Application of profilometry and fractal analysis to the characterization of coatings surface roughness

Quantitation of the analysis of coatings surface roughness by a contact profilometer was undertaken to obtain improved repeatability and meaningfulness of data. This effort involved interfacing the profilometer to a personal computer for data acquisition and analysis, optimizing operational variables involved in the measurement process and improving methods for quantitative data analysis of the roughness profiles. The quantitative methods of data analysis explored included the use of various surface profile roughness averages, power spectrum analysis through zone integrals, auto-correlation function analysis and fractal analysis of the surface roughness profile. Quantitative parameters obtained from the above methods were correlated with visual and optical methods for evaluating appearance for a variety of coatings. The superiority of correlation with evaluations of appearance and repeatability of multiple runs will be demonstrated for fractal numbers obtained from a fractal analysis of surface roughness profiles.     

Behavior of mercury release during thermal decomposition of coals

The mercury release behavior during thermal decomposition of three Chinese coals with different types was studied under nitrogen, carbon dioxide and air at temperatures of 800, 900, 1,000 and 1,100 °C. The thermal treatment experiments were carried out in a quartz tube reactor. Results showed that the release ratio of total mercury during thermal decomposition of coals increases with the increasing temperature. The order of the amount of mercury released under the three atmospheres is nitrogen<carbon dioxide<air for all three coals during thermal decomposition. This indicates that air and carbon dioxide can promote the mercury release due to their reactivity with coal. However, the order of amount of elemental mercury released under the three atmospheres is nitrogen>carbon dioxide>air for all three coals. The release behavior of the total mercury under air is independent of the coal type. Under the other two atmospheres the release behavior is distinguished by the coal type. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

Modeling changes of fractal pore structures in coal pyrolysis

Coal pyrolysis processes are numerically investigated in mathematically produced coal pore models which simulate real coal pores in the parameters of the porosity and fractal dimension. The simulations include FG-DVC chemical reaction model, gas molecular diffusion in pores, energy conservation model and coal swelling model. Numerical results are verified by experimental results qualitatively, and they revealed that both the porosity and volatile contents of the parent coal can affect the fractal dimension of the final char pores after pyrolysis linearly. A formula to predict the fractal dimension of char pores from its parent coal properties is obtained by curve fitting in numerous results.     

Evolution of porous fractal properties during coal devolatilization

The evolution of pore structures during coal devolatilization was studied using the mercury porosimetry to classify pore structures as micro pores or macro pores based on fractal theory. Pyrolysis caused few changes in the total specific surface areas and micro pore surface areas of most samples. However, the specific macro pore surface areas and the ratio of the specific macro pore surface areas to the total specific surface areas were significantly increased, mostly a result of the shapes of some micro pores becoming less complex after pyrolysis. After devolatilization, the fractal dimensions of the macro pores, which reflect the complexity of the geometrical shapes and hence, the resistances to gas diffusion increased. The fractal geometric factor β, which combines the effects of the ratio of the macro pore surface area to the total surface areas and the fractal dimension of the macro pores after char combustion presented in the previous study is also increased. The volatile content in the parent coal affects the changes of the pore structures.     

Studies of relationship between petrography and elemental analysis with grindability for Kentucky coals

The effects of macerals, ash, elemental analysis and moisture of wide range of Kentucky coal samples from calorific value of 23.65-34.68 MJ/kg (10,170-14,910 (BTU/lb)) on Hardgrove Grindability Index (HGI) have been investigated by multivariable regression method. Two sets of input: (a) macerals, ash and moisture (b) macerals, elemental analysis and moisture, were used for the estimation of HGI. The least square mathematical method shows that increase of the TiO₂ and Al₂O₃ contents in coal can decrease HGI. The higher Fe₂O₃ content in coal can result in higher HGI. With the increase of micrinite and exinite contents in coal, the HGI has been decreased and higher vitrinite content in coal results in higher HGI. The multivariable studies have shown that input set of macerals, elemental analysis and moisture in non-linear condition can be achieved an acceptable correlation, R = 90.38%, versus R = 87.34% for the input set of macerals, ash and moisture. It is predicted that elemental analysis of coal can be a better representative of mineral matters for the prediction of HGI than ash.     

Comparison of fractal properties of porous structures during coal devolatilization

This paper investigates fractal property changes of pore structures during coal devolatilization. Similar to char pores, coal pores can also be classified as micro pores and macro pores based on their fractal dimensions. The specific surface area and fractal dimension of micro pores in coal particles are basically unchanged after devolatilization. However, the specific surface area and fractal dimension of macro pores, which are key factors in char combustion, are increased after devolatilization. In fact, the fractal dimensions are basically doubled. These parameters will affect another fractal geometrical factor β in char pores that is correlated to char combustion rate. Since the rate of char combustion can be predicted from their fractal pore properties, it may be possible to predict char combustion directly from the properties of their parent coal pores in the future. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Textural analysis for better correlation of the char yield of pyrolysed lignocellulosic materials

A new empirical formula, based on the surface fractal dimension, the porosity, the botanical composition and the ash content of the precursor is proposed for the assessment of the char yield, Y (wt %) of lignocellulosic materials pyrolysed in a 600-900 °C temperature range. The following equation is proposed:

     

Micromorphological characterization of polymer-oxide nanocomposite thin films by atomic force microscopy and fractal geometry analysis

The purpose of this study was to evaluate the 3-D surface micromorphology of polymer-oxide thin films spin-coated from a composite of poly-methyl-methacrylate as the matrix and elongated titania nanorods as the filler particles. The surfaces of these composite films were investigated by atomic force microscopy and characterized by fractal geometry analysis. The effect of increasing loading of the fillers between 0 and 30% by weigth relative to the matrix was assessed. An increasing roughness was observed, with typical emergence of protruding ripples progressively extending into larger stripes. The amplitude parameters of the surfaces were determined by analysis of the height distributions. The fractal analysis of roughness revealed that the films have fractal geometry. Triangulation method based on the linear interpolation type was applied to determine the fractal dimension. A connection was observed between the surface morphology and the physical properties of the coatings as assessed in previous works.     

Study on some factors affecting the results in the use of MIP method in concrete research

Effects of rate of pressure application and forms and type of sample on porosity and pore size distribution of concrete estimated through mercury intrusion porosimetry (MIP) are presented in this experimental work. Two different forms of concrete sample, namely, crushed chunks of concrete and small core drilled out from the concrete beam specimens, were used for this study. The results exhibit that the rate of pressure application in mercury porosimetry has little effect on porosity and pore size distribution of concrete. It is also demonstrated that small cores drilled out from large concrete specimens are preferable as samples for performing porosimetry test on concrete.     

Petrophysical characterization of coals by low-field nuclear magnetic resonance (NMR)

Nuclear magnetic resonance (NMR) has been widely used in petrophysical characterization of sandstones and carbonates, but little attention has been paid in the use of this technique to study petrophysical properties of coals, which is essential for evaluating coalbed methane reservoir. In this study, two sets of NMR experiments were designed to study the pore types, pore structures, porosity and permeability of coals. Results show that NMR transverse relaxation (T₂) distributions strongly relate to the coal pore structure and coal rank. Three T₂ spectrum peaks identified by the relaxation time at 0.5-2.5 ms, 20-50 ms and >100 ms correspond to pores of <0.1 μm, >0.1 μm and cleats, respectively, which is consistent with results from computed tomography scan and mercury intrusion porosimetry. Based on calculated producible and irreducible porosities through a T₂ cutoff time method, we propose a new NMR-based permeability model that better estimates the permeability of coals. In combination with mercury intrusion porosimetry, we also propose a NMR-based pore structure model that efficiently estimates the pore size distribution of coals. The new experiments and modeling prove the applicability of NMR in petrophysical characterization of intact coal samples, which has potential applications for NMR well logging in coalbed methane exploration.     

A new approach for the characterization of the pore structure of dual porosity rocks

For the realistic representation of the pore space of dual porosity rocks, a new method of pore structure characterization is developed by combining experimental Hg intrusion/retraction curves with back-scattered scanning electron microscope (BSEM) images and inverse modeling algorithms. The pore space autocorrelation function measured by processing the digitized BSEM images is combined with the surface fractal dimension estimated from the high pressure Hg intrusion (MIP) data to derive a synthetic small-angle neutron scattering (SANS) intensity function, the inversion of which provides a volume-based pore body radius distribution (PBRD). The volume-based PBRD is fitted with a multimodal number-based PBRD consisting of two component distributions: one representing the macroporosity and another one representing the microporosity. Based on arguments of percolation theory, analytical mathematical models are developed to describe the Hg intrusion in and retraction from dual pore networks in terms of the complete PBRD, pore throat radius distribution (PTRD) of macroporosity, drainage accessibility functions (DAFs) of both porosities, and imbibition accessibility functions (IAFs) of both porosities. Inverse modeling of the Hg intrusion data set enables us to estimate the PTRD and DAFs. Inverse modeling of the Hg retraction datasets enables us to estimate a set of primary and secondary IAFs. The method is demonstrated by the pore structure characterization of four outcrop samples of carbonate and sandstone rocks. Analytic approximate equations developed from the critical path analysis (CPA) of percolation theory enable us to calculate explicitly the absolute permeability and the formation factor of the porous rocks using the estimated parameters (PBRD, PTRD, DAF) of the macroporosity. The measured permeability of cores is predicted satisfactorily and observed discrepancies may be attributed to large length-scale macro-heterogeneities which are not evident in BSEM images and Hg porosimetry data.     

Effects of pore fractal structures of ultrafine coal water slurries on rheological behaviors and combustion dynamics

The ultrafine coal water slurry (CWS) with the particle size of 1-10 μm, ash content of 1-2%, solid concentration of 50% is a promising substitute fuel for diesel oil. The effects of pore fractal structures of three ultrafine CWSs on their rheological behaviors and combustion dynamics were studied in this paper. When the pore fractal dimensions of Yanzhou, Huainan and Shenhua ultrafine CWSs increase, their apparent viscosities all increase and the increase extents gradually enlarge with decreasing shear rates, while their ignition temperatures and apparent activation energies all decrease. For example, when the pore fractal dimension of Yanzhou coal increases from 2.31 to 2.43, the CWS apparent viscosity at a low shear rate of 12 s⁻¹ increases from 75 mPa s to 2400 mPa s, and that at a high shear rate of 100 s⁻¹ increases from 80 mPa s to 820 mPa s. Meanwhile, the ignition temperature of Yanzhou CWS decreases from 445 °C to 417 °C at a heating rate of 12.5 °C/min, and the apparent activation energy decreases from 104 kJ/mol to 32 kJ/mol.     

Identification of organochlorines and organobromines in coals

Four Chinese bituminous coals were extracted with CS₂, n-hexane, benzene, methanol, acetone, tetrahydrofuran (THF) and THF/methanol (1: 3 vol/vol) mixed solvent sequentially. The resulting 28 extracts were analyzed with GC/MS. Six organochlorines (OCs) and two organobromines (OBs) were identified in eight extracts from the coals. Our experiments provide, for the first time, the information on the molecular structure of OCs and OBs in coals.     

Proximate analysis based multiple regression models for higher heating value estimation of low rank coals

In this paper, multiple nonlinear regression models for estimation of higher heating value of coals are developed using proximate analysis data obtained generally from the low rank coal samples as-received basis. In this modeling study, three main model structures depended on the number of proximate analysis parameters, which are named the independent variables, such as moisture, ash, volatile matter and fixed carbon, are firstly categorized. Secondly, sub-model structures with different arrangements of the independent variables are considered. Each sub-model structure is analyzed with a number of model equations in order to find the best fitting model using multiple nonlinear regression method. Based on the results of nonlinear regression analysis, the best model for each sub-structure is determined. Among them, the models giving highest correlation for three main structures are selected. Although the selected all three models predicts HHV rather accurately, the model involving four independent variables provides the most accurate estimation of HHV. Additionally, when the chosen model with four independent variables and a literature model are tested with extra proximate analysis data, it is seen that that the developed model in this study can give more accurate prediction of HHV of coals. It can be concluded that the developed model is effective tool for HHV estimation of low rank coals.     

New developments in the theory and modeling of mercury oxidation and binding on activated carbons in flue gas

Recent advances in the mechanistic understanding of mercury oxidation on a carbon surface in flue gas are reviewed in this paper. Theoretical calculations were performed to determine whether the energetics are feasible for a proposed detailed model for oxidative addition of elemental mercury on a carbon edge structure. The results of the calculation show that mercury complexation with a carbenium ion formed at a zigzag edge carbon has a small positive ΔG, but attack of chloride on the complex will proceed with negative ΔG. The energetics rule out a direct covalent bond formation between mercury and the carbenium ion. Alternative concerted reaction models and double-charged models for the mechanism are also feasible but have not yet been computed.     

Chemometric analysis of trace elements distribution in raw and thermally treated high sulphur coals

In the present study, chemometric analysis is applied as a tool to evaluate the release behaviour of trace elements (TEs) during coal utilization processes. Principal component analysis (PCA) and linear discriminant Analysis (LDA) were applied on the TE concentrations of raw and thermally treated coals. PCA and LDA successfully predicted the association of 21 trace elements (Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, Te, Pb) contained in coal and their thermal behavior at various temperatures. Application of chemometric on thermally treated coals shows that at temperature 450 °C, elements like Na, P, K, Fe, Ca, Mg, Al and Si have affinity with mineral matter and therefore have low volatility. Elements like Te, Sb and Ti may form their chlorides, which enhance the volatilities of these elements, while Co and Pb may form sulfides like Co₂S₄ and PbS. In the temperature range of 600-850 °C, either coal undergones an intense degradation of its structure during pyrolysis and the elements released may be adsorbed on coal surface or be volatile. The elements Cr, Co, V, Ni may react with sulphurous gases evolved during pyrolysis. At temperature 1000 °C, wide dispersion in data elements interact with carbon and sulphur compounds of coals. The formation of compounds like Si carbide, bassanite, gehlenite, anarthite may also be responsible for low volatilities of the elements Si, Al and Ca at higher temperatures. Predictive capabilities of PCA and LDA were evaluated in terms of TEs volatilities at different temperatures. The results of chemometric analysis are not only in good agreement with volatilities of TEs present in coals at various temperatures but also with FTIR analysis.     

Porometry, porosimetry, image analysis and void network modelling in the study of the pore-level properties of filters

We present fundamental and quantitative comparisons between the techniques of porometry (or flow permporometry), porosimetry, image analysis and void network modelling for seven types of filter, chosen to encompass the range of simple to complex void structure. They were metal, cellulose and glass fibre macro- and meso-porous filters of various types. The comparisons allow a general re-appraisal of the limitations of each technique for measuring void structures. Porometry is shown to give unrealistically narrow void size distributions, but the correct filtration characteristic when calibrated. Shielded mercury porosimetry can give the quaternary (sample-level anisotropic) characteristics of the void structure. The first derivative of a mercury porosimetry intrusion curve is shown to underestimate the large number of voids, but this error can be largely corrected by the use of a void network model. The model was also used to simulate the full filtration characteristic of each sample, which agreed with the manufacturer's filtration ratings. The model was validated through its correct a priori simulation of absolute gas permeabilities for track etch, cellulose nitrate and sintered powder filters.     

Direct image-based fractal characterization of micromorphology of calcium carbonate fouling crystals

Researches on macroscopic fouling behavior and micromorphology are usually conducted separately. In this paper, the relationship between the macroscopic fouling behavior and micromorphology on different materials is established. A direct fractal-characterization approach based on the micrographs of calcium carbonate fouling crystals is presented. The box-counting method is used to characterize the fouling crystals. For fractal measurements, t-distribution tests of linear regression hypothesis are performed at the significance level of 0.01. If all listed absolute t-statistics with the minimum of 164 are higher than the corresponding t value, the fouling crystals are determined as fractal, with a confidence level of 99%. The fractal dimensions obtained from the micrographs of different visual fields of a specimen are demonstrated to be almost identical, with maximum and minimum relative values of 4.42% and 0.75%, respectively, and standard deviations ranging from 0.0062 to 0.0266. The irregularity of the crystal morphology indicates larger fractal dimensions. Comparison and analysis of the relationship between macroscopic fouling behavior and micromorphology show that the larger fractal dimension of crystal morphology suggests a small amount of surface fouling. Thus, the reasons for the differences in the macroscopic fouling behaviors of different materials are revealed geometrically.     

The traps in characterisation of PAN and carbon fibers by the mercury porosimetry method

The mechanical properties of a fiber relate to an average pore size or the pore size distribution in the fiber. In this study, the effects of testing sample preparation, crystallization rate, humidity, sizing agent, composition and processing conditions on the pore size distribution measurements were analyzed and discussed.     

Thermal and hygric properties of Portland cement mortar after high-temperature exposure combined with compressive stress

Thermal conductivity λ, water vapor permeability δ, and liquid moisture diffusivity κ of cement mortar are measured on specimens subjected to four types of pretreatment, namely, unloaded, mechanically loaded to 90% of compressive strength, thermally loaded by subjecting to a temperature of 800 °C for 2 h, and loaded both mechanically and thermally. The values of λ and κ are found to depend very significantly on the loading mode. The maximum differences observed compared to the unloaded samples are almost one order of magnitude for λ and as much as three orders of magnitude for κ. In contrast, the values of δ are found to increase by only about 40% compared to the basic unloaded material. It is proposed that the observed large differences in λ and κ are due to the formation of cracks and the increase of total pore volume, which were shown by visual analysis and mercury porosimetry.