Micromechanical Effects Research Articles

Effect of aggregate size on the slump and uniaxial compressive strength of concrete: a DEM study

The aggregate size and particle-size distribution (PSD) can change the packing density, slump, and strength of concrete. The micromechanical effects of aggregate size on the slump and strength remain unclear. The current numerical study examined concrete behavior using slump and uniaxial compressive strength (UCS) tests considering the aggregate size distribution using the discrete element method. The effect of the aggregate size on the packing density, UCS, and slump of the concrete was analyzed. To accomplish this, we evaluated how variations in the uniformity and curvature coefficients of the PSD, as well as the specific surface area of the samples, were affected by changes in aggregate size. Although the simulations were based on standard specimens from the laboratory, the results showed good agreement with the documented experimental results. Briefly, at a 40–60% fine aggregate content, the packing density and compressive strength of the concrete reached their peaks and caused a decrease in the height of the slump. The uniformity and curvature coefficients did not influence the slump height. The induced shear band could be tracked during the UCS tests and the crack angles could be measured. At the optimum fine content (40–60%), the shear bands were primarily localized and propagated through the samples having different fine contents.

Understanding the influence of drained cyclic preloading on liquefaction resistance of sands using DEM-clump modeling

The soils in situ are subjected to various types of preloading histories. Extensive work has been devoted to understanding the impact of undrained preloading with different strain histories on the reliquefaction resistance of sands. This study primarily examines the effects of drained cyclic preloading histories on the liquefaction resistance of soils using DEM-clump modeling. The effects of preloading stress path and preloading deviatoric stress amplitude on the drained cyclic behavior and subsequent undrained liquefaction response are discussed. Moreover, the evolution of two microscale descriptors, including coordination number Z and fabric anisotropy degree ac, during the total process is analyzed. The results demonstrate that a smaller preloading stress amplitude and an increasing preloading cycle generally increase the liquefaction resistance of sandy soils. In comparison, a larger preloading stress amplitude significantly reduces the liquefaction resistance. We also reveal that drained cyclic preloading histories induce soil samples with different relative densities and fabrics. The relationship between relative density and liquefaction resistance of soils is not unique. Essentially, Z and ac are good indexes for determining the liquefaction resistance of soils with various drained cyclic preloading histories. The primary objective of this study is to elucidate the micromechanical effects of drained cyclic preloading on the liquefaction resistance of sandy soils.

Combination of scanning electron microscopy and digital image correlation for micrometer-scale analysis of shear-loaded adhesive joints

ABSTRACT To understand adhesive bonds and their macroscopic behavior, a new experimental method is presented in this paper that allows to investigate micromechanical effects down to nanometer scale under load. The method combines ion milled cross sections, low-voltage scanning electron microscopy (SEM), digital image correlation, and a miniaturized testing machine in the SEM-chamber. Experimental results from shear-loaded adhesively bonded carbon fiber-reinforced polymer specimens illustrate the method’s benefits. Through a plasma etching process, the specimen cross section is textured, creating a stochastically distributed speckle pattern visible in SEM images. A miniaturized testing machine placed in the SEM is used to apply a load to the specimens while capturing images simultaneously. The resulting image series can be analyzed by image correlation algorithms. This method enables precise statements regarding strain distribution on the specimen at micro- and nanometer scales. While conventional coupon tests on bonded specimens can only depict the effects of a composite in a homogenized manner, the new method allows to gain additional insights into the underlying mechanisms.

Micromechanical effects of substrate hardness on graphene nano-cutting quality

In the nanocutting process of graphene, the mechanism on the atomic scale of the effect of substrate hardness on the edge quality of graphene nanoribbons has not been thoroughly investigated. In this paper, we construct a diamond probe (radius of 5 Å) to cut graphene (190 Å × 113 Å) models with different substrates (silicon/sapphire/silicon carbide), molecular dynamics simulations were used to study the effect of substrate hardness and cutting depth on the atomic structure of graphene nanoribbon edges by observing the atomic morphology, the number of C-C bonds, the radial distribution function and friction. The results show that during the nanoindentation stage, when graphene is in the critical damage state, the substrate with high hardness has high deformation strength, the substrate deformation is small, and graphene undergoes deformation is also small, but the force Fz on the probe, the critical graphene stress σz and the equivalent stress are all large, and the number of C atoms with CN=3 is large; At the nano-cutting stage, the breakage of C-C bonds and the generation of edge defects are caused by local stress concentration, and the graphene stress σxx along the x-direction has a clear directionality. With the same cutting depth (critical damage depth of silicon substrate), silicon substrate hardness is small, the graphene nanoribbon obtained has less number of circular defects generated at the edge, less total number of defective atoms, more number of CN=3 atoms, large peak of radial distribution function of graphene after cutting, and graphene integrity is better. The hardness of the silicon carbide substrate is large, and the number of C-C bond breaks in graphene during the cutting process is high. Each substrate is cut at its own critical damage depth, and the substrate hardness has no significant effect on the number of C-C bond breaks, the number of circular defects, the total number of defective atoms, and the number of CN=3 atoms in graphene. When the silicon substrate was used, the stable force of the probe is small, the edge structure of graphene has little impact, the edge effect obtained is good. The cutting depth and substrate hardness have little effect on the graphene temperature during the nano-cutting process. In this paper, the atomic structure of graphene edges after cutting is analysed and investigated on the atomic scale, and the above results are combined to provide theoretical guidance for obtaining efficient and high-quality and low-damage graphene nanoribbon cutting.

A novel multiscale model for mixed-mode fatigue crack growth in laminated composites

A multiscale model is developed to predict mixed-mode fatigue crack growth (FCG) behavior in laminated composites by considering the micromechanical effects of fiber bridging. The proposed model consists of a micromechanical part dedicated to the fiber bridging mechanism near the crack tip, a macroscopic FCG model based on the maximum principal strain criterion, and an effective crack tip processing zone (i.e., an equivalent critical distance) connecting the two parts of the model. The core novelty of the presented model is to connect two scales (micro and meso) through a measurable physical quantity – called equivalent critical distance – accounting for various micromechanical as well as macroscopic phenomena occurring at both scales. The suggested model is validated against FCG test data available in the literature for laminated glass fiber composites under mode I, mode II, and mixed mode I/II conditions. It is found that the proposed framework is superior to its conventional (pure macroscopic) version, which eliminates fiber bridging effects, in the prediction of the cyclic mixed-mode crack propagation behavior in laminated composites. The multiscale nature of the proposed FCG model offers less complexity than fully micromechanical approaches while providing higher accuracy as compared to pure macroscopic models that ignore micromechanical phenomena occurring at the fiber scale.

Investigation of strain rate dependent microscopic failure mechanisms in short fiber reinforced plastics using finite element simulations

For predicting the strain rate dependent failure of short fiber reinforced plastics (SFRP) a two-phase simulation model is developed using the finite element method and comparing the results to microscopic specimen tests for uniaxial tension under quasi-static (0.007/s) and dynamic loads (250/s). Experimentally the failure behavior of SFRP is observed to be strain rate dependent. The global strain at failure and the absorbed energy increase with strain rate. Moreover, locally an influence of the strain rate on the amount of material involved in the deformation can be observed. The suggested model can represent these effects accurately. Also, the present micro-mechanical effects and their influence on the strain distribution are investigated by unit cell simulations. Thereby the material model of the fibers, the matrix, and the boundary layer are varied respectively. These reveal the important role of strain rate dependent decohesion leading to a correct representation of the plastically deformed volume. Consequently, the distortion energy density is evaluated and is found to be constant at failure for all strain rates.

Contactless mechanical stimulation of tissue engineered constructs: Development and validation of an air-pulse device

ObjectiveTissue engineering (TE) is the study and development of biological substitutes to restore, maintain or improve tissue function. Tissue engineered constructs (TECs) still present differences in mechanical and biological properties compared to native tissue. Mechanotransduction is the process through which mechanical stimulation triggers proliferation, apoptosis, and extracellular matrix synthesis, among other cell activities. Regarding that aspect, the effect of in vitro stimulations such as compression, stretching, bending or fluid shear stress loading modalities have been extensively studied. A fluid flow used to produce contactless mechanical stimulation induced by an air pulse could be easily achieved in vivo without altering the tissue integrity. MethodsA new air-pulse device for contactless and controlled mechanical simulation of a TECs was developed and validated in this study conducted in the following three phases: 1) conception of the controlled air-pulse device combined with a 3D printed bioreactor; 2) experimental and numerical mechanical characterization of the air-pulse impact by digital image correlation; and 3) achieving sterility and noncytotoxicity of the air-pulse and of the 3D printed bioreactor using a novel dedicated sterilization process. ResultsWe demonstrated that the treated PLA (polylactic acid) was noncytotoxic and did not influence cell proliferation. An ethanol/autoclaved sterilization protocol for 3D printed objects in PLA has been developed in this study, enabling the use of 3D printing in cell culture. A numerical twin of the device was developed and experimentally characterized by digital image correlation. It showed a coefficient of determination R2 = 0.98 between the numerical and averaged experimental surface displacement profiles of the TEC substitute. ConclusionThe results of the study assessed the noncytotoxicity of PLA for prototyping by 3D printing the homemade bioreactor. A novel sterilization process for PLA was developed in this study based on a thermochemical process. A numerical twin using fluid-structure interaction method has been developed to investigate the micromechanical effects of air pulses inside the TEC, which cannot all be measured experimentally, for instance, wave propagation generated during the air-pulse impact. The device could be used to study the cell response to contactless cyclic mechanical stimulation, particularly in TEC with fibroblasts, stromal cells and mesenchymal stem cells, which have been shown to be sensitive to the frequency and strain level at the air-liquid interface.

What can micromechanics tell us about the surface integrity of shot-peened materials?

Standard techniques for assessing shot peening include XRD and EBSD for measuring residual stresses and severe deformation beneath the surface; however, these techniques do not consider the localised micromechanical behaviour. Here, single-grain micropillar compression tests in a Ni-base superalloy reveal that the micromechanical effect of shot peening could be insignificant due to the machining-induced pre-strained condition of the surface. Further, it is shown that shot-peening-induced strengthened layer can extend much less (∼50%) than the depth at which compressive stresses are still present. This work highlights the need for employing micromechanics as a complementary shot peening assessment technique for machined components.

A variational fracture method based on Eshelby transformation

We propose a variational fracture simulation method based on Eshelby’s transformation. The fracture zone is viewed as an inclusion with non-zero eigenstrain, and the fracture energy can be derived from the inclusion interaction energy within the eigendeformation framework. For the common crack-type inclusions, the method turns to be a phase field model. Eshelby’s inclusion tensor is used to construct a novel degradation function. The yield surface of the variational fracture method resembles the plastic potential of Gurson-type fracture models, which indicates that hydrostatic dependency and micromechanical effects have been incorporated. The efficiency and capability of this method are validated by plane strain tension and shear tests. Micro-structural softening associated with growth and coalescence of the micro-cracks may largely promote the initiation and evolution of fractures.

Micro-mechano-morphology-informed continuum damage modeling with intrinsic 2nd gradient (pantographic) grain–grain interactions

In a previous work, we have shown that a granular micromechanics approach can lead to load path dependent continuum models. In the present work, we generalize such a micromechanical approach introducing an intrinsic 2nd gradient energy storage mechanism (resembling pantographic micromechanism), in the grain–grain interaction. Such a mechanism, represents long-range effects but could also be thought as deriving from the utilization of an actual pantographic connection between two grains in a granular metamaterial. Taking advantage of the homogenization approach developed in previous works, we determine the mechanical behavior of the macro-scale continuum and carry out parametric analyses with respect to the averaged intergranular distance and with respect to the stiffness associated to the pantographic term. We show that with the inclusion of the pantographic term mentioned above, the desired thickness of the localization zone can be modeled and finely tuned successfully. We also show that the complex mechanics of load-path dependency can be predicated by the micromechanical effects and the introduced pantographic term.

(Invited) Atomic-Scale Aspects of Nucleation and Growth at Liquid-Liquid Interfaces

Interfaces between liquid metals and liquid electrolytes, in particular the liquid Hg - electrolyte interface, have played a key role in the development of the theory of the electrical double layer and electrochemical adsorption. More recently, liquid-liquid interfaces have regained interest in the field of material synthesis. Unlike solid interfaces, where strain and stress, heterogeneities, and defects strongly influence growth processes, fluid systems provide soft, defect- and stress-free interfaces. In addition, the growth process profits from the high mobility of atoms, molecules, and particles in both liquids, which allows growth from both sides of the phase boundary. A large variety of metallic and non-metallic nanomaterials has been prepared via electrochemical and electroless deposition at such liquid-liquid interfaces. As demonstrated by Maldonado and coworkers, electrodeposition at liquid metal electrodes even allows the growth of nanostructured crystalline semiconductors via a simple one-step, room-temperature electrochemical process [1].Understanding of the fundamental processes in nucleation and growth at liquid-liquid interfaces is hampered by difficulties in studying these interfaces experimentally on the atomic scale. Most surface-sensitive techniques, especially also scanning probe microscopy methods, cannot access these fluidic phase boundaries. For this reason, the majority of studies relies on electrochemical measurements, optical microscopy, and ex situ investigation of the deposit and thus provide little insight on the initial steps of the growth process. We have shown in the past that hard X-ray scattering methods, such as X-ray reflectivity (XRR) and grazing incidence X-ray scattering (GIXS), are unique tools for determining the atomic liquid-liquid interface structure. In this talk, we present case studies of electrochemically induced growth at liquid interfaces from the first monolayer up to several ten nanometer thick films.The first part discusses the growth of ionic compounds, using lead halides on Hg electrodes as an example. In PbBr2 containing NaF we observed previously growth of a PbBrF layer by operando X-ray scattering. This growth exhibited a complex nucleation and growth behavior, involving a crystalline precursor layer prior to 3D crystal growth [2]. The well-defined subnanometer thick precursor layer provided a template for the subsequent quasi-epitaxial growth of oriented 3D crystallites. Detailed studies on the potential-dependent nucleation and growth kinetics revealed with increasing overpotential a crossover from a low surface density film of large crystals to a compact PbBrF deposit with a saturation thickness of 25 nm [3,4]. In addition, growth on the liquid substrate was found to involve micromechanical effects, such as crystal reorientation and film breakup during dissolution. More recently, we extended these studies to growth in solutions containing only one type of halide anion (Br, Cl, or F). Also here, the formation of precursor layers was observed, indicating that this growth behavior is a general phenomenon.In the second part, joint X-ray scattering studies with Maldonado and coworkers on the electrochemical liquid-liquid-solid deposition of semiconductors from aqueous electrolyte are presented, focusing on Ge electrodeposition on Hg and HgxIn1-x alloy electrodes [5]. We provide evidence for the adsorption of GeO3 - anions on the liquid metal surface and the formation of a crystalline GeO2 adlayer at the positive end of the double layer region. Ge electrodeposition results in nanocrystals, which are separated from the Hg electrode by a water cushion. Furthermore, pronounced Hg surface segregation is found in HgxIn1-x, which protects the electrode surface from oxidation in the potential regime of Ge deposition.[1] Carim, A. I., Collins, S. M., Foley, J. M. & Maldonado, J. Am. Chem. Soc. 133, 13292 (2011)[2] A. Elsen, S. Festersen, B. Runge, C.T. Koops, B. M. Ocko, M. Deutsch, O. Seeck, B. M. Murphy, O. M. Magnussen, Proc. Nat. Acad. Sci., 110, 6663 (2013)[3] B.M. Murphy, S. Festersen, O.M. Magnussen, Nanoscale, 8, 13859 (2016)[4] S. Festersen, B. Runge, C. Koops, F. Bertram, B.M. Ocko, M. Deutsch, B.M. Murphy, O.M. Magnussen, Langmuir, 36, 10905 (2020)[5] D. Pattadar, Q. Cheek, A. Satori, Y. Zhao, P.R. Giri, B. Murphy, O.M. Magnussen, S. Maldonado, Cryst. Growth Des., 21, 1645 (2021)

Study on Interfacial Interlocking Effect of Ultrasonic Vibration-Assisted Adhesive Bonding.

Carbon fiber reinforced polymer (CFRP) blades are often exposed to wild and even harsh environments. The durability of the blade can be greatly improved by adhesively bonding a Ni erosion shield to the leading edge. In a traditional bonding process, the permeation of adhesive is poor at the interface, which gives an insufficient micromechanical interlocking. In this study, ultrasonic vibration was applied during the bonding process of sandblasted Ni plates and CFRP laminates. The values of shear strength were measured by tensile tests to verify the strengthening effect of applying ultrasonication. The cross-section of the bonded interface was characterized by scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS), and the surfaces with different treatments were explored by atomic force microscopy (AFM). The cross-sectional morphology and failure model of the samples were investigated. The strengthening mechanism was then studied by a molecular dynamics method. For the simulation of molecular dynamics, the CFRP/Ni bonding interface model was designed using the Materials Studio software package. The Perl scripts were used to simulate the ultrasonic vibration with different frequencies and amplitudes. The results showed that the ultrasonic process could improve the permeability and uniformity of the adhesive, enhancing the micromechanical interlocking effect.

Comparative analysis of dynamic progressive failure of CFRPs using the scale-span and macroscopic modeling method in drilling

The focus of this paper is to explore the effects of different failure criteria, including Tsai-Wu, Hashin, Chang-Chang and micromechanics of failure criterion, on the dynamic progressive failure properties of carbon fiber reinforced polymers (CFRPs) in drilling. First, a unified finite element (FE) formulation on the dynamic intra-laminar damage and inter-laminar delamination of laminates was developed. Then, the intra-laminar damage model using four failure criteria were implemented by the explicit FE subroutine ABAQUS/VUMAT. Meanwhile, the delamination is simulated by the developed bilinear cohesive elements (CEs) model with mixed-mode failure criterion. Finally, numerical analysis and experiments were performed on drilling T700S-12K/YP-H26 CFRPs laminates to compare the predicted thrust force, torque and the visualized damage phenomenon. Results show that the prediction accuracy of the thrust force and torque is significantly improved. The actual damage behaviors which appear the tearing at the entry, pits of hole-wall’s surface, burrs and interlayer delamination at the exit are simulated when adopts the scale-span modeling method. In contrast, it is required to take more slightly simulation time under the same condition. This research provides fundamental support for appropriate selection and use of different failure criteria to achieve high-efficiency and high-fidelity simulation in the drilling of composites.

Micromechanical Effect of Martensite Attributes on Forming Limits of Dual-Phase Steels Investigated by Crystal Plasticity-Based Numerical Simulations

This study analyses the effect of martensite grain size and its volume fraction in dual-phase (DP) steel on (1) the formability limit, (2) average global behavior under different loading conditions, and (3) damage initiation. The virtual RVEs (Representative Volume Elements) were constructed using DREAM.3D software with a variation of microstructural attributes. The numerical simulations were carried out using DAMASK, which evaluates the polycrystalline material point behavior and solves versatile constitutive equations using a spectral solver. The simulations were post-processed to obtain global and local stress, strain, and damage evolution in constructed RVEs. The global results were processed to obtain FLDs according to Keeler-Brazier (K-B) and Marciniak and Kuczynski (M-K) criteria. In this work, the capability of microstructure-based numerical simulations to analyze the FLDs has been established successfully. From Forming Limit Diagrams (FLDs), it was observed that formability changes by changing the strain hardening coefficients (n-values), the martensite fraction, and martensite grain sizes of DP steels. The improved formability was observed with lower martensite fraction, i.e., 17%, decreased martensite grain size, i.e., 2.6 µm, and higher strain hardening coefficient. The M-K approach shows the better capability to predict the formability by various loading conditions and clarifies the necking marginal zone of FLD. The damage propagation is also strongly affected by the loading conditions. The current study would be a good guide for designers during the manufacturing and selecting of appropriate DP steels based on the service loading conditions.

A fracture mechanics approach to hydrogen assisted microdamage and failure analysis of high-strength pearlitic steel wires: Resembling Michelangelo Stone Sculpture Texture

A fracture mechanics approach to hydrogen-assisted microdamage and failure analysis of high-strength pearlitic steel wires is presented. Fractographic analysis revealed micromechanical effects of hydrogen in the form of tearing topography surface(TTS). The progress of this microdamage is modelled as a macroscopic crack that extends the original fatigue precrack and involves linear elastic fracture mechanics (LEFM) principles. In this case, the change from hydrogen-assisted microdamage (HAMD) in the form of TTS (subcritical mode) to cleavage-like topography (critical regime associated with failure) takes place when a critical stress intensity factor (KH) is reached, and this value depends on the amount of hydrogen which penetrated the vicinity of the actual crack tip (the fatigue precrack plus the TTS extension). It is seen that the crack growth by TTS corresponds to the horizontal part (plateau) in the crack growth kinetics (CGK) curve da/dt-K until reaching the critical level KH.

Smooth or not: Robust fused silica micro-components by femtosecond-laser-assisted etching

Recent progress in manufacturing now enables the efficient fabrication of complex oxide-glass components at the micrometer– to sub-micrometer scale. This benefits both the industry and fundamental research as such miniature glass parts have numerous applications. However, at these length-scales, the mechanical properties of glasses can no longer be predicted based on bulk material characteristics. Here it is shown that fused silica micro-pillars fabricated by laser-assisted etching are almost ten times stronger than their bulk-sized counterparts. The relatively rough surface typical for this process does not much impair this strength. Additionally, it is demonstrated that annealing of the as-fabricated structures at 1200 °C in air results in significantly smoother surfaces. The accompanying increase in mechanical strength from approximately 8 GPa to 10 GPa is due to the reduction of stress concentrations at the surface, as demonstrated by finite element simulations. It is also demonstrated that the gain in mechanical resistance of glass components due to downsizing occurs already for parts as large as almost 20 µm – orders of magnitude above the critical size reported for other micro-mechanical effects. These micro-mechanical properties of selective laser-assisted etching structured fused silica components are key to a reliable use of glass micro-components.

Micromechanical effect of pores on elastic properties of polymer matrix composites

AbstractAdvanced composite polymer matrix and their different manufacturing processes tend to develop pores of varying size and play a major limiting role in residual stress, damage initiation, matrix cracking, strength, and durability. Direct imaging or simulations to understand the pore formation mechanism in the viscous polymer is difficult. Ultimately, the mechanical performance of the solidified matrix needs better prediction. This paper presents a stochastic micromechanical model, including the effect of pores' formation on the polymer matrix's elastic properties. Theoretical homogenization based micromechanical models for polymer composites is reviewed in the first part. Later, a micromechanical model is proposed considering the different stages of pore formation in a polymer matrix. Polymer samples are fabricated for determining the pore distribution parameters and used appropriately in the proposed model to estimate the elastic properties for a given distribution and volume fraction of the pores. A modified Mori‐Tanaka homogenization approach and a differential scheme of inclusion of pores are incorporated in the model. Results obtained from the proposed model are compared with the experimental measurements, and a significant correlation is found.

Analysis of shape, orientation and interface properties of Mo[formula omitted]C precipitates in Fe using ab-initio and finite element method calculations

We study the Mo2C precipitate, a carbide commonly used for secondary hardening in steels, and its interface to the Fe matrix using a combination of ab-initio density functional theory and finite element simulations. For Mo2C and Fe, the elastic properties as a function of temperature are determined and different interfaces of the carbide to the matrix are characterized. With finite element simulations that use the derived elastic properties and interface energies as input, the energy contributions from elasticity and creep are evaluated. Combining the results from atomic to micro scale allows to explain the specific needle shape of these precipitates that has been reported experimentally. For one selected interface, also the full elastic properties are determined with ab-initio methods and compared to the Grimsditch-Nizzoli approach, where we find good agreement. Our study shows how a combination of the ab-initio and the finite element method may be used to characterize and understand the micro-mechanical effects of precipitates.

The study of bubble size distribution in reservoir during foam flooding and optimization design of gas alternating foaming liquid injection

Foam flooding is one of the enhanced oil recovery (EOR) technologies that have great development potentials. The theoretical models of foam flooding at present include empirical models and mechanism models. The empirical models usually simplify the blocking effect of foam system in porous medium as a reduction coefficient of fluid mobility (mainly for gas phase). The mechanism models introduce the processes of foam propagation and decay, and its numerical simulation theory views these two processes as chemical reactions that involve reactants and products. However, these two kinds of foam models do not represent the micro-mechanical effects between the gas bubble and pore-throat in porous medium. In this work, a geometric model of pore-throat was established based on the core data of rate-controlled porosimetry. Then, the snap-off time of generating gas bubble in core sample was calculated with the data of foam flooding experiment. Finally, combined with numerical simulation, the distribution of bubble size in reservoir during foam flooding was calculated. Comparing different plans of gas alternating foaming liquid injection, it was found that when consuming the same amount of gas and foaming liquid, the increasing-ratio of gas alternating foaming liquid injection has a larger sweep range of foam and a more extended zone of effective-sized bubble than the constant-ratio injection does, which indicates that the increasing-ratio of gas alternating foaming liquid injection has a higher efficiency.

Nucleation and Growth of PbBrF Crystals at the Liquid Mercury-Electrolyte Interface Studied by Operando X-ray Scattering.

Detailed in operando studies of electrochemically induced PbBrF deposition at the liquid mercury/liquid electrolyte interface are presented. The nucleation and growth were monitored using time-resolved X-ray diffraction and reflectivity combined with electrochemical measurements, revealing a complex potential-dependent behavior. PbBrF deposition commences at potentials above -0.7 V with the rapid formation of an ultrathin adlayer of one unit cell thickness, on top of which (001)-oriented three-dimensional crystallites are formed. Two potential regimes are identified. At low overpotentials, slow growth of a low surface density film of large crystals is observed. At high overpotentials, crossover to a potential-independent morphology occurs, consisting of a compact PbBrF deposit with a saturation thickness of 25 nm, which forms within a few minutes. This potential behavior can be rationalized by the increasing supersaturation near the interface, caused by the potential-dependent Pb2+ deamalgamation, which changes from a slow reaction-controlled process to a fast transport-controlled process in this range of overpotentials. In addition, growth on the liquid substrate is found to involve complex micromechanical effects, such as crystal reorientation and film breakup during dissolution.