Nucleation Of New Grains Research Articles

Computer Simulation Study on Dynamic Recrystallization Mechanism of Magnesium Alloy during Compound Deformation

The evolution law of dynamic recrystallization structure in the process of indentation-flattening compound deformation technology (IFCDT) of AZ31 magnesium alloy was studied. A computer simulation method for dynamic recrystallization structure evolution process was proposed based on cellular automata theory (CA method). Firstly, the material model of cellular automata method is established. Secondly, the performance parameters and compound deformation parameters of AZ31 magnesium alloy were determined. Finally, the dynamic recrystallization process of AZ31 magnesium alloy during compound deformation was analyzed. During the compound deformation of AZ31 magnesium alloy, the dynamic recrystallization mechanism is initial state, nucleation of new grains, generation of new grains, growth of new grains, continuous growth of new grains, and covering of original large grains. Compared simulation results with experimental results, the maximum relative errors is 15.4%. It is proved that cellular automaton method may be used to predict the microstructure evolution of AZ31 magnesium alloy during indentation-flattening compound deformation.

A new micromechanics based full field numerical framework to simulate the effects of dynamic recrystallization on the formability of HCP metals

This paper presents a new full-field, efficient and mesh-free numerical framework to model microstructure evolution, dynamic recrystallization (DRX) and formability in hexagonal closed-packed (HCP) metals such as magnesium alloys at warm temperatures. A rate tangent-fast Fourier transform-based elasto-viscoplastic crystal plasticity constitutive model for HCP metals (RTCP-FFT-HCP) is coupled with a probabilistic cellular automata (CA) approach to model DRX (CA-DRX). Furthermore, this new model is coupled with the Marciniak-Kuczynski (M-K) approach to model formability of magnesium alloys at elevated temperatures. The RTCP-FFT-HCP model computes macro stress-strain, twinning volume fraction, micromechanical fields, texture evolution and local dislocation density. Nucleation of new grains and their subsequent growth is modeled using the cellular automata approach with probabilistic state switching rule. First, the proposed RTCP-FFT-HCP model is validated by comparing the predicted stress-strain responses and texture evolution under uniaxial tension and compression with experimental measurements for AZ31 sheet alloy at room temperature. The coupled CA-RTCPFFT-HCP model is further validated by comparing the predicted stress-strain responses and texture evolution in uniaxial compression with experimental measurements at 100 °C, 200 °C and 300 °C for the AZ31 sheet alloy. Next, the forming limit diagrams (FLDs) with and without including the effects of DRX are simulated at 100 °C, 200 °C and 300 °C for AZ31 sheet alloy. The predicted FLDs with DRX show very good agreement with the experimental measurements and clearly demonstrate the need for an accurate DRX model. The study reveals that the DRX strongly affects the deformed grain structure, grain size and texture evolution and also highlights the importance accounting for DRX during FLD simulations at high temperatures.

In-Situ Synchrotron X-Ray Diffraction of Ti-6Al-4V During Thermomechanical Treatment in the Beta Field

This work aims to identify the mechanisms of restoration occurring in Ti-6Al-4V during hot plastic deformation and subsequent heat treatment. The allotropic phase transformation that occurs during cooling distorts the interpretation of the restoration mechanisms taking place at high temperatures. Therefore, analysis of deformed samples by conventional microscopy have led to controversies in the interpretation of the main dynamic restoration mechanism. Additionally, static restoration of the microstructure can occur during slow cooling, modifying the microstructure. These facts were mainly the reasons why discontinuous dynamic recrystallization and/or dynamic recovery has been reported as the main dynamic restoration mechanism for Ti-6Al-4V. In this work, we use in-situ synchrotron X-ray diffraction combined with conventional microscopy to determine the dynamic and static mechanisms of restoration during and after deformation at different strain rates. The results show dynamic recovery as main mechanism of restoration during deformation in the β field, denoted by sub-grain formation and a misorientation dependency of the strain rate. After deformation, static recrystallization, grain growth, and coarsening of the β grains can be observed, especially at strain rates higher than 0.1s−1. It is also demonstrated that the nucleation of new grains can occur within the very first seconds of the isothermal heat treatment.

Recrystallization and grain growth at the interface of a bimetallic colaminated strip composed of two different Fe-Ni alloys

Roll bonding is a solid-state welding process widely used to manufacture layered metal composites. Particular properties may thus be obtained using the physical features of each material of the composite. Bimetal plates consisting of two different Fe-Ni alloys were made by roll bonding followed by heat treatment for 90 minutes at various annealing temperatures. The effects of post-rolling heat treatments on the bonding strength of a bimetal strip were investigated in relation to the interface microstructure evolution. Both recrystallization and grain growth took place at the interface during annealing. In particular, nucleation of new grains as well as growing grains crossing the interface may have contributed to the improvement of the bonding strength. Moreover, diffusion through the interface was found to drastically enhance the bonding strength from 850°C up to 1050°C. However, excessive grain growth associated to porosity occurrence probably caused the saturation of the bonding strength beyond 1050°C.

Crystal Plasticity modeling of dynamic recrystallization in CP Ti

The present work is an attempt at modeling the phenomenon of dynamic recrystallization (DRX) in commercial purity α-titanium. DRX is associated with increase in number of grains along with loss of strength. Thus it is critical to understand its occurrence while structural metal components and parts are processed. A dislocation density hardening based approach accounts for the occurrence of DRX subject to achieving a critical value of dislocation density for each grain. A model describing nucleation and probability of DRX is integrated into a polycrystal plasticity framework. Only slip deformation modes are considered. In the present work, multiple parametric studies have been carried out. The formation of new DRX grains with deformation has been highlighted. Due to applying a probabilistic criterion for addition of new DRX grains, this number is less than the number of grains having dislocation density more than critical value that is required for occurrence of DRX. The average dislocation density over all grains has been shown to decrease with deformation due to nucleation of new grains. A modified algorithm for modeling dynamic recrystallization has henceforth been demonstrated for CP Ti via evolution of flow stress, dislocation density and grain weights of ‘old’ and ‘new’ grains with deformation.

Microstructural Evidence for Grain Boundary Migration and Dynamic Recrystallization in Experimentally Deformed Forsterite Aggregates

Plastic deformation of peridotites in the mantle involves large strains. Orthorhombic olivine does not have enough slip systems to satisfy the von Mises criterion, leading to strong hardening when polycrystals are deformed at rather low temperatures (i.e., below 1200 °C). In this study, we focused on the recovery mechanisms involving grain boundaries and recrystallization. We investigated forsterite samples deformed at large strains at 1100 °C. The deformed microstructures were characterized by transmission electron microscopy using orientation mapping techniques (ACOM-TEM). With this technique, we increased the spatial resolution of characterization compared to standard electron backscatter diffraction (EBSD) maps to further decipher the microstructures at nanoscale. After a plastic strain of 25%, we found pervasive evidence for serrated grain and subgrain boundaries. We interpreted these microstructural features as evidence of occurrences of grain boundary migration mechanisms. Evaluating the driving forces for grain/subgrain boundary motion, we found that the surface tension driving forces were often greater than the strain energy driving force. At larger strains (40%), we found pervasive evidence for discontinuous dynamic recrystallization (dDRX), with nucleation of new grains at grain boundaries. The observations reveal that subgrain migration and grain boundary bulging contribute to the nucleation of new grains. These mechanisms are probably critical to allow peridotitic rocks to achieve large strains under a steady-state regime in the lithospheric mantle.

Effect of preliminary heterogenization on the structure and hardness of cryorolled aluminum alloy D16

The effect of preliminary heat treatment on transformations of the grain structure of the aluminum alloy D16 under isothermal rolling at the temperature of liquid nitrogen and subsequent annealing was investigated. It was found that heterogenization by intensifying the nucleation of new grains facilitates the nanostructuring of the alloy during cryorolling, as well as the formation of a fine-grained structure upon static recrystallization at post-deformation annealing.

In-situ observations of recrystallization and microstructural evolution in cerium-containing rolled magnesium alloys

The recrystallization and microstructural evolution of rolled Mg-2Zn-xCe (x = 0.2 and 0.6 wt%) were studied by combining annealing with in-situ electron backscatter diffraction (EBSD) analysis. Sequential EBSD orientation maps of the same microstructural patch were obtained at increasing temperatures, 298 K, 423 K, and from 473 K to 598 K in 25 K increments. In both alloys, the nucleation of new grains was first observed at 473 K, and recrystallization was complete by 573 K. It was found that greater Ce additions led to a higher fraction of recrystallized grains and an overall finer grain size. New grains with a misorientation angle-axis relationship of 60° about <101¯0>, 56° about <112¯0>, and 86° about <112¯0> were observed. Although the twin evolution during heating was not captured, the misorientation axis relationships along <101¯0>, <112¯0>, <101¯1> were characterized for the recrystallized grains. The misorientation angles were uniformly distributed between 30° and 90° in both alloys. The results are discussed and compared with Mg-3Al-1Zn (wt%).

Replacement reactions and deformation by dissolution and precipitation processes in amphibolites

AbstractThe deformation of the middle to lower crust in collisional settings occurs via deformation mechanisms that vary with rock composition, fluid content, pressure, and temperature. These mechanisms are responsible for the accommodation of large tectonic transport distances during nappe stacking and exhumation. Here, we show that fracturing and fluid flow triggered coupled dissolution–precipitation and dissolution–precipitation creep processes, which were responsible for the formation of a mylonitic microstructure in amphibolites. This fabric is developed over a crustal thickness &gt;500 m in the Lower Seve Nappe (Scandinavian Caledonides). Amphibolites display a mylonitic foliation that wraps around albite porphyroclasts appearing dark in panchromatic cathodoluminescence (CL). The albite porphyroclasts were dissected and fragmented by fractures preferentially developed along the (001) cleavage planes and display lobate edges with embayments and peninsular features. Two albite/oligoclase generations, bright in CL, resorbed and overgrew the porphyroclasts, sealing the fractures. Electron backscattered diffraction shows that the two albite/oligoclase generations grew both pseudomorphically and topotaxially at the expense of the albite porphyroclasts and epitaxially around them. These two albite/oligoclase generations also grew as neoblasts elongated parallel to the mylonitic foliation. The amphibole crystals experienced a similar microstructural evolution, as evidenced by corroded ferrohornblende cores surrounded by ferrotschermakite rims that preserve the same crystallographic orientation of the cores. Misorientation maps highlight how misorientations in amphibole are related to displacement along fractures perpendicular to its c‐axis. No crystal plasticity is observed in either mineral species. Plagioclase and amphibole display a crystallographic preferred orientation that is the result of topotaxial growth on parental grains and nucleation of new grains with a similar crystallographic orientation. Amphibole and plagioclase thermobarometry constrains the mylonitic foliation development to the epidote amphibolite facies (˜600°C, 0.75–0.97 GPa). Our results demonstrate that at middle to lower crustal levels, the presence of H2O‐rich fluid at grain boundaries facilitates replacement reactions by coupled dissolution–precipitation and favours deformation by dissolution–precipitation creep over dislocation creep in plagioclase and amphibole.

Syn-kinematic hydration reactions, grain size reduction, and dissolution–precipitation creep in experimentally deformed plagioclase–pyroxene mixtures

Abstract. It is widely observed that mafic rocks are able to accommodate high strains by viscous flow. Yet, a number of questions concerning the exact nature of the involved deformation mechanisms continue to be debated. In this contribution, rock deformation experiments on four different water-added plagioclase–pyroxene mixtures are presented: (i) plagioclase(An60–70)–clinopyroxene–orthopyroxene, (ii) plagioclase(An60)–diopside, (iii) plagioclase(An60)–enstatite, and (iv) plagioclase(An01)–enstatite. Samples were deformed in general shear at strain rates of 3×10−5 to 3×10−6 s−1, 800 °C, and confining pressure of 1.0 or 1.5 GPa. Results indicate that dissolution–precipitation creep (DPC) and grain boundary sliding (GBS) are the dominant deformation mechanisms and operate simultaneously. Coinciding with sample deformation, syn-kinematic mineral reactions yield abundant nucleation of new grains; the resulting intense grain size reduction is considered crucial for the activity of DPC and GBS. In high strain zones dominated by plagioclase, a weak, nonrandom, and geometrically consistent crystallographic preferred orientation (CPO) is observed. Usually, a CPO is considered a consequence of dislocation creep, but the experiments presented here demonstrate that a CPO can develop during DPC and GBS. This study provides new evidence for the importance of DPC and GBS in mid-crustal shear zones within mafic rocks, which has important implications for understanding and modeling mid-crustal rheology and flow.

Effect of La content and extrusion temperature on microstructure, texture and mechanical properties of Mg-Zn-Zr magnesium alloy

The microstructure, texture and mechanical properties of Mg-6wt%Zn-0.5 wt%Zr (ZK60) alloys with different La contents (0, 0.5 and 1 wt%) were investigated. The alloys were produced by low-pressure die casting and extruded at 300 °C and 400 °C, following homogenization at 400 °C for 24 h. La addition to ZK60 alloy resulted in a formation of Mg-Zn-La ternary phase, generating a semi-continuous network structure in their as-cast state. After extrusion, secondary phases were broken into fine particles distributed along the extrusion direction. These fragmented particles led to a nucleation of new grains around them i.e. particle stimulated nucleation (PSN), and promoted dynamic recrystallization (DRX) during extrusion. Therefore, increasing La content led to an increase in DRX fraction. Higher extrusion temperature resulted in larger DRXed grains and higher DRX fraction. The basal texture intensity was also decreased with increasing La addition and extrusion temperature by PSN mechanism and solute atoms of La. The ZK60-1La alloy extruded at 300 °C showed a superior yield strength of 311 MPa and ultimate tensile strength of 360 MPa as a result of significant grain refinement and dispersion strengthening. Increasing extrusion temperature resulted in a decrease in yield and ultimate tensile strengths and increase in ductility.

Effect of Hot Rolling on the Microstructure and Mechanical Properties of Nitrogen Alloyed Austenitic Stainless Steel

In the present investigation, the effect of multi-pass hot rolling in the temperature range of 700–1000 °C on the microstructure and mechanical properties of nitrogen alloyed austenitic stainless steel was studied with the aid of optical microscopy, tensile testing and x-ray diffraction measurements. The microstructural changes that occurred in the hot rolled specimens were elongation of grains in rolling direction, nucleation of new grains at the grain boundaries of elongated grains and growth of nucleated grains to form fully recrystallized grains. Elongated grains formed at lower rolling temperature (700–800 °C) due to inadequate strain/temperature for the initiation of dynamic recrystallization. At higher rolling temperature (900–1000 °C), fine grains formed due to dynamic recrystallization. Tensile properties showed strong dependency on the rolling temperature. Tensile strength increased with the decrease in the rolling temperature at the cost of ductility. Maximum strength was observed in samples hot rolled at 700 °C with yield strength of 917 MPa and ductility of 25%. This variation in the tensile properties with the rolling temperature is attributed to changes in the dislocation density and grain structure. The estimated yield strength from the dislocation density, solid solution and grain boundary strengthening closely matched with experimentally determined yield strength confirming the role of dislocation density and grain size in the strengthening.

Interactive microstructural phenomena during non-isothermal annealing of an Al-Mg-Si-Cu alloy

Interactions between precipitation, recovery and recrystallization during a non-isothermal annealing process in an Al-Mg-Si-Cu alloy have been investigated through a comprehensive experimental analysis. Non-isothermal annealing with a slow heating rate that starts from a low temperature is found to promote homogeneous nucleation of precipitates. The uniformly distributed precipitates limit the extent of recovery, which in turn facilitates extensive nucleation of new grains within the deformed microstructure. The growth of the recrystallized grains is strongly controlled through pinning of grain boundaries by precipitates. During the final stages of annealing, enhanced diffusion at the recrystallization front leads to preferential precipitate coarsening, release of grain boundaries from precipitates pinning, and completion of recrystallization. These interactive microstructural phenomena explain the effectiveness of a non-isothermal annealing route combined with an adequate level of deformation in obtaining a fine-grained recrystallized structure.

On the role of twinning and stacking faults on the crystal plasticity and grain refinement in magnesium alloys

We have investigated the detailed microstructural mechanisms associated with the excellent crystal plasticity and ultra-fine grain refinement observed under high strain-rate deformation of Mg alloys, focusing on ZK60. Firstly, we have identified the clear formation of stacking faults in deformation-induced twinned crystal segments. Specifically, we have found that intrinsic I1 and I2 stacking faults bounded by 16<2¯ 023> and 13<101¯ 0> partial dislocations, respectively, were found to occur in very high number densities within the twins. This was due to the high Schmid factor for stacking fault shearing in twins and the critical role that twin boundaries played in emitting partial dislocations. Secondly, we have clarified the interplay between twinning and stacking faults on the enhanced crystal plasticity. Apart from the strain accommodated by the extensive twinning itself, we propose that the improved plasticity during high strain-rate deformation is mainly due to the nucleation of 13<11¯ 23>{112¯ 2} dislocation within twins, which provides enough independent slip systems to achieve a homogeneous deformation in the material. Finally, we have demonstrated the interplay between twinning and stacking fault formation on the nucleation of new grains via dynamic recrystallisation. The twin boundaries and stacking faults, especially those of the I1 type, facilitate the formation of low-angle grain boundaries that can subsequently transition into high-angle grain boundaries, and form ultra-fine dynamically recrystallised grains.

Microstructural evolution of Nimonic 80a during hot forging under non-isothermal conditions of screw press

The microstructural evolution of nickel base superalloy Nimonic 80a during hot forging was studied in order to explore the suitability of this alloy to be hot forged under non-isothermal conditions of screw press, considering aspects such as deformation inhomogeneity, flow localization and shear bands formation. Hot forging trials in screw press with double truncated cones were carried out at three different temperatures, 950, 1050 & 1150°C. The microstructure in the as-preheated condition was analysed in order to understand the impact of soaking temperature on the evolution of both grain size and precipitates/carbides prior to hot forging operations. In the as-forged condition, the impact of forging temperature, strain, strain rate and chilling effect of the dies on the microstructural evolution of Nimonic 80a was studied. No evidences of shear bands or flow localisation associated to adiabatic heating were found in the hot forged double truncated cones, indicating the suitability of Nimonic 80a to be processed in screw press. However, the non-isothermal conditions of screw press resulted into the development of heterogeneous structures across the thickness. Highly or fully unrecrystallized structures were observed in those areas in contact with bottom die, in contrast with top positions, where highly recrystallized structures were found. Soaking treatments play a very important role on microstructural evolution during hot forging for Nimonic 80a due to its strong impact on both grain growth and dissolution/precipitation of precipitates/carbides. For the present work, discontinuous dynamic recrystallization (DDRX) was found to be the main recrystallization mechanism for Nimonic 80a. Clear evidences of nucleation of new DRX grains by the formation of bulges in serrated grain boundaries with the subsequent growth by twinning were observed at the three forging temperatures. Particle-stimulated nucleation mechanism (PSN) is also operating in Nimonic 80a enhancing the heterogeneous nucleation of new grains in the interior of deformed grains.

Grain Nucleation and Growth in Deformed NiTi Shape Memory Alloys: An In Situ TEM Study

The present study investigates the evolution of nanocrystalline (NC) and ultrafine-grained (UFG) microstructures in plastically deformed NiTi. Two deformed NiTi alloys were subjected to in situ annealing in a transmission electron microscope (TEM) at 400 and 550 °C: an amorphous material state produced by high-pressure torsion (HPT) and a mostly martensitic partly amorphous alloy produced by wire drawing. In situ annealing experiments were performed to characterize the microstructural evolution from the initial nonequilibrium states toward energetically more favorable microstructures. In general, the formation and evolution of nanocrystalline microstructures are governed by the nucleation of new grains and their subsequent growth. Austenite nuclei which form in HPT and wire-drawn microstructures have sizes close to 10 nm. Grain coarsening occurs in a sporadic, nonuniform manner and depends on the physical and chemical features of the local environment. The mobility of grain boundaries in NiTi is governed by the local interaction of each grain with its microstructural environment. Nanograin growth in thin TEM foils seems to follow similar kinetic laws to those in bulk microstructures. The present study demonstrates the strength of in situ TEM analysis and also highlights aspects which need to be considered when interpreting the results.

Template-Free Electroless Plating of Gold Nanowires: Direct Surface Functionalization with Shape-Selective Nanostructures for Electrochemical Applications.

Metal nanowires (NWs) represent a prominent nanomaterial class, the interest in which is fueled by their tunable properties as well as their excellent performance in, for example, sensing, catalysis, and plasmonics. Synthetic approaches to obtain metal NWs mostly produce colloids or rely on templates. Integrating such nanowires into devices necessitates additional fabrication steps, such as template removal, nanostructure purification, or attachment. Here, we describe the development of a facile electroless plating protocol for the direct deposition of gold nanowire films, requiring neither templates nor complex instrumentation. The method is general, producing three-dimensional nanowire structures on substrates of varying shape and composition, with different seed types. The aqueous plating bath is prepared by ligand exchange and partial reduction of tetrachloroauric acid in the presence of 4-dimethylaminopyridine and formaldehyde. Gold deposition proceeds by nucleation of new grains on existing nanostructure tips and thus selectively produces curvy, polycrystalline nanowires of high aspect ratio. The nanofabrication potential of this method is demonstrated by producing a sensor electrode, whose performance is comparable to that of known nanostructures and discussed in terms of the catalyst architecture. Due to its flexibility and simplicity, shape-selective electroless plating is a promising new tool for functionalizing surfaces with anisotropic metal nanostructures.

Effects of film growth kinetics on grain coarsening and grain shape.

We study models of grain nucleation and coarsening during the deposition of a thin film using numerical simulations and scaling approaches. The incorporation of new particles in the film is determined by lattice growth models in three different universality classes, with no effect of the grain structure. The first model of grain coarsening is similar to that proposed by Saito and Omura [Phys. Rev. E 84, 021601 (2011)PLEEE81539-375510.1103/PhysRevE.84.021601], in which nucleation occurs only at the substrate, and the grain boundary evolution at the film surface is determined by a probabilistic competition of neighboring grains. The surface grain density has a power-law decay, with an exponent related to the dynamical exponent of the underlying growth kinetics, and the average radius of gyration scales with the film thickness with the same exponent. This model is extended by allowing nucleation of new grains during the deposition, with constant but small rates. The surface grain density crosses over from the initial power law decay to a saturation; at the crossover, the time, grain mass, and surface grain density are estimated as a function of the nucleation rate. The distributions of grain mass, height, and radius of gyration show remarkable power law decays, similar to other systems with coarsening and particle injection, with exponents also related to the dynamical exponent. The scaling of the radius of gyration with the height h relative to the base of the grain show clearly different exponents in growth dominated by surface tension and growth dominated by surface diffusion; thus it may be interesting for investigating the effects of kinetic roughening on grain morphology. In growth dominated by surface diffusion, the increase of grain size with temperature is observed.

Modeling of Grain-Boundary Mobility and Nucleation Rate during Discontinuous Dynamic Recrystallization in Ni-Nb Alloys and a High-Purity Alloy Derived from SAE 304L

A simple mesoscale model has been developed for discontinuous dynamic recrystallization. Each grain is considered in turn as an inclusion, embedded in a homogeneous equivalent matrix, the properties of which are obtained by averaging over all the grains. The model includes: (i) a grain-boundary migration-equation driving the evolution of grain size via the mobility of grain boundaries, which is coupled with (ii) a single-internal-variable (dislocation density) constitutive model for strain hardening and dynamic recovery, and (iii) a nucleation equation governing the total number of grains by the nucleation of new grains. All the system variables tend to asymptotic values at large strains, in agreement with the experimentally observed steady-state regime.With some assumptions, both steady-state stress and grain-size are derived in closed forms, allowing immediate identification of the mobility of grain boundaries and the rate of nucleation. An application to Ni–Nb-pure-binary model alloys and high-purity 304L stainless steel with Nb addition is presented. More specifically on one hand, from experimental steady-state stresses and grain sizes, variations of the grain boundary mobility and the nucleation rate with niobium content are addressed in order to quantify the solute-drag effect of niobium in nickel. And on the other hand, the Derby exponents were investigated varying separately the strain rate or the temperature.

Homogenization conditions and mechanical properties of ingots of calcium-doped AV alloy

The influence of calcium microalloying on the homogenization temperature of ingots of AV grade alloys of the Al–Mg–Si–Cu system is studied. It is shown that, to provide the maximum dissolution of excess phases, the homogenization temperature of ingots should be chosen in a range of 560–575°C. The microstructure of ingots of the calcium-doped AV alloy has two types of phase components over boundaries of dendrite cells: light skeleton-like and dark compact round shapes. The calcium microalloying additive results in the formation of dispersed particles of excess intermetallide phases in the AV alloy with variable composition of AlxSiyCa and AlxSiyMgzCa, which promote nucleation of new grains. It is likely that calcium as the surfaceactive element changes the contribution of grain-boundary energy. This is the constraint for collective recrystallization.