Nucleation Model Research Articles

A data-driven strategy for phase field nucleation modeling

We propose a data-driven strategy for parameter selection in phase field nucleation models using machine learning and apply it to oxide nucleation in Fe-Cr alloys. A grand potential-based phase field model, incorporating Langevin noise, is employed to simulate oxide nucleation and benchmarked against the Johnson-Mehl-Avrami-Kolmogorov model. Three independent parameters in the phase field simulations (Langevin noise strength, numerical grid discretization and critical nucleation radius) are identified as essential for accurately modeling the nucleation behavior. These parameters serve as input features for machine learning classification and regression models. The classification model categorizes nucleation behavior into three nucleation density regimes, preventing invalid nucleation attempts in simulations, while the regression model estimates the appropriate Langevin noise strength, significantly reducing the need for time-consuming trial-and-error simulations. This data-driven approach improves the efficiency of parameter selection in phase field models and provides a generalizable method for simulating nucleation-driven microstructural evolution processes in various materials.

Modeling of the perovskite nickelate SmNiO3 nucleation from amorphous thin films: A Volmer's thermodynamical approach

We present a thermodynamical model based on Volmer's nucleation theory adapted to the case of the perovskite nickelate SmNiO3 crystallization (SNO) from an amorphous (aSNO) thin film. This amorphous phase is synthesized via reactive magnetron sputtering and then subsequently annealed in air at temperatures between 725 and 925 K to crystallize it. This model allows to predict the theoretical nucleation rate of the crystallized perovskite phase according to the annealing temperature, the type of the nucleation (homogeneous and heterogeneous mechanisms) and to estimate some physical and thermodynamical data related to this transformation. A theoretical evaluation of the nucleation rate shows that the optimum temperature for crystallization is close to 800 K for which the nucleation rate can reach 1021 m-3.s-1 if considering both homogeneous and heterogeneous nucleation mechanisms. As the annealing temperature moves away from 800 K, the theoretical nucleation rate drops drastically, as observed experimentally by X-ray Diffraction (XRD) when we annealed 200 nm thick aSNO films. The good agreement between the presented model and the experimental crystallization results allows us to numerically evaluate some physical parameters not yet reported to date in the literature for SNO perovskites such as the surface energy between the amorphous and the crystallized SNO phases, the strain energy when the crystallization occurs and the enthalpy associated with crystallization.

Evaluating the influence of the initial high molecular weight level on monoclonal antibody particle formation kinetics using a short-term chemical stress study

Protein formulations may form proteinaceous particles that vary in size from nanometers to millimeters. Monitoring the kinetics of protein particle formation, e.g., through accelerated degradation studies, is an attempt to understand and assess the rate and progression of particle populations. Little is known about whether the initial level of high molecular weight (HMW) species, or initial HMW level (IHL), of a protein solution influences the propagation of protein particle formation, and thus affects the storage stability of proteins.In this study, we have established a method to generate protein solutions of different IHLs by thermal stress. We have evaluated a 16-week thermal stability study at 40 °C of two monoclonal antibodies (mAb-A and mAb-B) at different IHLs using size exclusion chromatography (SEC) and sub-visible particle analysis. We have performed an isothermal stress study with guanidinium hydrochloride (GuaHCl) at room temperature for 300-min to evaluate the formation of HMWs analysed by SEC. The application of the Finke-Watzky (F-W) two-step nucleation model allowed us to mathematically describe the kinetics of HMW formation and to extract kinetic parameters of this process.For mAb-A, the IHLs had a marginal influence on the loss of monomer rate; instead, mAb-A exhibited fragmentation at 40 °C, which was independent of the IHL. Nevertheless, above a threshold of ≥ 7 % IHL, existing trimers/tetramers undergo conversion into higher-order oligomers at 40 °C, which is not observed at lower IHLs. In contrast, mAb-B exhibited an increased HMW formation rate above a threshold of ≥ 4 % IHL, which was reflected in the monomer decay rates at 40 °C and the F-W kinetic parameters of the chemical stress study.This case study shows that the initial level of HMWs exerts a differential influence on the progression of HMW formation. In one instance, there is a discernible acceleration in the formation of HMWs with rising IHLs. Conversely, in another example, the IHL exerts only a slight influence on HMW formation. Moreover, the results of our short-term chemical stress study are in accordance with those of a classical storage stability study conducted at 40 °C, which evaluated different IHLs. The analysis of HMW formation kinetics will enhance our understanding of the protein particle formation process and facilitate the formulation development of biotherapeutics.

Electroanalytical Studies on Codeposition of Cobalt with Ruthenium from Acid Chloride Baths

The aim of this study was to systematically analyze the influence of potential and the Co(II)–Ru(III) molar ratio on the electrochemical behavior of the Co–Ru system during codeposition from acidic chloride electrolytes. The equilibrium speciation of the baths was investigated spectrophotometrically and compared with theoretical calculations based on the stability constants of Co(II) and Ru(III) complexes. The codeposition of the metals was characterized using electroanalytical methods, including cyclic voltammetry, chronoamperometry, and anodic stripping linear voltammetry. The alloys obtained at different potentials were analyzed for their elemental composition (EDS, mapping), phase composition (XRD), and surface morphology (SEM). The morphology and composition of the alloys were mainly dependent on the deposition potential, which controlled the cobalt incorporation. Ruthenium–rich alloys were produced at potentials of −0.6 V and −0.7 V (vs. SCE). In these conditions, cobalt anomalously codeposited due to the formation of the CoOH+ intermediate, triggered by the intense hydrogen evolution on the ruthenium sublayer. Bulk cobalt electrodeposition began at a potential of around −0.8 V, resulting in the formation of cobalt-rich alloys. The early stages of the electrodeposition were investigated using different nucleation models. A transition from 2D progressive nucleation to 3D instantaneous nucleation at around −0.8 V was identified as being caused by cobalt incorporation. This was well correlated with electroanalytical data, partial polarization curves of alloy deposition, elemental mapping analysis, and the structure of the deposits.

Global modeling of aerosol nucleation with a semi-explicit chemical mechanism for highly oxygenated organic molecules (HOMs)

Abstract. New particle formation (NPF) involving organic compounds has been identified as an important process affecting aerosol particle number concentrations in the global atmosphere. Laboratory studies have shown that highly oxygenated organic molecules (HOMs) can make a substantial contribution to NPF, but there is a lack of global model studies of NPF with detailed HOM chemistry. Here, we incorporate a state-of-the-art biogenic HOM chemistry scheme with 96 chemical reactions to a global chemistry–climate model and quantify the contribution to global aerosols through HOM-driven NPF. The updated model captures the frequency of NPF events observed at continental surface sites (normalized mean bias changes from −96 % to −15 %) and shows reasonable agreement with measured rates of NPF and sub-20 nm particle growth. Sensitivity simulations show that compared to turning off the organic nucleation rate, turning off organic initial growth results in a more substantial decrease in aerosol number concentrations. Globally, organics contribute around 45 % of the annual mean vertically integrated nucleation rate (at 1.7 nm) and 25 % of the vertically averaged growth rate. The inclusion of HOM-related processes leads to a 39 % increase in the global annual mean aerosol number burden and a 33 % increase in cloud condensation nuclei (CCN) burden at 0.5 % supersaturation compared to a simulation with only inorganic nucleation. Our work predicts a greater contribution of organic nucleation to NPF than previous studies due to the semi-explicit HOM mechanism and an updated inorganic NPF scheme. The large contribution of biogenic HOMs to NPF on a global scale could make aerosol sensitive to changes in biogenic emissions.

Sulfur fixation performance of calcium-bearing carbonates in iron ore roasting process: Thermodynamics, phase transition, microstructure evolution, and kinetics

Roasting technology is increasingly used in the beneficiation of refractory iron ores. During the roasting process, the presence of pyrite in some iron ores leads to the formation of SO2, requiring effective sulfur fixation techniques. This study proposed an innovative in-situ sulfur fixation method by pre-oxidation roasting, in which sulfur was fixed during the oxidation roasting process before reduction roasting. The effects of the main iron mineral (hematite), primary gangue mineral (quartz), and common calcium-containing carbonate minerals (calcite and dolomite) on sulfur migration during pyrite roasting were investigated, with particular emphasis on the sulfur fixation capabilities of calcite and dolomite. The study included thermodynamic equilibrium analysis, phase transitions and microstructural evolution in different reaction systems. The results showed that calcite and dolomite effectively reduced SO2 emissions by forming CaSO4 and MgSO4, with calcite exhibiting a stronger sulfur fixation capacity for the same mass. Kinetic analysis indicated that pyrite pyrolysis followed a two-step random nucleation and growth model. Furthermore, the addition of calcite increased the apparent activation energy of SO2 formation and altered the reaction pathway, providing insight into the sulfur fixation mechanism of calcite from a kinetic perspective.

Pyrolysis kinetic analysis of molten bioplastics based on the combination of real-time characterization and Guassian deconvolution: Case study of poly(lactic acid) materials.

Pyrolysis remains a promising method for the utilization of biogradable plastics. However, the kinetics and mechanisms of molten polymer pyrolysis are not well understood, and the effect of additives (mainly inorganic nucleating agents) on the reaction pathway has not been widely explored. In this work, we conducted a method using the thermogravimetric analysis-Fourier transform infrared spectrometry (TG-FTIR) combined with a model-fitting method, instead of a traditional method subjectively selecting a reaction model. The FTIR curves provided information for sub-reaction determination, and the detailed parameters were determined using Gaussian deconvolution. The calculation results revealed that the whole process of poly(latic acid) (PLA) pyrolysis is the random nucleation and nuclei growth model. The introduction of inorganic nucleating agents provided nuclei for PLA decomposition, decreasing the initial activation energy (E) from approximately 136 kJ·mol-1 to 88 and 79 kJ·mol-1 at a conversion rate of 0.01. However, the nucleating agent could hinder the generation of nuclei from PLA ontology, which led to the increase of E value after the nucleating agents were occupied.

Exploring the mechanisms of benzanilide crystal growth and morphology: Crystal surface structure, solvent diffusion and solvent-interface interactions

Flaky crystals are fragile, rendering them unsuitable for various applications including use, processing, storage and transportation. This work investigates the growth and morphology regulation mechanisms of flaky crystals using benzanilide as a model material. Initially, block-like crystals are prepared by solvent screening and cooling crystallization with its morphology greatly improved. Subsequently, growth kinetics of (111), (1–10) and (020) faces are established with crystal growth experiments. The crystal growth of (001) face is also determined to follow a two-dimensional nucleation model with the microscopic surface analysis using atomic force microscopy. The changes of the surface integration resistance and the growth step height are regarded as kinetic mechanisms of the growth behavior and crystal morphology modulation by solvent and supersaturation. Finally, the molecular mechanism of the modulation of the solvent in crystal morphology is revealed base on crystal surface structure analysis and molecular dynamics simulations. The weak solvent-interface polar interactions facilitate the incorporation of benzanilide molecules into the weak polarity (001) face, leading to the surface roughening and increased crystal thickness when employing strongly polar solvents such as acetonitrile. Unlike the former, the relatively weak hydrogen bonding interactions between solvents and strong polarity (020) face, and the higher diffusion ability of molecules promote the rapid growth and disappearance of (020) face in ethanol and acetonitrile with strong hydrogen bond formation ability. This study can contribute to a deeper understanding of the solvent effect on crystal morphology and provide guidance for optimizing crystallization conditions to obtain shape-tailored crystal products.

Parametrically Upscaled Constitutive and Crack Nucleation Models for Investigating the Effects of Specimen Geometry and Microstructure on Fatigue Crack Nucleation in Ti Alloys Containing Micro-texture Regions

Parametrically Upscaled Constitutive and Crack Nucleation Models for Investigating the Effects of Specimen Geometry and Microstructure on Fatigue Crack Nucleation in Ti Alloys Containing Micro-texture Regions

Role of silicon in the growth of ZSM-5 synthesized with coal fly ash as raw materials

In this work, single-phase ZSM-5 zeolite was synthesized using solid waste coal fly ash (CFA) as raw material, providing a potential alternative for creating high-value-added products from this waste. X-ray diffraction (XRD), scanning electron microscopy, X-ray fluorescence, Fourier transform infrared spectroscopy, N2 physisorption, and other techniques were used to evaluate the crystallization and morphology of the ZSM-5 obtained. The results indicated that ZSM-5 can be synthesized by the simple method of mixing, stirring, and heating. A well-defined hexagonal shape of ZSM-5 with a specific surface area of 162 m2/g and mesoporous structure was obtained at the temperature of 160 °C during hydrothermal treatment for 72 h. Theoretically, the mechanism of crystal growth of ZSM-5, i.e. the liquid phase nucleation and step growth models, was clarified. These results open the possibility of exploring the crystallization of ZSM-5 and the utilization of CFA. Simultaneously, the critical roles of silicon in framework formation and crystallization control during the formation and growth of zeolites were elucidated.

Location-Dependent Phase Transformation Kinetics During Laser Wire Deposition Additive Manufacturing of Ti–6Al–4V

This work models the microstructural evolution as a function of position in laser-wire deposited Ti–6Al–4V parts using a classical multi-component JMAK nucleation and growth model with additive isothermal time-steps. Model predictions are compared to experimental observations. The model can be used to interpret nucleation and growth kinetics of various characteristic features of the microstructure that are inaccessible by experiments. It explains the presence of “layer bands” at specific locations unrelated to the weld bead structure. The last re-heating (of multiple thermal cycles) of a solidified layer, and where it peaks, plays a key role in increasing the nucleation density at specific locations, resulting in full α\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha $$\\end{document}-colony microstructures constituting the “layer bands,” while the rest of the build is predominantly basketweave. Additionally, changes in the basketweave α\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha $$\\end{document}-lath thickness as a function of the distance from the substrate are studied and compared with an Arrhenius-type function, with results highlighting a more complex relationship than an Arrhenius-type function would suggest.

Phase-field modeling of interdiffusion between dissimilar Fe-Cr-Ni alloys during non-isothermal hot isostatic pressing

Powder metallurgy hot isostatic pressing (PM-HIP) has emerged as a promising alternative to welding for joining dissimilar metals. During HIP, interfacial bonding is mediated by solid state diffusion. The interdiffusion zone across the interface depends on processing conditions, calling for the need for accurate numerical tools capable of simulating interdiffusion and possible phase transformation in order to optimize processing parameters. Here, a phase-field (PF) model based on CALPHAD-based free energy functionals is developed to simulate the interdiffusion and phase evolution between dissimilar Fe–Cr–Ni based steels undergoing HIP and is demonstrated using the interface between 316L and SA508 steels. To overcome the numerical challenges caused by the singular magnetic and entropy terms in the CALPHAD free energy models in the Fe–Cr-Ni system, polynomial functions are fitted with temperature dependent coefficients represented by Fourier series to accurately describe the phase stability of both fcc and bcc phases in the composition and temperature space. This enables simulations of non-isothermal HIP cycles. Diffusivity data from commercial software and literature are taken to parameterize the kinetic parameters. A discrete nucleation model is incorporated for possible phase transformation. The modified thermodynamic models are validated against previous experiments at 923 K and 1273 K. The interdiffusion kinetics are benchmarked against new HIP experiments joining powder and bulk 316L to bulk SA508 with three different HIP cycles. The good agreement between simulations and experiments on both phase stability and interdiffusion indicate that the model is suitable for simulating interdiffusion between Fe–Cr–Ni alloys during HIP cycles. It is also found that using powder and bulk 316L gives similar interdiffusion profiles at elevated temperature when a dense interface forms during HIP.

The crack propagation behaviors, microstructure and mechanical properties of T-welded joints for TIGW with crystal plasticity model and XFEM

In view of the significant impact of welding defects on the fracture behaviors involving the strength, stress concentration and bearing capacity of welded joint, etc., the propagation behaviors and mechanical properties of welded joints with porosity and micro crack are deeply investigated using a multiscale method. In this work, a crack nucleation and propagation model based on crystal plasticity theory, combined with the extended finite element method (XFEM), is established for the T-welded joint. The maximum slip on the predominant slip system method is applied to predict the crack propagation path of pores and micro cracks in the weld zone (WZ), and the effect of crystal orientation on crack growth is explored. Then, a continuous model is used to analyze the micro and macro fracture behaviors near the weld under tensile load, combined with the maximum principal stress method. The WZ and heat affected zone (HAZ) are observed using electron backscatter diffraction (EBSD) to study the microstructure evolution. Considering grain boundaries, the image information of crystal morphology is processed through binary image analysis for FE modeling. The local mechanical properties testing is carried out using micro-specimens of HAZ and WZ to calibrate the crystal plastic parameters. The results show that the resolved shear stress of the predominant slip system of crack initiation and propagation elements is increased by pore and crack defects. The fracture positions of tensile specimens through numerical simulation are in good agreement with the macroscopic experimental results. It will provide an analysis basis for preventing fracture failure and improving the service performance of thin-walled structures in future.

Interfacial Zn2+-solvation regulator towards reversible and stable Zn anode

Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface, predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution. Particularly, the intricate mechanisms behind the electrochemical discrepancies induced by interfacial Zn2+-solvation and deposition behavior demand comprehensive investigation. Organic molecules endowed with special functional groups (such as hydroxyl, carboxyl, etc.) have the potential to significantly optimize the solvation structure of Zn2+ and regulate the interfacial electric double layer (EDL). By increasing nucleation overpotential and decreasing interfacial free energy, these functional groups facilitate a lower critical nucleation radius, thereby forming an asymptotic nucleation model to promote uniform Zn deposition. Herein, this study presents a pioneering approach by introducing trace amounts of n-butanol as solvation regulators to engineer the homogenized Zn (H-Zn) anode with a uniform and dense structure. The interfacial reaction and structure evolution are explored by in/ex-situ experimental techniques, indicating that the H-Zn anode exhibits dendrite-free growth, no by-products, and weak hydrogen evolution, in sharp contrast to the bare Zn. Consequently, the H-Zn anode achieves a remarkable Zn utilization rate of approximately 20% and simultaneously sustains a prolonged cycle life exceeding 500 h. Moreover, the H-Zn//NH4V4O10 (NVO) full battery showcases exceptional cycle stability, retaining 95.04% capacity retention after 400 cycles at a large current density of 5 A g−1. This study enlightens solvation-regulated additives to develop Zn anode with superior utilization efficiency and extended operational lifespan.

Investigation of kinetics, reaction mechanisms, thermodynamics, and synergetic effects in co-pyrolysis of wood sawdust and linear low-density polyethylene using the thermogravimetric approach.

This study focused on investigating thermal degradation behaviors, kinetics, reaction mechanisms, synergistic effects, and thermodynamic parameters of wood sawdust (WSD), linear low-density polyethylene (LLDPE), and their blends (LW1:3, LW1:1, and LW3:1) during co-pyrolysis in a thermogravimetric analyzer (TGA). Thermal behavior exhibited a LW1:3 blend (25 wt.% LLDPE) showing significant mass loss at lower temperatures (150 to 300°C) compared to the individual feedstocks, such as 150 to 400°C and 300 to 520°C for WSD and LLDPE, respectively. The iso-conversional methods (KAS, FWO, and FM) were used to determine the kinetic parameters (Ea and A), and the activation energy drop was highest for the LW1:3 blend. According to the master plots, the third-order reaction (O3), nucleation (P2/3), and diffusional model (D4) were the predominant reaction mechanisms for the co-pyrolysis of the LW1:3, LW1:1, and LW3:1 blend, respectively. The thermodynamic parameters demonstrate that a small amount of plastic addition into WSD can improve the reactivity of the blend, shorten the reaction time, and cause less energy-intensive reactions. The values of ΔH, ΔG, and ΔS also confirmed the co-pyrolysis process's spontaneity and endothermic nature. The Fourier transforms infrared spectrometer (FTIR) spectra of raw feedstock, blends, and their biochar revealed some of the peaks were shifted, the intensity was reduced, and disappearance can happen when the temperature was increased. Using the experimental and theoretical/predicted activation energies, the parity chart illustrates the synergistic effects of co-pyrolysis of different blends, and the LW1:3 blend has a favorable synergistic impact. These results could be helpful in process optimization and designing an effective reactor system for co-pyrolysis.

Density functional investigation of the heterogeneous nucleation of graphite on divalent metal oxides and sulfides

Controlling the nucleation of graphite during solidification of spheroidal and lamellar graphite irons is achieved through minor additions of certain active elements such as Mg, Ca, Sr, Ba and Mn. In the present work, interfaces of graphite with alkaline earth oxides, sulfides and MnS are investigated by density functional simulations of model structures where interfacial strain has been optimized by controlling the twisting angle between the two materials. The bulk stabilities, surface energies and interfacial energies between the nucleant phases, graphite and iron are calculated. A new graphite nucleation model for estimating undercooling based on interfacial energies is proposed. It is found that CaS is the most potent nucleant particle in spheroidal graphite iron and MnS in lamellar graphite iron. The main driver of nucleation potency is found to be of chemical nature rather than related to lattice misfit.

Ice nucleation in supercooled water under shear

Classical nucleation theory (CNT) provides a good framework for understanding the nucleation phenomenon in metastable conditions. However, there is still no satisfactory understanding of the shear effect. Here, we propose an ice nucleation model considering the rebounded deformation energy to analyze the ice nucleation rate. It is concluded that: (1) The effect is more pronounced by changing the contact angle to regulate the free energy when both the supercooled degree and the shear rate are small. (2) The variation trend of the nucleation ratio Jhet,sh/Jhet,no increases at first but it may decrease when the contact angle is small, or keeps increasing when the contact angle is large. (3) The probability of the shear nucleation is about several ten orders of magnitude to that of static nucleation. (4) The key factor in the acceleration of the supercooled liquid nucleation is the released deformation energy after encountering the obstruction.

Silica particle size and polydispersity control from fundamental practical aspects of the Stöber method

Silica-based nanoparticles have been continuously investigated for their physical and chemical properties, which have made them adaptable for a wide range of scientific purposes, from adsorption in an aqueous medium to target-specific drug delivery in biological fluids. The achievement of these properties is, in general, possible by controlling the synthesis of the nanomaterial, and the Stöber method is one of the most commonly employed approaches for silica-based nanoparticles. In this study, experiments were carried out to investigate several parameters of the Stöber method for controlling the diameter and size dispersion of silica nanoparticles. The results of these experiments were supported by and contrasted with the theoretical aspects of silica particle nucleation and growth models. In this scenery, practical aspects of the Stöber Method such as the effects of variations in catalyst concentration, colloidal stability and drying approach on particle size and polydispersity were examined in detail for providing an organized basis of experimental and theoretical data about it for who aims at work with silica nanoparticle synthesis through the Stöber Method.

Thermal evolution of mercury from waste rare earth phosphor: Effect of thermal treatment conditions and kinetic analysis

Waste phosphor (WP) from fluorescent lamp is a hazardous waste and an important secondary resource for recycling mercury and rare earths. To avoid mercury pollution during rare earth recovery, it is necessary to conduct deep mercury removal before rare earth recovery. However, the mechanism of mercury removal in WP is not clear, which restricts the progress of efficient mercury removal methods. Effects of treatment temperature and time on thermal evolution of WP were analyzed by different characterization methods. Model-free, model-fitting and z(α) master plots method are used in combination to explain the complex mechanism of mercury removal in WP. The mechanism of mercury removal will change gradually with the process of mercury removal. The average Eα for mercury removal is 100.76 kJ/mol and 190.36 kJ/mol at conversion α (i.e. mercury removal efficiency) of 0.1–0.3 and 0.3–0.9, respectively. Simple mercury compounds are decomposed at α less than 0.3 (∼600 °C), according with the model of random nucleation and subsequent growth. A large amount of tightly combined mercury is released rapidly at α of 0.3–0.75 (600–700 °C), ascribing to the decomposition of carbonate and the structure transformation of silicon oxide. The process mechanism gradually change from 1D/2D diffusion to 3D diffusion, increasing the mass transfer resistance of mercury diffusion. Thermal desorption of residual bound mercury at α larger than 0.75 (∼700 °C) is controlled by phase boundary reaction. More efficient mercury removal effects can be obtained by adding additives to roasting. The results are beneficial to the research of deep mercury removal methods of WP.

FIRST RESULTS OF SPATIAL PLANNING IN THE HABSBURG MILITARY FRONTIER: FRONTIER REGIMENTS, NUCLEATED SETTLEMENTS AND CADASTRAL SURVEY (C. 1745–1785)

There are numerous examples of spatial planning on the periphery of the Habsburg Monarchy, which was organised within the regiments of the Military Frontier in the second half of the 18th century. Our focus was on the territory of the Slavonian-Syrmian Military Frontier, the Šajkaš Battalion, and the Banat Military Frontier, where flat landscapes enabled various forms of state spatial intervention, approximately at the same time – around 1770. This paper presents some aspects important for understanding this complex topic, such as the influence of militarisation and centralisation, colonisation and spatial planning of settlements (following the nucleated settlement model), as well as the tight structuring of rural areas and parcelisation of arable land, and their final results in the form of land and tax reforms (cadastral surveying).