Pore Size Distribution Analysis Research Articles

Understanding the role of natural pozzolana in regulating the early hydration reaction process and microstructure of Portland cement

The present study examines the regulatory role of natural pozzolana (NP) on the early-age hydration process and microstructural development of Portland cement. Through a series of experiments, including low-field nuclear magnetic resonance (NMR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and scanning electron microscopy (SEM), it was found that NP significantly influences the hydration kinetics and chemical shrinkage of cement paste. The addition of NP was shown to reduce the early-age chemical shrinkage and refine the microstructure by decreasing the quantity of harmful pores and increasing harmless pores, as evidenced by the bimodal distribution observed in pore size distribution (PSD) analysis. XRD and TG results indicate that NP reacts with calcium hydroxide to form additional calcium silicate hydrate (C-S-H) gel, thus improving the interfacial transition zone and resistance to carbonation. SEM micrographs further confirm the improved microstructure with fewer microcracks. The findings suggest that NP can be effectively utilized to optimize the early-age performance of concrete, offering a sustainable approach to improving its durability and long-term structural integrity.

Determination on the thickness of superficially weathered layer of historical stones from Guanzhong area in China

Superficial weathering in the form of granular disaggregation, powdering and flaking on stone surface is one of the most serious damages to stone heritages, since the surface carries most of the artistic, historical information. The determination of the thickness of the superficially weathered layer of historical stones is critical to their conservation. However, the methodology for quantitative analyses of such thickness remains very limited. In this study, we carefully study the vapor absorption and pore structure evolution of historical sandstones from Guanzhong area with respect to their weathering. We find out that the thickness of superficial weathered layer of Guanzhong sandstones can be derived by following the changes in vapor absorption or pore structure. Such data achieved from various methods developed in this work are consistent with each other and in good agreement with the results obtained by using current techniques such as drilling resistance measurement, the Ruxton method and ultrasonic testing. Among all methods used, pore size distribution analysis requires less sample preparation and measures the thickness of superficial weathered layer of Guanzhong sandstones around 7 mm.

Changes in filtration and capacitance properties of highly porous reservoir in underground gas storage: CT-based and geomechanical modeling

The paper presents the results of comprehensive studies of filtration and capacitance properties of highly porous reservoir rocks of the aquifer of an underground gas storage facility. The geomechanical part of the research included studying the dependence of rock permeability on the stress-strain state in the vicinity of the wells, and physical modeling of the implementation of the method of increasing the permeability of the wellbore zone - the method of directional unloading of the reservoir. The digital part of the research included computed tomography (CT)-based computer analysis of the internal structure, pore space characteristics, and filtration properties before and after the tests. According to the results of physical modeling of deformation and filtration processes, it is found that the permeability of rocks before fracture depends on the stress-strain state insignificantly, and this influence is reversible. However, when downhole pressure reaches 7-8 MPa, macrocracks in the rock begin to grow, accompanied by irreversible permeability increase. Porosity, geodesic tortuosity and permeability values were obtained based on digital studies and numerical modeling. A weak degree of transversal anisotropy of the filtration properties of rocks was detected. Based on the analysis of pore size distribution, pressure field and flow velocities, high homogeneity and connectivity of the rock pore space is shown. The absence of pronounced changes in pore space characteristics and pore permeability after non-uniform triaxial loading rocks was shown. On the basis of geometrical analysis of pore space, the reasons for weak permeability anisotropy were identified. The filtration-capacitance properties obtained from the digital analysis showed very good agreement with the results of field and laboratory measurements. The physical modeling has confirmed the efficiency of application of the directional unloading method for the reservoir under study. The necessary parameters of its application were calculated: bottomhole geometry, stage of operation, stresses and pressure drawdown value.

Optimal selection of inversion method for gas-adsorption pore characterization of shales in Wufeng and Longmaxi Formation, Sichuan Basin

The pore space in gas shale spans multiple scales, ranging from nanometers to micrometers with an extremely complex structure and strong microscopic heterogeneity. Existing low-temperature gas adsorption (LTGA) pore size distribution (PSD) analysis models are based on the assumption of a one-dimensional tubular model and there is a lack of sufficient basis for selecting the most appropriate inversion model among the various types available. In this study, a comprehensive characterization of numerous samples from the Wufeng and Longmaxi Formation in the southern Sichuan Basin was conducted using different methods and inversion models. Based on multiple dimensions, such as fitting errors, the correlation between different methods including low-temperature CO2 adsorption (LTCA), nitrogen adsorption (LTNA), and large-scale mosaic Scanning Electron Microscopy (LAM-SEM), the most suitable one-dimensional models for LTCA and LTNA PSD analysis for the studied shale samples are determined. The simulation of gas condensation processes on LAM-SEM images yielded pore volume (PV) in the range of 32–48 nm comparable to the PV characterized by LTNA. Furthermore, the differences observed in PSDs between the gas condensation simulation procedure and the equivalent circular area diameter method indicate that irregular corner regions within larger pores are attributed to the volume of smaller-sized pores during gas adsorption characterization. It is revealed that the correlation between stitched surface area (SA) and maximum methane adsorption is stronger than individual characterizations, indicating that both micropores and mesopores contribute significantly to adsorption, and both characterization methods need to be employed to obtain SSA that influences methane adsorption. The research findings are helpful to the improvement of the multi-scale pore characterization level and evaluation of shale reservoirs.

Characterizations and quantification of freeze-thaw behaviors of recycled brick aggregate concrete

The use of recycled brick aggregates (RBAs) in concrete could provide sustainable solution in construction industry by reducing the consumption of natural resources and protecting the environment by saving landfill sites. However, the use of RBAs is uncommon due to limited available research studies investigating its mechanical and durability behavior, especially the freeze-thaw (FT) behavior. Despite a few studies on FT resistance of RBA concrete (RBAC), the FT deterioration mechanism in RBAC is not fully understood, particularly at the microscale. This lack of understanding hinders the widespread adoption of RBAC in sustainable construction practices, particularly in cold regions. Therefore, this study investigates the FT deterioration mechanism in RBAC using macro and microscale experiments and proposes a Weibull damage model to accurately describe the damage variation in RBAC. RBAC specimens with different water-cement (w/c) ratios of 0.65, 0.5 and 0.35 and RBA replacement levels of 0%, 25%, 50% and 100% were produced and tested under rapid FT cycles. Surface scaling, mass loss, relative dynamic modulus of elasticity, and compressive strength reduction were evaluated. X-ray computed tomography (XCT) was used to characterize pore structure and microcracking alterations during FT cycles. The results showed that the deterioration of RBAC increased with the increase in RBA replacement level. XCT revealed increased porosity and microcracking within the RBA particles, which was linked to the significant damage observed in RBAC compared to reference concrete. Quantitative analysis of pore size distribution before and after FT cycling revealed a substantial increase in small pores (<1 mm3) in RBAC. The proposed Weibull distribution damage model accurately described the damage variation in RBAC with different w/c ratios. This study provides new insights into multiscale FT deterioration mechanisms affecting RBAC, aiding in optimizing RBAC mix designs to balance sustainability and durability.

Performance and mechanism of benzene adsorption on ZnCl2 one-step modified corn cob biochar.

Utilizing cost-effective corn cob, zinc chloride-modified biochar was synthesized through one-step method for benzene adsorption from air. Study on impregnation ratio impact showed optimal benzene adsorption at ZnCl2:CC ratio of 1.5:1, with capacity reaching 170.53mgg-1. Characterization using BET, SEM, FTIR, and XPS was conducted. BET results indicated specific surface area of Zn1.5BC at 1260.63 m2g-1 and maximum pore volume of 0.546 m3g-1. SEM analysis revealed microporous-mesoporous structure in Zn1.5BC, marking significant improvement over original biomass. DFT pore size distribution and FTIR analysis suggested post-modification dehydration and elimination reactions, leading to volatile compound release, functional group reduction, and pore widening. XPS analysis showed decrease in O = C-OH content with increased impregnation ratio, enhancing biochar's π-π electron diffusion for benzene. Langmuir isotherm and pseudo-second-order kinetic models effectively described experimental data, indicating multilayer benzene adsorption on biochar controlled by complex physicochemical adsorption and pore diffusion. Adsorption condition assessment, including adsorption temperature (20-120℃) and benzene concentration in inlet phase (159.73-383.36 mg L-1), was performed. Yoon-Nelson model fitting indicated adsorption site loss at higher temperatures and reduced capture ability due to increased adsorbate molecule kinetic energy. Higher adsorbate concentrations aided adsorption molecule diffusion to biochar surface and internal pores, increasing adsorption rate and shortening equilibrium time. Overall, zinc chloride-modified biochar facilitates benzene adsorption through pore filling and π-π interactions, with pore filling as primary mechanism. Produced biochar shows excellent regeneration properties and reusability.

Hollow core mesoporous carbon spheres as catalyst support for improved platinum utilization in phosphoric acid fuel cells

Using a well-known sol-gel technique, monodispersed silica spheres measuring 380 nm in size are generated in situ. These silica spheres serve as a template for the synthesis of hollow core mesoporous shell (HCMS) carbon spheres. Inside the pores of the template, a polymer is synthesized using azoisobutyronitrile and divinylbenzene polymerization route. Polymer carbonization followed by template remotion yielded HCMS carbon spheres. This HCMS carbon is mesoporous and offers uniform Pt crystallite distribution for acid fuel cell applications. As-prepared HCMS carbon is examined by field emission gun SEM, TEM, nitrogen adsorption/desorption isotherm (BET surface area and BJH pore size distribution analysis), and apparent density using Helium pycnometry. The HCMS carbon obtained demonstrates a BET surface area of 623 m2g-1, showcasing a uniform pore size distribution centered at 3.8 nm. This specific characteristic renders it an ideal support material for fuel cell catalysts. The electrochemical studies reveal the key parameters like corrosion resistance, bulk electrical conductivity, the electrochemical surface area of Pt chemically deposited on HCMS carbon, and unit fuel cell performance under phosphoric acid environment. These parameters are compared with the standard carbon powder, Vulcan XC72R and a commercial catalyst to evaluate the HCMS carbons’ suitability for fuel cell applications.

Three-Dimensional Porous PVDF Foam Imprinted Membranes with High Flux and Selectivity toward Artemisinin/Artemether.

In this study, a new 3D porous PVDF-foam-imprinted membrane (PPIM) for the selective separation of artemisinin (ART) was first prepared via the dopamine adhesion of pre-synthesized MIPs into the interior of the PPIM. In the PPIM, the pre-synthesized molecularly imprinted polymers (MIPs) with artesunate (ARU) as a dummy template were uniformly loaded on the interior of the membrane, avoiding the defects of recognition site encapsulation found in the conventional membrane. This membrane also exhibited excellent flux, which is beneficial in practical separation applications. The PPIM was systematically characterized via FT-IR, SEM, pore-size distribution analysis, water contact angle test, membrane flux, and mechanical performance analysis, respectively. In the static adsorption experiment, the pseudo-second-order kinetic model better fitted the rebinding data of ART. Under dynamic conditions, the ART adsorption capacity of the PPIM could be further remarkably improved by tailoring the flow rate to 3 mL min-1. In the selective separation experiment, with artemether (ARE) as the competition substrate, the selective separation ability (α) of the PPIM towards ART/artemether (ARE) reached its peak value (3.16) within only 10 min at this flow rate, which is higher than that of porous PVDF foam non-imprinted membranes (PPNM) (ca. 1.5), showing great separation efficiency in a short time. Moreover, the PPIM can be reused five times without a significant decrease in its adsorption capacities, showing good regeneration performance. This work highlights a simple strategy for constructing new MIMs with high flux and great mechanical strength to achieve the efficient selective separation of ART and ARE in practical applications.

Unleashing the dye adsorption potential of polyaminoimide homopolymer: DFT, statistical physics, site energy and pore size distribution analyses

The efficient removal of Congo Red (CR) dye from aqueous solutions is an important issue in environmental protection. This study presents the synthesis and optimization of a polyaminoimide homopolymer (PHP) adsorbent for the removal of CR dye. To optimize the synthesis of PHP, ten different compositions of maleic anhydride and ethylene diamine were tested, with PHP3 demonstrating the highest efficacy. The adsorption process was further enhanced by optimizing pH, temperature, adsorbent dose, and initial dye concentration. Isotherm and kinetic studies revealed that the Langmuir-Freundlich model and the pseudo-second-order kinetics best described the adsorption process. Moreover, PHP3 demonstrated significantly greater selectivity for CR compared to Synozol yellow, and Sulfasalazine. Advanced statistical models were used to analyze the adsorption data, and the single-layer model with single energy (M1) being the most suitable, suggesting that CR molecules were adsorbed onto PHP3 in a perpendicular position through a multimolecular process, the adsorption process is physical, endothermic, spontaneous and specific surface area of PHP3 increased from 54.31 to 115.74 m2 g−1 as temperature rose from 288 to 318 K. Site energy distribution and pore size distribution studies showed that PHP3 has a heterogeneous energy distribution on its surface, and that the adsorption of CR dye primarily takes place in the macropores of PHP3. Density Functional Theory analysis indicated that PHP3 has electron-rich amine groups that can interact with electron-deficient sulfonate groups in CR, while electron-poor amide groups in the polymer can interact with the electron-rich azo group in Congo Red. It also shows that the presence of NaF, Na2SO4, and KCl salts did not significantly affect the CR adsorption, indicating the potential affinity/selectivity of PHP3 towards CR dye. The findings suggest that PHP3 could be an effective and promising adsorbent for industrial applications in wastewater treatment.

A novel Chitosan-Barbituric acid hydrogel supersorbent for sequestration of chromium and cyanide ions: Equilibrium studies and optimization through RSM

The objective of this study is to transform chitosan biopolymer by crosslinking with barbituric acid into an amine-rich product that could be applied as a water treatment agent. Chitosan-barbituric acid (CBA) was synthesized by lyophilization process and characterized using FT-IR, XRD, TGA-DTA, SEM-EDX, BET surface area and BJH pore size distribution analysis. The pHpzc was found to be 7.7 indicating applicability towards both cations and anion adsorption. The CBA was used for seizure of CrVI and CN– from aqueous solutions in batch adsorption as well as fixed bed column experiments. Response surface methodology (RSM) was used as a statistical tool to optimize the functioning parameters resulting in more than 90 % removal of these ions. As shown by isotherm and kinetics data, Langmuir isotherm and pseudo second order kinetics exhibited a good fit for the adsorption process. The maximum adsorption capacities of CBA towards CrVI and CN– evaluated using Langmuir isotherm fitment were 534.75 mg g−1 and 251.66 mg g−1 at pH 4.0 and 6.0 respectively. Thermodynamic studies indicated spontaneous and enthalpy driven course with large negative enthalpy changes of −56.39 and −31.81 kJ mol−1 respectively. Fixed bed column studies showed that the material could be used for larger sample volume treatment even at 200 mg/L CrVI and 100 mg/L CN−1 concentration. Regeneration studies of adsorbent was conducted over five adsorption–desorption cycles with removal efficiency more than 50 %indicating reusability of the adsorbent. Analysis of adsorbent sustainability revealed that the synthesis was eco-friendly as indicated by low value of E-factor of 0.32.

Deinterpenetration of IRMOF-9.

One of the iconic characteristics of metal-organic frameworks (MOFs) is the possesssion of guest-accessible pores. Increasing pore size has a direct and often beneficial impact on a MOF's adsorption and separation properties. However, as pore size increases, the resulting void spaces are often filled by interpenetrated frameworks, where one or more networks crystallize within the pore system of another identical network, reducing the MOF's free volume and pore size. Furthermore, due to the thermodynamic favorability of interpenetration during solvothermal synthesis, techniques to synthetically differentiate interpenetrated from non-interpenetrated MOFs are paramount. Herein we report the synthesis of deinterpenetrated IRMOF-9 via halide mediated deinterpenetrative conversion of Zn4O-derived IRMOF-9. IRMOF-9, when treated with ethylammonium bromide, is quasi-selectively etched, revealing the non-interpenetrated analogue, IRMOF-10 (deinterpenetrated IRMOF-9), which can be isolated prior to complete dissolution by the bromide solution. Dye adsorption, surface area and pore size distribution analysis, powder X-ray diffraction, and elemental analysis are consistent with successful deinterpenetration.

Magnesium oxychloride cement with hydrophobic pore network for utilizing as oil well cement

Magnesium oxychloride cement (MOC) possesses some excellent characteristics, which can be used as oil well cement, to deal with the complex environmental conditions in oil and gas wells. However, the water resistance property of MOC is poor. In this study, a new type of magnesium oxychloride cement (MOC) with improved water resistance was developed by modifying the pore structure of pure MOC using hydrophobic admixtures. To assess the performance of the new MOC, a range of tests were performed, including compressive strength, softening coefficient, capillary water absorption, pore size distribution, mineral composition and microstructure analysis. The results showed that the pore size distribution of the MOC was altered from a large pore-dominant structure to a small pore-dominant one. The hydrophobic admixture and the gel substance formed on the strength-providing phases prevented them from water erosion, resulting in enhanced strength and water resistance. This new type of MOC has the potential to be used in challenging environments, such as oil and gas wells and underwater structures.

Sophisticated strategies for designing fast-charging lithium-ion batteries without sacrificing the energy density

The use of electric vehicles (EVs) is a green approach to mitigating climate change and pollution associated with the emissions of internal combustion engines. Therefore, research on lithium-ion batteries (LIBs), which are major EV components, has become vital. LIBs in EVs should be characterised by high energy and power densities for long-term use. In this study, the electrochemical performance during fast charging was examined with the active material (AM) content kept constant at 94 wt% so as not to sacrifice energy density, and the ratio of conducting agent (CA) to binder altered to account for the remaining 6 wt% of the composition. We evaluated the charging properties of Ni-rich cathodes and carried out cyclic voltammetry, electrochemical impedance spectroscopy, cross-sectional field-emission scanning electron microscopy and pore size distribution analyses. Evidence reveals that when the CA:binder ratio is 4:6, AM is hampered by the binder, which inhibits electronic conduction and hence increases its resistance to electrochemical reactions. On the other hand, at 7:3 CA:binder ratio, the void spaces in the cathode are filled by CA, decreasing porosity and hindering Li+ transfer through the electrolyte. As a result, a 6:4 CA:binder ratio is optimal for fast-charging in terms of electronic and ionic conduction. The results of this study indicate that electrochemical performance can be controlled by the inactive components' ratio, and our research proposes the best electrode composition with respect to the CA:binder ratio for fast-charging.

Clinoptilolite—A Sustainable Material for the Removal of Bisphenol A from Water

Bisphenol A is a remarkable chemical compound as it has many applications, mainly in the plastics industry, but it also has toxic effects on the environment and human health. This article presents a comparative study regarding the adsorption of BPA on Active carbon and zeolitic tuff, ZTC. In this paper, the characterization of the zeolitic tuff, adsorbent, was carried out from an elemental and mineralogical point of view, and it noted the pore size and elemental distribution, using SEM, EDAX, and XRD analysis. The pore size varies from 30 nm to 10 µm, the atomic ratio is Si/Al ≥ 4, and 80% of the mineralogical composition represents Ca Clinoptilolite zeolites and Ca Clinoptilolite zeolites ((Na1.32K1.28Ca1.72Mg0.52) (Al6.77Si29.23O72)(H2O)26.84). Moreover, a comparative study of the adsorption capacity of bisphenol A, using synthetic solutions on an activated carbon type—Norit GAC 830 W, GAC—as well as on Clinoptilolite-type zeolitic tuff—ZTC, was carried out. The experiments were carried out at a temperature of 20 °C, a pH of 4.11, 6.98, and 8.12, and the ionic strength was assured using 0.01 M and 0.1 M of KCl. The adsorption capacities of GAC and ZTC were 115 mg/g and 50 mg/g, respectively, at an 8.12 pH, and an ionic strength of 0 M. The Langmuir mathematical model best describes the adsorption equilibrium of BPA. The maximum adsorption capacity for both adsorbents increased with an increasing pH, and it decreased with increasing ionic strength.

Development of heparinized and hepatocyte growth factor-coated acellular scaffolds using porcine carotid arteries.

Tissue-engineered blood vessel substitutes have been developed due to the lack of suitable small-diameter vascular grafts. Xenogeneic extracellular matrix (ECM) scaffolds have the potential to provide an ideal source for off-the-shelf vascular grafts. In this study, porcine carotid arteries were used to develop ECM scaffolds by decellularization and coating with heparin and hepatocyte growth factor (HGF). After decellularization, cellular and nucleic materials were successfully removed with preservation of the main compositions (collagen, elastin, and basement membrane) of the native ECM. The ultimate tensile strength, suture strength, and burst pressure were significantly increased after cross-linking. Pore size distribution analysis revealed a porous structure within ECM scaffolds with a high distribution of pores larger than 10 μm. Heparinized scaffolds exhibited sustained release of heparin in vitro and showed potent anticoagulant activity by prolonging activated partial thromboplastin time. The scaffolds showed an enhanced HGF binding capacity as well as a constant release of HGF as a result of heparin modification. When implanted subcutaneously in rats, the modified scaffolds revealed good biocompatibility with enzyme degradation resistance, mitigated immune response, and anti-calcification. In conclusion, heparinized and HGF-coated acellular porcine carotid arteries may be a promising biological scaffold for tissue-engineered vascular grafts.

Characterization of the pore structure in Chinese anthracite coal using FIB-SEM tomography and deep learning-based segmentation

Coalbed methane (CBM) is an unconventional natural gas that possesses significant impacts on energy supply, mining safety, and environmental conservation. CBM is primarily stored within the pores of coal, highlighting the significance of pore structures for both methane storage and migration. However, comprehensively understanding the intricate pore structures in coal pose challenges. This study employed focused ion beam-scanning electron microscopy (FIB-SEM) tomography and deep learning-based segmentation to characterize the pore structures within a Chinese anthracite sample. The obtained pore structures exhibited a considerable degree of disconnection, comprising numerous separate pore components. Isolated pores prevailed in number, while connected pores dominated in surface area and pore volume. Mesopores (100–1000 nm) contributed the most to pore number, surface area, and pore volume. Pore size distribution analysis revealed distinct patterns among different pore structure properties, with pore number exhibiting an intensive distribution while surface area and pore volume displaying dispersed distributions. Pore structure connectivities exhibited a hierarchical nature and held distinct meanings at the levels of pore, pore component, and pore network. The pore structure characteristics observed in this study have implications for primary CBM recovery, emphasizing the necessity to improve connectivity between pore components and fractures to enhance production rates and recoverability.

Hexatopic Vertex-Directed Approach to Vinylene-Linked Covalent Organic Frameworks with Heteroporous Topologies.

A D3h-symmetric hexatopic monomer was first prepared by attaching the three-fold ditopic moiety 2,6-dimethylpyridine to the meta-positions of a phenyl ring. It was further condensed at its six pyridylmethyl carbons with linear ditopic aromatic dialdehydes, resulting in two vinylene-linked COFs with heteroporous topologies, as revealed by powder X-ray diffraction (PXRD), nitrogen sorption, and pore-size distribution analyses, as well as transmission electron microscopy (TEM) image. The linear- and cross-conjugations, respectively, arising from the 2,6-linked pyridines and meta-linked phenylenes in the hexatopic nodes rendered the resultant COFs with well-patterned π-delocalization, allowing for efficiently catalyzing the bromination of aromatic derivatives with the pore-size-dependent conversion yields and regioselectivity under the irradiation of green light.

High surface area peat moss biochar and its potential for Chromium metal adsorption from aqueous solutions

Activated carbons (ACs) have been synthesized using local peat moss biomass for adsorption of heavy metal ions. Adsorbents with different surface areas and pore sizes were obtained using a chemical activation route with different impregnation ratios (20%, 30%, and 40%) of phosphoric acid. The carbonization process was carried out in a tubular furnace under flow of nitrogen (N2) at 500 °C, and 600 °C. Physicochemical properties of developed activated carbon have been evaluated by several techniques such as; X-ray diffraction, Scanning Electron Microscopic, Energy Dispersive X-ray Spectroscopy, Nitrogen adsorption isotherm, Pore size distribution analysis, and Fourier-transform analysis. Moreover, adsorption of chromium ions (Cr+2) from an aqueous solution under different variables was carried out. Heavy metal concentration (20 - 200) ppm, the dosage of adsorbent (0.1 – 0.5) g/L, the time of contact (0 - 220) min, and initial pH (2 - 8) were studied. Results showed that a synthesis route by chemical activation with 30% H3PO4 concentration at 600 °C for 3 h gave the highest BET surface area and pore volume (1692.6 m2/g and 1.55 cm3/g) respectively, compared with other prepared samples. As well as, the removal results show that the maximum adsorption capacity was 493.3 mg/g at 200 mg/L of initial heavy metal concentration, 6.5 pH, 0.3 g/L activated carbon dosage, and 180 min contact time. The Freundlich isotherm was the better description of the adsorption equilibrium data, while the pseudo-second-order model shows the most accurately describes of adsorption kinetics, which indicates that chemisorption is dominant in the adsorption process. Temperature and thermodynamics parameters were studied. The positive value of enthalpy indicates that the adsorption was endothermic.

Microstructure of Dry Mortars without Cement: Specific Surface Area, Pore Size and Volume Distribution Analysis

The evolution of the microstructure of the wastepaper sludge ash-based dry-mortar mixtures is characterized. Mixtures have been prepared with a large volume of wastepaper sludge ash (WSA) and ground granulated blast-furnace slag (GGBS) as a binder matrix mixed with water. Two ratios of water/binder (w/b) = 0.5 and 0.6 were selected. Both of these two industrial by-products are well-known as supplementary cementitious materials in the construction industry and they constitute a convenient replacement for cement. A series of these dry mortars for two ratios w/b were activated by three different chemical activators. They were placed in 4 × 4 × 16 cm3 molds and then compacted at the same compaction energy of 600 kN·m/m3. The influence of water quantity, compaction level and activators on the microstructure of these mortars was investigated by measuring the specific surface area, pore size and volume. Different series of samples have been compared in terms of adsorption/desorption hysteresis and pores network. The influences of water quantity and energy level were first discussed on non-activated dry mortars and this analysis led to the selection of an optimal energy for the comparative study of activated dry mortars. A significant difference in behavior was observed between the studied activators in terms of specific surface area, adsorption property and pore distribution. Then, the microstructure of the three activated dry mortars is observed and analyzed considering the two w/b ratios, the mechanical strength obtained and the type and dosage of activator used. Dry mortars show micropores regardless the quantity of water and the dosage of activator.

Micropore sites in ferrihydrite are responsible for its higher affinity towards As(III) relative to As(V)

Poorly-crystalline ferrihydrite is ubiquitous in the environment and contributes to controlling the fate of arsenic in sediments and soils. Although there is evidence that ferrihydrite has a higher affinity towards As(III) relative to As(V), little is known about how and why As(III) is readily immobilized by ferrihydrite. In this study, ferrihydrite was employed to evaluate the As(III) and As(V) adsorption behavior. The properties of ferrihydrite such as morphology, pore size distribution, arsenic adsorption species, and adsorption energies of arsenic at different sites were carefully examined using TEM-EDS mapping, positron annihilation lifetime (PAL) spectroscopy, X-ray absorption spectroscopy (XAS), N2 adsorption isotherms, and theoretical calculations of density function theory (DFT). Batch adsorption experiments revealed that the maximum adsorption of As(III) (839.7 μmol g−1) on ferrihydrite, fitted by Langmuir model, was considerably larger than that of As(V) (372.4 μmol g−1). PAL characterization and pore size distribution analysis demonstrated that ferrihydrite had an abundance of vacancy cluster-like micropores, which consisted of 10–20 atom deficiencies (V10-20). The calculated hydrated ion size of As(III) species (4.22 Å) at pH 6.0 was smaller than the size of As(V) (5.90 Å). The higher As(III) adsorption to ferrihydrite was attributed to its surface adsorption sites as well as its abundant micropore adsorption sites, which are available only to As(III) due to their size matching well with the size of the ferrihydrite micropores, thus significantly contributing to greater As(III) immobilization.