temperature, various types of impact copolymer PP (ICPP) that incorporate elastomers/rubbers into HPP to increase impact strength have been successfully commercialized. Crystallization kinetics of an isotactic HPP, an ICPP, and their composites were studied in this work understand the composites’ behaviors better. The Avrami-Jeziorny model was used to describe the crystallization process. For most samples, the Avrami exponent, n, was greater than 3, indicating the crystal grew in three dimensions with spherical geometry. However, the n value could drop below 3 when the ICPP content was 80 wt.% or higher and the cooling rate was 7.5°C/min or lower, implying that the crystals could grow in two dimensions and some lamella structures could be formed under those conditions. The nucleation activity increased with the increase of the ICPP content, demonstrating that the rubber phase in the ICPP acted as a nucleation agent and facilitated the nucleation process. The decrease in crystallization rate after the ICPP content exceeded 60 wt.% might be caused by the excessive amount of crystal nuclei induced by the high ICPP content, which caused strong crystal-crystal interactions and limited the crystal growth space. The nucleation activity and the n value showed high correlations to the mechanical and thermal properties of the materials. The quantitative study of the kinetics of crystallization in this work could be a helpful reference for manufacturing ICPP and HPP/ICPP mixtures.

Keywords: polypropylene, crystallization kinetics, Avrami-Jeziorny model, crystallization activation energy, Nucleation activity

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Authors: Zhe Li, Tao Ju, Liguo Zhang, Zehong Zhang, Baoshun Zhang

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In-grow stacking-faults (IGSFs) in 4H-SiC epilayers can cause increased leakage current and reduce the blocking voltage of 4H-SiC power devices. Double Shockley stacking fault (2SSF) is a common type of IGSF with double slips on the basal planes. In this study, a 2SSF in the 4H-SiC epilayer grown by chemical vaper deposition (CVD) is characterized. The nucleation site of the 2SSF is discussed, and a model for the 2SSF nucleation is proposed. Homo-epitaxial 4H-SiC is grown on a commercial 4 degrees off-cut substrate by a home-built hot-wall CVD. Defect-selected-etching (DSE) is conducted with melted KOH at 500 degrees Celsius for 1-2 min. Room temperature cathodoluminescence (CL) is conducted at a 20 kV acceleration voltage. Low-temperature photoluminescence (LTPL) is conducted at 3.6 K with the 325 nm He-Cd laser line. In the CL image, a triangular area with bright contrast is observed. Two partial dislocations (PDs) with a 20-degree angle in between show linear dark contrast on the edges of the IGSF. CL and LTPL spectrums are conducted to verify the IGSF’s type. The CL spectrum shows the maximum photoemission at 2.431 eV and negligible bandgap emission. In the LTPL spectrum, four phonon replicas are found at 2.468 eV, 2.438 eV, 2.420 eV and 2.410 eV, respectively. The Egx is estimated to be 2.512 eV. A shoulder with a red-shift to the main peak in CL, and a slight protrude at the same wavelength in LTPL are verified as the so called Egx- lines. Based on the CL and LTPL results, the IGSF is identified as a 2SSF. Back etching by neutral loop discharge and DSE are conducted to track the origin of the 2SSF, and the nucleation site is found to be a threading screw dislocation (TSD) in this sample. A nucleation mechanism model is proposed for the formation of the 2SSF. Steps introduced by the off-cut and the TSD on the surface are both suggested to be two C-Si bilayers height. The intersections of such two types of steps are along [11-20] direction from the TSD, while a four-bilayer step at each intersection. The nucleation of the 2SSF in the growth is proposed as follows. Firstly, the upper two bilayers of the four-bilayer step grow down and block the lower two at one intersection, and an IGSF is generated. Secondly, the step-flow grows over the IGSF successively, and forms an AC/ABCABC/BA/BC stacking sequence. Then a 2SSF is formed and extends by the step-flow growth. In conclusion, a triangular IGSF is characterized by CL approach. Base on the CL and LTPL spectrums, the estimated Egx is 2.512 eV and the IGSF is identified to be a 2SSF. By back etching, the 2SSF nucleation site is found to be a TSD. A model for the 2SSF nucleation from an intersection of off-cut- and TSD- introduced steps is proposed.

Keywords: cathodoluminescence, defect-selected-etching, double Shockley stacking fault, low-temperature photoluminescence, nucleation model, silicon carbide

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Authors: A. Kaćunić, M. Ćosić, N. Kuzmanić

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Interaction between mixing and crystallization is often ignored despite the fact that it affects almost every aspect of the operation including nucleation, growth, and maintenance of the crystal slurry. This is especially pronounced in multiple impeller systems where flow complexity is increased. By choosing proper mixing parameters, what closely depends on the knowledge of the hydrodynamics in a mixing vessel, the process of batch cooling crystallization may considerably be improved. The values that render useful information when making this choice are mixing time and power consumption. The predominant motivation for this work was to investigate the extent to which radial dual impeller configuration influences mixing time, power consumption and consequently the values of metastable zone width and nucleation rate. In this research, crystallization of borax was conducted in a 15 dm3 baffled batch cooling crystallizer with an aspect ratio (H/T) of 1.3. Mixing was performed using two straight blade turbines (4-SBT) mounted on the same shaft that generated radial fluid flow. Experiments were conducted at different values of N/NJS ratio (impeller speed/ minimum impeller speed for complete suspension), D/T ratio (impeller diameter/crystallizer diameter), c/D ratio (lower impeller off-bottom clearance/impeller diameter), and s/D ratio (spacing between impellers/impeller diameter). Mother liquor was saturated at 30°C and was cooled at the rate of 6°C/h. Its concentration was monitored in line by Na-ion selective electrode. From the values of supersaturation that was monitored continuously over process time, it was possible to determine the metastable zone width and subsequently the nucleation rate using the Mersmann’s nucleation criterion. For all applied dual impeller configurations, the mixing time was determined by potentiometric method using a pulse technique, while the power consumption was determined using a torque meter produced by Himmelstein & Co. Results obtained in this investigation show that dual impeller configuration significantly influences the values of mixing time, power consumption as well as the metastable zone width and nucleation rate. A special attention should be addressed to the impeller spacing considering the flow interaction that could be more or less pronounced depending on the spacing value.

Keywords: dual impeller crystallizer, mixing time, power consumption, metastable zone width, nucleation rate

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Authors: E. Poupelloz, S. Gauffinet

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Ettringite Ca₆Al₂(SO₄)₃(OH)₁₂26H₂O is one of the major hydrates formed during cement hydration. Ettringite forms in Portland cement from the reaction between tricalcium aluminate Ca₃Al₂O₆ and calcium sulfate. Ettringite is also present in calcium sulfoaluminate cement in which it is the major hydrate, formed by the reaction between yeelimite Ca₄(AlO₂)₆SO₄ and calcium sulfate. About the formation of ettringite, numerous results are available in the literature even if some issues are still under discussion. However, almost all published work about ettringite was done on cementitious systems. Yet in cement, hydration reactions are very complex, the result of dissolution-precipitation processes and are submitted to various interactions. Understanding the formation process of a phase alone, here ettringite, is the first step to later understand the much more complex reactions happening in cement. This study is crucial for the comprehension of early cement hydration and physical behavior. Indeed formation of hydrates, in particular, ettringite, will have an influence on the rheological properties of the cement paste and on the need for admixtures. To make progress toward the understanding of existing phenomena, a specific study of nucleation and growth processes of ettringite was conducted. First ettringite nucleation was studied in ionic aqueous solutions, with controlled but different experimental conditions, as different supersaturation degrees (β), different pH or presence of exogenous ions. Through induction time measurements, interfacial ettringite crystals solution energies (γ) were determined. Growth of ettringite in supersaturated solutions was also studied through chain crystallization reactions. Specific BET surface area measurements and Scanning Electron Microscopy observations seemed to prove that growth process is favored over the nucleation process when ettringite crystals are initially present in a solution with a low supersaturation degree. The influence of stirring on ettringite formation was also investigated. Observation was made that intensity and nature of stirring have a high influence on the size of ettringite needles formed. Needle sizes vary from less than 10µm long depending on the stirring to almost 100µm long without any stirring. During all previously mentioned experiments, initially present ions are consumed to form ettringite in such a way that the supersaturation degree with regard to ettringite is decreasing over time. To avoid this phenomenon a device compensating the drop of ion concentrations by adding some more solutions, and therefore always have constant ionic concentrations, was used. This constant β recreates the conditions of the beginning of cement paste hydration, when the dissolution of solid reagents compensates the consumption of ions to form hydrates. This device allowed the determination of the ettringite precipitation rate as a function of the supersaturation degree β. Taking samples at different time during ettringite precipitation and doing BET measurements allowed the determination of the interfacial growth rate of ettringite in m²/s. This work will lead to a better understanding and control of ettringite formation alone and thus during cements hydration. This study will also ultimately define the impact of ettringite formation process on the rheology of cement pastes at early age, which is a crucial parameter from a practical point of view.

Keywords: cement hydration, ettringite, morphology of crystals, nucleation-growth process

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Authors: Kirsten Techmer, Jan-Erik Rybak, Simon Rudolph

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Natural formed pyrites (FeS2) are frequent sulfides in sedimentary and metamorphic rocks. Growth textures of idiomorphic pyrite assemblages reflect the conditions during their formation in the geologic sequence, furtheron the local texture analyses of the growth patterns of pyrite assemblages by EBSD reveal the possibility to resolve the growth conditions during the formation of pyrite at the micron scale. The spatial resolution of local texture measurements in the Scanning Electron Microscope used can be in the nanomete scale. Orientation contrasts resulting from domains of smaller misorientations within larger pyrite crystals can be resolved as well. The electron optical studies have been carried out in a Field-Emission Scanning Electron Microscope (FEI Quanta 200) equipped with a CCD camera to study the orientation contrasts along the surfaces of pyrite. Idiomorphic cubic single crystals of pyrite, polycrystalline assemblages of pyrite, spherically grown spheres of pyrite as well as pyrite-bearing ammonites have been studied by EBSD in the Scanning Electron Microscope. Samples were chosen to show no or minor secondary deformation and an idiomorphic 3D crystal habit, so the local textures of pyrite result mainly from growth and minor from deformation. The samples studied derived from Navajun (Spain), Chalchidiki (Greece), Thüringen (Germany) and Unterkliem (Austria). Chemical analyses by EDAX show pyrite with minor inhomogeneities e.g., single crystals of galena and chalcopyrite along the grain boundaries of larger pyrite crystals. Intergrowth between marcasite and pyrite can be detected in one sample. Pyrite may form intense growth twinning lamellae on {011}. Twinning, e.g., contact twinning is abundant within the crystals studied and the individual twinning lamellaes can be resolved by EBSD. The ammonites studied show a replacement of the shale by newly formed pyrite resulting in an intense intergrowth of calcite and pyrite. EBSD measurements indicate a polycrystalline microfabric of both minerals, still reflecting primary surface structures of the ammonites e.g, the Septen. Discs of pyrite (“pyrite dollar”) as well as pyrite framboids show growth patterns comprising a typical microfabric. EBSD studies reveal an equigranular matrix in the inner part of the discs of pyrite and a fiber growth with larger misorientations in the outer regions between the individual segments. This typical microfabric derived from a formation of pyrite crystals starting at a higher nucleation rate and followed by directional crystal growth. EBSD studies show, that the growth texture of pyrite in the samples studied reveals a correlation between nucleation rate and following growth rate of the pyrites, thus leading to the characteristic crystal habits. Preferential directional growth at lower nucleation rates may lead to the formation of 3D framboids of pyrite. Crystallographic misorientations between the individual fibers are similar. In ammonites studied, primary anisotropies of the substrates like e.g., ammonitic sutures, influence the nucleation, crystal growth and habit of the newly formed pyrites along the surfaces.

Keywords: Electron Back Scatter Diffraction (EBSD), growth pattern, Fe-sulfides (pyrite), texture analyses

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Authors: Amanuel Bekuma, Rebecca Swift, Sarah Jackson, Ben Biddulph

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Economic loss to frost damage is increasing over the past years in the Western Australian Wheatbelt. Agronomic, genetic, and climatic works have still found a weak correlation between temperature and frost damage. One possibility that has not been explored within the Australian cropping system is whether ice nucleation active bacteria (INB) either present in situ on crop residue or introduced by rainfall could be responsible for the increased sensitivity of cereal plants to frost at different stages of development. This study investigated upper and lower leaf canopy, stubble, and soil as a potential site of ice nucleation activity (INA) and tracked the changes in INA during the plant development. We found that older leaves of wheat are the primary sites of ice nucleation (-4.7 to -6.3°C) followed by stubble (-5.7 to -6.7°C) which increases the risk of frost damage during heading and flowering (the most susceptible stages). However, healthy and green upper canopy leaves (flag and flag-2) and the soil have lower INA (< -11°C) during the frost-sensitive stage of wheat. We anticipate the higher INA on the stubble and older leaves to be due to the presence of biologically active ice-nucleating bacteria (INB), known to cause frost injury to sensitive plants at -5°C. Stubble retained or applied during the growing season further exacerbates additional frost risk by potentially increasing the INB load. The implications of the result for stubble and frost risk management in a frost-prone landscape will be discussed.

Keywords: frost, ice-nucleation-activity, stubble, wheat

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Authors: Jie Yin, Jun Zhang

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Measuring the growth performance and critical supersaturation of particle group have a high reference value for constructing a supersaturated water vapor environment that can improve the removal efficiency of the high-concentration particle group. The critical supersaturation and the variation of the growth performance with supersaturation for high-concentration particles were measured by a flow cloud chamber. Findings suggest that the influence of particle concentration on the growth performance will reduce with the increase of supersaturation. Reducing residence time and increasing particle concentration have similar effects on the growth performance of the high-concentration particle group. Increasing particle concentration and shortening residence time will increase the critical supersaturation of the particle group. The critical supersaturation required to activate a high-concentration particle group is lower than that of the single-particle when the minimum particle size in the particle group is the same as that of a single particle.

Keywords: sub-micron particles, heterogeneous condensation, critical supersaturation, nucleation

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Authors: Maddumage Don Sandeepa Lakshad Wimalananda, Jae-Kwan Kim, Ji-Myon Lee

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Graphene is an extraordinary 2D material that shows superior electrical, optical, and mechanical properties for the applications such as transparent contacts. Further, chemical vapor deposition (CVD) technique facilitates to synthesizing of large-area graphene, including transferability. The abstract is describing the use of high surface free energy (SFE) and nano-scale high-density surface kinks (rough) existing Cu foil for CVD graphene growth, which is an opposite approach to modern use of catalytic surfaces for high-quality graphene growth, but the controllable rough morphological nature opens new era to fast synthesis (less than the 50s with a short annealing process) of graphene as a continuous film over conventional longer process (30 min growth). The experiments were shown that high SFE condition and surface kinks on Cu(100) crystal plane existing Cu catalytic surface facilitated to synthesize graphene with high monolayer and continuous nature because it can influence the adsorption of C species with high concentration and which can be facilitated by faster nucleation and growth of graphene. The fast nucleation and growth are lowering the diffusion of C atoms to Cu-graphene interface, which is resulting in no or negligible formation of bilayer patches. High energy (500W) Ar plasma treatment (inductively Coupled plasma) was facilitated to form rough and high SFE existing (54.92 mJm-2) Cu foil. This surface was used to grow the graphene by using CVD technique at 1000C for 50s. The introduced kink-like high SFE existing point on Cu(100) crystal plane facilitated to faster nucleation of graphene with a high monolayer ratio (I2D/IG is 2.42) compared to another different kind of smooth morphological and low SFE existing Cu surfaces such as Smoother surface, which is prepared by the redeposit of Cu evaporating atoms during the annealing (RRMS is 13.3nm). Even high SFE condition was favorable to synthesize graphene with monolayer and continuous nature; It fails to maintain clean (surface contains amorphous C clusters) and defect-free condition (ID/IG is 0.46) because of high SFE of Cu foil at the graphene growth stage. A post annealing process was used to heal and overcome previously mentioned problems. Different CVD atmospheres such as CH4 and H2 were used, and it was observed that there is a negligible change in graphene nature (number of layers and continuous condition) but it was observed that there is a significant difference in graphene quality because the ID/IG ratio of the graphene was reduced to 0.21 after the post-annealing with H2 gas. Addition to the change of graphene defectiveness the FE-SEM images show there was a reduction of C cluster contamination of the surface. High SFE conditions are favorable to form graphene as a monolayer and continuous film, but it fails to provide defect-free graphene. Further, plasma modified high SFE existing surface can be used to synthesize graphene within 50s, and a post annealing process can be used to reduce the defectiveness.

Keywords: chemical vapor deposition, graphene, morphology, plasma, surface free energy

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Authors: Bartlomiej S. Witkowski, Lukasz Wachnicki, Sylwia Gieraltowska, Rafal Pietruszka, Marek Godlewski

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Zinc oxide is extensively studied II-VI semiconductor with a direct energy gap of about 3.37 eV at room temperature and high transparency in visible light spectral region. Due to these properties, ZnO is an attractive material for applications in photovoltaic, electronic and optoelectronic devices. ZnO nanorods, due to a well-developed surface, have potential of applications in sensor technology and photovoltaics. In this work we present a new inexpensive method of the ultra-fast growth of ZnO nanorods from the aqueous solution. This environment friendly and fully reproducible method allows growth of nanorods in few minutes time on various substrates, without any catalyst or complexing agent. Growth temperature does not exceed 50ºC and growth can be performed at atmospheric pressure. The method is characterized by simplicity and allows regulation of size of the ZnO nanorods in a large extent. Moreover the method is also very safe, it requires organic, non-toxic and low-price precursors. The growth can be performed on almost any type of substrate through the homo-nucleation as well as hetero-nucleation. Moreover, received nanorods are characterized by a very high quality - they are monocrystalline as confirmed by XRD and transmission electron microscopy. Importantly oxygen vacancies are not found in the photoluminescence measurements. First results for obtained by us ZnO nanorods in sensor applications are very promising. Resistance UV sensor, based on ZnO nanorods grown on a quartz substrates shows high sensitivity of 20 mW/m2 (2 μW/cm2) for point contacts, especially that the results are obtained for the nanorods array, not for a single nanorod. UV light (below 400 nm of wavelength) generates electron-hole pairs, which results in a removal from the surfaces of the water vapor and hydroxyl groups. This reduces the depletion layer in nanorods, and thus lowers the resistance of the structure. The so-obtained sensor works at room temperature and does not need the annealing to reset to initial state. Details of the technology and the first sensors results will be presented. The obtained ZnO nanorods are also applied in simple-architecture photovoltaic cells (efficiency over 12%) in conjunction with low-price Si substrates and high-sensitive photoresistors. Details informations about technology and applications will be presented.

Keywords: hydrothermal method, photoresistor, photovoltaic cells, ZnO nanorods

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Authors: Esam I. Jassim

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The main aim of this paper is to demonstrate the prediction of the model capability of predicting the nucleation process, the growth rate, and the deposition potential of second phase particles in gas flowlines. The primary objective of the research is to predict the risk hazards involved in the marine transportation of compressed natural gas. However, the proposed model can be equally used for other applications including production and transportation of natural gas in any high-pressure flow-line. The proposed model employs the following three main components to approach the problem: computational fluid dynamics (CFD) technique is used to configure the flow field; the nucleation model is developed and incorporated in the simulation to predict the incipient hydrate particles size and growth rate; and the deposition of the gas/particle flow is proposed using the concept of the particle deposition velocity. These components are integrated in a comprehended model to locate the hydrate deposition in natural gas flowlines. The present research is prepared to foresee the deposition location of solid particles that could occur in a real application in Compressed Natural Gas loading and offloading. A pipeline with 120 m length and different sizes carried a natural gas is taken in the study. The location of particle deposition formed as a result of restriction is determined based on the procedure mentioned earlier and the effect of water content and downstream pressure is studied. The critical flow speed that prevents such particle to accumulate in the certain pipe length is also addressed.

Keywords: hydrate deposition, compressed natural gas, marine transportation, oceanography

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Authors: Rebecca Dewfall, Mark Coleman, Vladimir Basabe

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Oxide scale growth is an inevitable byproduct of the high temperature processing of steel. Blister is a phenomenon that occurs due to oxide growth, where high temperatures result in the swelling of surface scale, producing a bubble-like feature. Blisters can subsequently become embedded in the steel substrate during hot rolling in the finishing mill. This rolled in scale defect causes havoc within industry, not only with wear on machinery but loss of customer satisfaction, poor surface finish, loss of material, and profit. Even though blister is a highly prevalent issue, there is still much that is not known or understood. The classic iron oxidation system is a complex multiphase system formed of wustite, magnetite, and hematite, producing multi-layered scales. Each phase will have independent properties such as thermal coefficients, growth rate, and mechanical properties, etc. Furthermore, each additional alloying element will have different affinities for oxygen and different mobilities in the oxide phases so that oxide morphologies are specific to alloy chemistry. Therefore, blister regimes can be unique to each steel grade resulting in a diverse range of formation mechanisms. Laboratory conditions were selected to simulate industrial hot rolling with temperature ranges approximate to the formation of secondary and tertiary scales in the finishing mills. Samples with composition: 0.15Wt% C, 0.1Wt% Si, 0.86Wt% Mn, 0.036Wt% Al, and 0.028Wt% Cr, were oxidised in a thermo-gravimetric analyser (TGA), with an air velocity of 10litresmin-1, at temperaturesof 800°C, 850°C, 900°C, 1000°C, 1100°C, and 1200°C respectively. Samples were held at temperature in an argon atmosphere for 10minutes, then oxidised in air for 600s, 60s, 30s, 15s, and 4s, respectively. Oxide morphology and Blisters were characterised using EBSD, WDX, nanoindentation, FIB, and FEG-SEM imaging. Blister was found to have both a nucleation and growth process. During nucleation, the scale detaches from the substrate and blisters after a very short period, roughly 10s. The steel substrate is then exposed inside of the blister and further oxidised in the reducing atmosphere of the blister, however, the atmosphere within the blister is highly dependent upon the porosity of the blister crown. The blister crown was found to be consistently between 35-40um for all heating regimes, which supports the theory that the blister inflates, and the oxide then subsequently grows underneath. Upon heating, two modes of blistering were identified. In Mode 1 it was ascertained that the stresses produced by oxide growth will increase with increasing oxide thickness. Therefore, in Mode 1 the incubation time for blister formation is shortened by increasing temperature. In Mode 2 increase in temperature will result in oxide with a high ductility and high oxide porosity. The high oxide ductility and/or porosity accommodates for the intrinsic stresses from oxide growth. Thus Mode 2 is the inverse of Mode 1, and incubation time is increased with temperature. A new phenomenon was reported whereby blister formed exclusively through cooling at elevated temperatures above mode 2.

Keywords: FEG-SEM, nucleation, oxide morphology, surface defect

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Authors: Junze Li, M. Li

Abstract:

Laser diodes fabricated from the III-nitride material system are emerging solutions for the next generation telecommunication systems and optical clocks based on Ca at 397nm, Rb at 420.2nm and Yb at 398.9nm combined 556 nm. Most of the applications require single longitudinal optical mode lasers, with very narrow linewidth and compact size, such as communication systems and laser cooling. In this case, the GaN based distributed feedback (DFB) laser diode is one of the most effective candidates with gratings are known to operate with narrow spectra as well as high power and efficiency. Given the wavelength range, the period of the first-order diffraction grating is under 100 nm, and the realization of such gratings is technically difficult due to the narrow line width and the high quality nitride overgrowth based on the Bragg grating. Some groups have reported GaN DFB lasers with high order distributed feedback surface gratings, which avoids the overgrowth. However, generally the strength of coupling is lower than that with Bragg grating embedded into the waveguide within the GaN laser structure by two-step-epitaxy. Therefore, the overgrowth on the grating technology need to be studied and optimized. Here we propose to fabricate the fine step shape structure of first-order grating by the nanoimprint combined inductively coupled plasma (ICP) dry etching, then carry out overgrowth high quality AlGaN film by metalorganic chemical vapor deposition (MOCVD). Then a series of gratings with different period, depths and duty ratios are designed and fabricated to study the influence of grating structure to the nano-heteroepitaxy. Moreover, we observe the nucleation and growth process by step-by-step growth to study the growth mode for nitride overgrowth on grating, under the condition that the grating period is larger than the mental migration length on the surface. The AFM images demonstrate that a smooth surface of AlGaN film is achieved with an average roughness of 0.20 nm over 3 × 3 μm2. The full width at half maximums (FWHMs) of the (002) reflections in the XRD rocking curves are 278 arcsec for the AlGaN film, and the component of the Al within the film is 8% according to the XRD mapping measurement, which is in accordance with design values. By observing the samples with growth time changing from 200s, 400s to 600s, the growth model is summarized as the follow steps: initially, the nucleation is evenly distributed on the grating structure, as the migration length of Al atoms is low; then, AlGaN growth alone with the grating top surface; finally, the AlGaN film formed by lateral growth. This work contributed to carrying out GaN DFB laser by fabricating grating and overgrowth on the nano-grating patterned substrate by wafer scale, moreover, growth dynamics had been analyzed as well.

Keywords: DFB laser, MOCVD, nanoepitaxy, III-niitride

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Authors: Abhishek Kumar

Abstract:

X70 pipeline steel was electrochemically charged with hydrogen for different durations in order to find crack nucleation and propagation sites. After 3 hours charging, suitable regions for crack initiation and propagation were found. These regions were studied by OM, SEM, EDS and later Vicker hardness test was done. The results brought out that HIC cracks nucleated from regions rich of inclusions and further propagated through the segregation area of some elements, such as manganese, carbon, silicon and sulfur. It is worth-mentioning that all these potential sites for crack nucleation and propagation appeared at the centre of cross section of the specimens. Additionally, cracked area has harder phase than the non-cracked area which was confirmed by hardness test.

Keywords: X70 steel, morphology of inclusions, SEM/EDS/OM, simulation, statistical data

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Authors: Markus Nordlund, Arkadiusz K. Kuczaj

Abstract:

Philip Morris International (PMI) is developing a range of novel tobacco products with the potential to reduce individual risk and population harm in comparison to smoking cigarettes. One of these products is the Tobacco Heating System 2.2 (THS 2.2), (named as the Electrically Heated Tobacco System (EHTS) in this paper), already commercialized in a number of countries (e.g., Japan, Italy, Switzerland, Russia, Portugal and Romania). During use, the patented EHTS heats a specifically designed tobacco product (Electrically Heated Tobacco Product (EHTP)) when inserted into a Holder (heating device). The EHTP contains tobacco material in the form of a porous plug that undergoes a controlled heating process to release chemical compounds into vapors, from which an aerosol is formed during cooling. The aim of this work was to investigate the aerosol formation characteristics for realistic operating conditions of the EHTS as well as for relevant gas mixture compositions measured in the EHTP aerosol consisting mostly of water, glycerol and nicotine, but also other compounds at much lower concentrations. The nucleation process taking place in the EHTP during use when operated in the Holder has therefore been modeled numerically using an extended Classical Nucleation Theory (CNT) for multicomponent gas mixtures. Results from the performed simulations demonstrate that aerosol droplets are formed only in the presence of an aerosol former being mainly glycerol. Minor compounds in the gas mixture were not able to reach a supersaturated state alone and therefore could not generate aerosol droplets from the multicomponent gas mixture at the operating conditions simulated. For the analytically characterized aerosol composition and estimated operating conditions of the EHTS and EHTP, glycerol was shown to be the main aerosol former triggering the nucleation process in the EHTP. This implies that according to the CNT, an aerosol former, such as glycerol needs to be present in the gas mixture for an aerosol to form under the tested operating conditions. To assess if these conclusions are sensitive to the initial amount of the minor compounds and to include and represent the total mass of the aerosol collected during the analytical aerosol characterization, simulations were carried out with initial masses of the minor compounds increased by as much as a factor of 500. Despite this extreme condition, no aerosol droplets were generated when glycerol, nicotine and water were treated as inert species and therefore not actively contributing to the nucleation process. This implies that according to the CNT, an aerosol cannot be generated without the help of an aerosol former, from the multicomponent gas mixtures at the compositions and operating conditions estimated for the EHTP, even if all minor compounds are released or generated in a single puff.

Keywords: aerosol, classical nucleation theory (CNT), electrically heated tobacco product (EHTP), electrically heated tobacco system (EHTS), modeling, multicomponent, nucleation

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Authors: Roaa Sait, Richard Cross

Abstract:

The synthesis and characterization of one dimensional nanostructure such as nanowires has received considerable attention. Much effort has concentrated on TiN material especially in the biological field due to its useful and unique properties in this field. Therefore, for the purpose of this project, synthesis of Titanium Nitride (TiN) nanowires (NWs) will be presented. They will be synthesised by growing titanium dioxide (Ti) NWs in an aqueous solution at low temperatures under atmospheric pressure. Then the grown nanowires will undergo a 'Nitrodation process' in which results in the formation of TiN NWs. The structure, morphology and composition of the grown nanowires will be characterized using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD) and Cyclic Voltammetry (CV). Obtaining TiN NWs is a challenging task since it has not been formulated before, as far as we acknowledge. This might be due to the fact that nitriding Ti NWs can be difficult in terms of optimizing experimental parameters.

Keywords: nanowires, dissolution-growth, nucleation, PECVD, deposition, spin coating, scanning electron microscopic analysis, cyclic voltammetry analysis

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Authors: Lablali Mohammed, Mes-Adi Hassan, Mazroui M’Hammed

Abstract:

To tackle the complexity of grasping atomic-scale structures and unraveling the factors affecting the development of thin films. In our work, we perform the deposition of Nb atoms on Cu substrates using the molecular dynamics simulation combined with the embedded atom method to describe the interaction between different atoms. We investigated the impact of varying deposition rates and thermal annealing processes on the microstructural, morphological, and mechanical characteristics of the deposited Nb film. Our findings reveal that Nb atom growth on the Cu substrate occurs in island mode, accompanied by the presence of nucleation phenomena during growth. On the other hand, mixing behavior was observed at the interface between the film and the substrate, where Nb penetration is initially limited to the first Cu layer, whereas Cu atoms diffuse until reaching the third layer in the Nb film. Furthermore, Nb exhibits a BCC structure, with a significant concentration observed at a rate of 5 atoms/ps, and annealing further amplifies these percentages. Deposition at different rates leads to distinct levels of compressive normal and biaxial stress.

Keywords: molecular dynamics, Nb thin film, structure and morphology, atomic penetration

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Authors: N. Masoudnia, M. Fatahi

Abstract:

An experimental study of saturated pool boiling on a single artificial nucleation site without and with the application of an electric field on the boiling surface has been conducted. N-pentane is boiling on a copper surface and is recorded with a high speed camera providing high quality pictures and movies. The accuracy of the visualization allowed establishing an experimental bubble growth law from a large number of experiments. This law shows that the evaporation rate is decreasing during the bubble growth, and underlines the importance of liquid motion induced by the preceding bubble. Bubble rise is therefore studied: once detached, bubbles accelerate vertically until reaching a maximum velocity in good agreement with a correlation from literature. The bubbles then turn to another direction. The effect of applying an electric field on the boiling surface in finally studied. In addition to changes of the bubble shape, changes are also shown in the liquid plume and the convective structures above the surface. Lower maximum rising velocities were measured in the presence of electric fields, especially with a negative polarity.

Keywords: single bubbles, electric field, boiling, effect

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Authors: Shahid Hussain Abro, F. Mufadi, A. Boodi

Abstract:

Microstructural study and phase transformation in steels is a basic and important step during the design of structural steel. There are huge efforts and study has been done so far on phase transformations, due to so many steel grades available commercially the phase development in steel has different consequences. In the present work an effort has been made to study the effect of heating rate on microstructural features of cold heading quality steel. The SEM, optical microscopy, and heat treatment techniques have been applied to observe the microstructural features in the experimental steel. It was observed that heating rate has the strong influence on phase transformation of CHQ steel under investigation. Heating rate increases the austenite formation kinetics with respect to holding time, and this austenite has been transformed to martensite upon cooling. Heating rate also plays a vital role on nucleation sites of austenite formation in the experimental steel.

Keywords: CHQ steel, austenite formation, heating rate, nucleation

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Authors: M. Beyzaiea, S. Mohammadia

Abstract:

High aspect ratio metallic (silver, cobalt) nanowire arrays were fabricated using ac electrodeposition techniques into the nanoporous alumina template. The template with long pore dept fabricated by hard anodization (HA) and thinned for ac electrodeposition. Template preparation was done in short time by using HA technique and high speed thing process. The TEM and XRD investigation confirm the three dimensional nucleation growth mechanism of metallic nanowire inside the nanoporous alumina that fabricated by HA process.

Keywords: metallic, nanowire, nanoporous alumina, ac electrodeposition

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Authors: A. Saravanan, B. R. Huang, C. J. Yeh, K. C. Leou, I. N. Lin

Abstract:

A new class of ultra-nano diamond-graphite nano-hybrid (DGH) composite materials containing nano-sized diamond needles was developed at low temperature process. Such kind of diamond- graphite nano-hybrid composite nanowires exhibit high electrical conductivity and excellent electron field emission (EFE) properties. Few earlier reports mention that addition of N2 gas to the growth plasma requires high growth temperature (800°C) to trigger the dopants to generate the conductivity in the films. High growth temperature is not familiar with the Si-based device fabrications. We have used a novel process such as bias-enhanced-grown (beg) MPECVD process to grow diamond films at low substrate temperature (450°C). We observed that the beg-N/UNCD films thus obtained possess high conductivity of σ=987 S/cm, ever reported for diamond films with excellent Electron field emission (EFE) properties. TEM investigation indicated that these films contain needle-like diamond grains about 5 nm in diameter and hundreds of nanometers in length. Each of the grains was encased in graphitic layers about tens of nano-meters in thickness. These materials properties suitable for more specific applications, such as high conductivity for electron field emitters, high robustness for microplasma cathodes and high electrochemical activity for electro-chemical sensing. Subsequently, other hand, the highly conducting DGH films were coated on vertically aligned ZnO nanorods, there is no prior nucleation or seeding process needed due to the use of BEG method. Such a composite structure provides significant enhancement in the field emission characteristics of the cold cathode was observed with ultralow turn on voltage 1.78 V/μm with high EFE current density of 3.68 mA/ cm2 (at 4.06V/μm) due to decoration of DGH material on ZnO nanorods. The DGH/ZNRs based device get stable emission for longer duration of 562min than bare ZNRs (104min) without any current degradation because the diamond coating protects the ZNRs from ion bombardment when they are used as the cathode for microplasma devices. The potential application of these materials is demonstrated by the plasma illumination measurements that ignited the plasma at the minimum voltage by 290 V. The photoresponse (Iphoto/Idark) behavior of the DGH/ZNRs based photodetectors exhibits a much higher photoresponse (1202) than bare ZNRs (229). During the process the electron transport is easy from ZNRs to DGH through graphitic layers, the EFE properties of these materials comparable to other primarily used field emitters like carbon nanotubes, graphene. The DGH/ZNRs composite also providing a possibility of their use in flat panel, microplasma and vacuum microelectronic devices.

Keywords: bias-enhanced nucleation and growth, ZnO nanorods, electrical conductivity, electron field emission, photo-detectors

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Authors: Noe Brice Nkoumbou Kaptchouang, Pierre-Guy Vincent, Yann Monerie

Abstract:

The present work addresses the modelling and the simulation of crack initiation and propagation in ductile materials which failed by void nucleation, growth, and coalescence. One of the current research frameworks on crack propagation is the use of cohesive-volumetric approach where the crack growth is modelled as a decohesion of two surfaces in a continuum material. In this framework, the material behavior is characterized by two constitutive relations, the volumetric constitutive law relating stress and strain, and a traction-separation law across a two-dimensional surface embedded in the three-dimensional continuum. Several cohesive models have been proposed for the simulation of crack growth in brittle materials. On the other hand, the application of cohesive models in modelling crack growth in ductile material is still a relatively open field. One idea developed in the literature is to identify the traction separation for ductile material based on the behavior of a continuously-deforming unit cell failing by void growth and coalescence. Following this method, the present study proposed a semi-analytical cohesive model for ductile material based on a micromechanical approach. The strain localization band prior to ductile failure is modelled as a cohesive band, and the Gurson-Tvergaard-Needleman plasticity model (GTN) is used to model the behavior of the cohesive band and derived a corresponding traction separation law. The numerical implementation of the model is realized using the non-smooth contact method (NSCD) where cohesive models are introduced as mixed boundary conditions between each volumetric finite element. The present approach is applied to the simulation of crack growth in nuclear ferritic steel. The model provides an alternative way to simulate crack propagation using the numerical efficiency of cohesive model with a traction separation law directly derived from porous continuous model.

Keywords: ductile failure, cohesive model, GTN model, numerical simulation

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Authors: Dhaladhuli Pranavi, Amirtham Rajagopal

Abstract:

There are various failure modes in ceramic matrix composites; notable ones are fiber breakage, matrix cracking and fiber matrix debonding. Crack nucleation and propagation in microstructure of such composites requires an understanding of interaction of crack with the multiple inclusion heterogeneous system and interfaces. In order to assess structural integrity, the material parameters especially of the interface that governs the crack growth should be determined. In the present work, a nonlocal phase field approach is proposed to model the crack interface interaction in such composites. Nonlocal approaches help in understanding the complex mechanisms of delamination growth and mitigation and operates at a material length scale. The performance of the proposed formulation is illustrated through representative numerical examples. The model proposed is implemented in the framework of the finite element method. Several parametric studies on interface crack interaction are conducted. The proposed model is easy and simple to implement and works very well in modeling fracture in composite systems.

Keywords: composite, interface, nonlocal, phase field

Procedia PDF Downloads 142

Authors: Masoud Gholam Ale Mohammad, Mojtaba Hafezi Birgani

Abstract:

An experimental study of saturated pool boiling on a single artificial nucleation site without and with the application of an electric field on the boiling surface has been conducted. N-pentane is boiling on a copper surface and is recorded with a high speed camera providing high quality pictures and movies. The accuracy of the visualization allowed establishing an experimental bubble growth law from a large number of experiments. This law shows that the evaporation rate is decreasing during the bubble growth, and underlines the importance of liquid motion induced by the preceding bubble. Bubble rise is therefore studied: once detached, bubbles accelerate vertically until reaching a maximum velocity in good agreement with a correlation from literature. The bubbles then turn to another direction. The effect of applying an electric field on the boiling surface in finally studied. In addition to changes in the bubble shape, changes are also shown in the liquid plume and the convective structures above the surface. Lower maximum rising velocities were measured in the presence of electric fields, especially with a negative polarity.

Keywords: single and double bubbles, electric field, boiling, rising

Procedia PDF Downloads 226

Authors: Thien X. Dinh, Peter Witt

Abstract:

A one-dimensional model for the simulation of condensation and solidification of a metallurgical vapor in the mixture of gas during supersonic expansion is presented. In the model, condensation is based on critical nucleation and drop-growth theory. When the temperature falls below the supercooling point, all the formed liquid droplets in the condensation phase are assumed to solidify at an infinite rate. The model was verified with a Computational Fluid Dynamics simulation of magnesium vapor condensation and solidification. The obtained results are in reasonable agreement with CFD data. Therefore, the model is a promising, efficient tool for use in the design process for supersonic nozzles applied in mineral processes since it is faster than the CFD counterpart by an order of magnitude.

Keywords: condensation, metallurgical flow, solidification, supersonic expansion

Procedia PDF Downloads 63