Failure evolution and instability prediction of fiber-reinforced polymer-confined cement mortar specimens under axial compression.

In geotechnical engineering, a large number of pillars are often left in underground space to support the overlying strata and protect the surface environment. To enhance pillar stability and prevent instability, this study proposes an innovative technology for pillar reinforcement. Specifically, local confinement of the pillar is achieved through fiber-reinforced polymer (FRP) strips, resulting in the formation of a more stable composite structure. In order to validate the effectiveness of this structural approach, acoustic emission characteristics and surface strain field characteristics were monitored during failure processes, while mathematical models were employed to predict specimen instability. The test results revealed that increasing FRP strip confinement width led to heightened activity in acoustic emission events during failure processes, accompanied by a decrease in shear cracks but an increase in tensile cracks. Moreover, ductility was improved and deformation resistance capacity was enhanced within specimens. Notably, initial crack generation occurred within unconfined regions of specimens during failures; however, both length and width as well as overall numbers of cracks significantly decreased due to implementation of FRP strips. Consequently, specimen failure speed was slowed down accordingly. Finally, the instability of the partial FRP-confined cement mortar could be more accurately predicted based on the model of FRP-confined concrete. It was verified by the test results.

Effect of a Simulated Coal Mine Environment on Polyurethane Grouting Material and a Proposed Polyurethane Strengthening Method.

When it comes to grouting in coal mines, polyurethane (PU) is often utilized. However, it is of vital importance to consistently improve the mineral PU, considering the significant amount of environmental deterioration to which it is prone. Laboratory experiments were used to model various coal mine conditions. Additionally, a workable technique for PU strengthening using ultrasonic waves was proposed. Compression tests and scanning electron microscopy (SEM) were used to describe the PU-gangue material's induration characteristics. The results showed that ultrasound has a positive impact on PU's mechanical strength. The final strength of the PU was significantly impacted by the size of the coal gangue particles, the amount of dust, and the amount of water. The induration made of gangue and PU with the same mass but differing particle sizes was noticeably different in its compressive strength. The strengthening mechanism showed that the average size of the rigid foam after the ultrasound treatment was smaller, and the 'honeycomb'-structured space in the inner section was more compact, resulting in the rigid PU foam having a higher compressive strength after ultrasound treatment. Furthermore, the dust content and water content of coal mines need to be controlled within a specific range to ensure the effective use of PU grouting materials.

Rheological and mechanical performance analysis and proportion optimization of cemented gangue backfill materials based on response surface methodology.

Cemented backfill mining is a green mining method that enhances the coal mining rate and the safety of mined-out regions. To transport the cemented gangue backfill material (CGBM) into the mined-out regions, it is essential to ensure high flowability and adequate compressive strength after hardening. Based on the response surface methodology (RSM), 29 experiments were conducted in this paper to test the yield stress and plastic viscosity of CGBM slurry. Cubic specimens with dimensions of 100 mm were prepared and underwent uniaxial compression tests to obtain the compressive strength at a curing age of 28 days. Quadratic polynomial regression models were established for yield stress, plastic viscosity, and compressive strength to explore the effects of fly ash content, water-cement ratio, mass concentration, and superplasticizer dosage on the properties of CGBM. Multi-objective optimization was conducted to determine the optimal material proportion of CGBM. The research results indicate that (1) the mass concentration most profoundly affected the yield stress and plastic viscosity of CGBM, and it increased with an increase in mass concentration. Fly ash content had an inverse relationship with compressive strength. Superplasticizer was found to improve the flowability and strength of CGBM. (2) The established response surface model could reflect the relationship between CGBM's material proportion and rheological and mechanical properties, and predict relevant parameters. (3) Multi-objective optimization determined the optimal proportion of CGBM to be 80% fly ash content, 54% water-cement ratio, 79% mass concentration, and 3% superplasticizer dosage. The research findings offer valuable guidance to mining backfill engineering.

Creep and strength characteristics of cemented gangue backfill under coupling effect of load and acid corrosion.

Cemented gangue backfill technology is beneficial to the reuse of solid waste and sustainable economic development. However, mine water has a great impact on the strength and deformation of cemented gangue backfill (CGB). In this study, the CGB specimens under load were placed in simulated acid mine water (H2SO4 solution). The changes in deformation, resistivity, and ultrasonic pulse velocity (UPV) of CGB were monitored. On the 360th day, the stress-strain curve and acoustic emission (AE) energy of the specimen during loading were recorded. The degradation mechanism of CGB was discussed by scanning electron microscope (SEM) and X-ray diffraction (XRD). The results showed that the deformation of CGB increased with time. The effect of H2SO4 solution concentration on the deformation was different in the early and late stages. Applying an 80% stress-strength ratio (SSR) reduced the strength and increased the deformation. The UPV and resistivity had different characteristics at different corrosion ages, which could be used for long-term stability monitoring of CGB. The CGB showed the strongest AE energy characteristics near the peak stress. The AE energy decreased with the increase of pH value in the pore compaction stage, and the AE activity of the CGB under 80% SSR was much greater than that of the CGB under 40% SSR. The erosion of the H2SO4 solution on the CGB was inhibited by applying a small load. Excessive load aggravated the erosion deterioration of CGB due to initial plastic damage. The research results can provide a reference for the durability design of CGB.

Post-anthesis supplementary irrigation improves grain yield and nutritional quality of drip-irrigated rice (Oryza sativa L.).

Introduction: Approximately 50% of irrigation water is saved during drip-irrigation of rice, which has tremendous potential for water-saving agriculture, particularly in areas where water resources are scarce. However, the grain yield and quality of drip-irrigated rice are adversely affected. Methods: In this study, we investigated the effects of different irrigation strategies on the grain yield and quality of drip-irrigated rice using field experiments. Four irrigation treatments were studied: whole growing season flooding (FI), whole growing season normal drip irrigation (DI, soil relative moisture (RSM) was maintained in the range of 90-100%), pre-anthesis drip irrigation and post-anthesis water stress (SAF, the RSM was maintained in the range of 80-90% after anthesis), pre-anthesis drip irrigation, and post-anthesis flooding (FAF). Results: The results showed that grain yield, harvest index, seed setting rate and 1000 grain weight in DI and SAF were significantly lower than in FI and FAF. These parameters were not significantly different between FI and FAF but were significantly greater in DI than in SAF. Compared with FI and FAF, the source capacity, source activity time, and sink activity of DI and SAF decreased, and the sink-source difference increased. The sink-source difference had a significant negative correlation with rice yield and 1000 grain weight. The activities of ADP-glucose pyrophosphorylase, starch branching enzyme, and amylopectin content in grains in the middle panicles of FAF were significantly higher than those of DI and SAF. SAF resulted in increased amylose/amylopectin ratio and total protein content in grains but decreased proportion of glutenin in total protein. Irrigation after anthesis of drip-irrigated rice narrowed the difference between sink sources in rice plants, increased the grain yield and harvest index by 29.2% and 11%, respectively, compared to DI, increased water productivity by 19% compared to FI, and improved the grain quality of drip-irrigated rice. Discussion: This study highlights that post-anthesis sufficient irrigation of drip-irrigated rice plays a positive role in maintaining the source-sink balance. This study serves as a foundation for the development of more effective rice farming methods that conserve water, while increasing the grain yield and quality of drip-irrigated rice.

Fracturing Behaviors and Mechanism of Serial Coal Pillar Specimens with Different Strength.

The fracturing behaviors of serial coal pillars is significant for understanding their failure mechanism. To reveal this, the bearing stress, acoustic emission, electrical resistivity, local strain, force chain distribution, and cracks evolution of serial coal pillars under uniaxial compression were evaluated by experiment and numerical simulation. The results show that four bearing stages are observed during the fracturing process (i.e., nonlinear growth, linear growth, yielding growth, and weakening stages). The acoustic emission features, electrical resistivity responses, strain develops, force chain distributions, cracks evolutions, and local displacement are highly consistent to illustrate the fracturing behaviors. System fracturing of serial coal pillar specimens is appeared along with the collapse of lower uniaxial compressive strength coal pillar specimen. The limit bearing capacity of serial coal pillar specimens is almost equal to the strength of lower uniaxial compressive strength coal pillar specimen. The unbalanced deformation characteristics of serial coal pillar specimens are presented due to the strength differences. The evolution of the key deformation element is the rooted reason for the overall fracturing mechanism of serial coal pillar specimens. For serial coal pillar specimens with different strengths, the critical condition of system fracturing is that the sum of secant modulus of upper and bottom coal pillars is zero, which is expected to predict the system fracturing of serial pillars in the underground coal mining.

Rheological properties of cemented gangue backfill material based on fractal characteristics of waste coal gangue.

The study herein was intended to evaluate the rheological properties of cemented gangue backfill material (CGBM). For this purpose, the rheological test of CGBM with fractal aggregate particle size distribution was carried out, and variations of static yield stress, dynamic yield stress, and plastic viscosity were investigated as a function of fractal dimension and time. The results reveal that aggregate particle size distribution exerts a significant influence upon the rheological properties of CGBM, and with the escalation of the fractal dimension of the aggregate, the yield stress and plastic viscosity initially decline and then increase. In addition, with elapsing time, the correlation between the static yield stress and the fractal dimension of CGBM specimens increases, while the correlations between the dynamic yield stress and the plastic viscosity and the fractal dimension decrease. The relationships between rheological parameters and fractal dimensions at different times are established based on the experimental results. The influence mechanism of aggregate particle size distribution on CGBM is analyzed from the perspective of the aggregate packing state. This study can provide a basis for the ratio design of CGBM in backfill mining.

Candidate genes potentially involved in molting and body size reduction in the male of the horned gall aphid, Schlechtendalia chinensis.

In general, insects grow (increase in body size) through molting. To the opposite, the body size of the males of the horned gall aphid, Schlechtendalia chinensis, gets smaller after molting and as they age. To understand the molecular bases of this rare phenomenon, transcriptomes were generated from 1-5 days old male and the data were analyzed via a weighted gene co-expression network analysis (WGCNA). A total of 15 partitioned modules with different topological overlaps were obtained, and four modules were identified as highly significant for male body length (p < 0.05). Kyoto Encyclopedia of Genes and Genomes (KEGG) enrichment analysis suggested that a portion of genes in the four modules are likely involved in autophagy and apoptosis. In addition, a total of 40 hub genes were obtained in the four modules, and among them eight genes were highly expressed in males compared to individuals of other generations of S. chinensis. These eight genes were associated with autophagy and apoptosis. Our results reveal the unique negative growth phenomenon in male S. chinensis after molting, and also suggest that the male S. chinensis with no ability to feed probably decompose their own substances via autophagy and apoptosis to provide energy for life activities such as germ cell development.

Maximum Block Energy Guided Robust Subspace Clustering.

Subspace clustering is useful for clustering data points according to the underlying subspaces. Many methods have been presented in recent years, among which Sparse Subspace Clustering (SSC), Low-Rank Representation (LRR) and Least Squares Regression clustering (LSR) are three representative methods. These approaches achieve good results by assuming the structure of errors as a prior and removing errors in the original input space by modeling them in their objective functions. In this paper, we propose a novel method from an energy perspective to eliminate errors in the projected space rather than the input space. Since the block diagonal property can lead to correct clustering, we measure the correctness in terms of a block in the projected space with an energy function. A correct block corresponds to the subset of columns with the maximal energy. The energy of a block is defined based on the unary column, pairwise and high-order similarity of columns for each block. We relax the energy function of a block and approximate it by a constrained homogenous function. Moreover, we propose an efficient iterative algorithm to remove errors in the projected space. Both theoretical analysis and experiments show the superiority of our method over existing solutions to the clustering problem, especially when noise exists.

Consistency-Induced Multiview Subspace Clustering.

Multiview clustering has received great attention and numerous subspace clustering algorithms for multiview data have been presented. However, most of these algorithms do not effectively handle high-dimensional data and fail to exploit consistency for the number of the connected components in similarity matrices for different views. In this article, we propose a novel consistency-induced multiview subspace clustering (CiMSC) to tackle these issues, which is mainly composed of structural consistency (SC) and sample assignment consistency (SAC). To be specific, SC aims to learn a similarity matrix for each single view wherein the number of connected components equals to the cluster number of the dataset. SAC aims to minimize the discrepancy for the number of connected components in similarity matrices from different views based on the SAC assumption, that is, different views should produce the same number of connected components in similarity matrices. CiMSC also formulates cluster indicator matrices for different views, and shared similarity matrices simultaneously in an optimization framework. Since each column of similarity matrix can be used as a new representation of the data point, CiMSC can learn an effective subspace representation for the high-dimensional data, which is encoded into the latent representation by reconstruction in a nonlinear manner. We employ an alternating optimization scheme to solve the optimization problem. Experiments validate the advantage of CiMSC over 12 state-of-the-art multiview clustering approaches, for example, the accuracy of CiMSC is 98.06% on the BBCSport dataset.

JPEG Steganography With Content Similarity Evaluation.

Content similarity is a representative property of natural images, for example, similar regions, which is utilized by modern steganalysis. Existing JPEG steganographic methods mainly focus on the complexity of content but ignore content similarity. This article investigates content similarity to improve the undetectability of JPEG steganography. Specifically, the content similarity of DCT blocks and the 64 parallel channels is used to design the distortion function. Given a JPEG image, initial embedding costs are assigned for quantized DCT coefficients using an appropriate algorithm among the existing distortion functions. Then, the similarities of blocks and channels are used to update the initial embedding costs, respectively. After combination, the final distortion function can be obtained. Using syndrome trellis coding (STC), which achieves minimal embedding distortion with respect to a given distortion function, secret data are embedded into the cover image with a final distortion function. Experimental results show that our scheme achieves better undetectability than current state-of-the-art JPEG steganographic methods.

Effects of width-height ratio and roof-floor strength on the mechanical characteristics of cemented gangue backfill pier-column.

Cemented gangue backfill pier-column (CGBP) which was made of coal gangue, fly ash, cement, and water is the supporting component of the goaf in partial backfill mining or constructional backfill mining for controlling the surface subsidence of coal mining. The width-height ratio and roof-floor strength directly affect the bearing capacity of CGBP under axial compression, which is essential for the design of CGBP. Herein, the effect of width-height ratio (1:3-1:1) on the mechanical characteristics of CGBP with different curing ages under uniaxial compression was system studied through experiment, and the damage process was analyzed by ultrasonic equipment and DIC. Based on the experimental results and discrete element theory, a three-phase numerical model for CGBP was established, which considered the real aggregate shape and distribution and the mechanical characteristics of each phase. Then, the effects of the end friction coefficient and the strength ratio of roof-CGBP-floor combination on the strength and failure characteristics of CGBP (large width-height ratio: 1:1-4:1) were investigated. The results show that CGBP shows the width-height ratio effect obviously and the strength and ductility increase with the increase of the width-height ratio, and the width-height ratio effect increases with the increase of curing age and strength ratio. The end friction constraint is the main reason for the width-height ratio effect, and the higher the friction coefficient is, the larger the width-height ratio effect shows, and the width-height ratio effect disappears without end friction constraint. The increase of the width-height ratio of CGBP and the strength ratio of the roof-CGBP-floor combination increases the strength of the combination. Whether the strength of the combination is greater than that of CGBP may have a roof-floor strength threshold or a strength ratio threshold, which are between 31.44-54.11 MPa and 3.75-6.44, respectively. When the strength of the roof and floor is different, the strength of the combination is mainly controlled by the weak carrier and increases with the increase of the strength of the weak carrier. The peak strain energy of CGBP and combination increases with the increase of end friction coefficient, width-height ratio, and strength of roof and floor. The experimental and simulation results can be used to guide the design of CGBP in constructional backfill mining or partial backfill mining.

Mechanical and Acoustic Emission Characteristics of Coal-like Rock Specimens under Static Direct Shear and Dynamic Normal Load.

In underground engineering, shear failure is a common failure type in coal-rock mass under medium and low strain-rate disturbance loads. Analyzing the shear failure mechanical properties of coal-rock mass under dynamic normal load is significant. In order to reveal the influence of disturbance load on the shear mechanical properties of coal rock, a dynamic and static load coupling electro-hydraulic servo testing machine was used to conduct the shear tests of coal-like rock materials under dynamic and constant normal load. The amplitude of dynamic load is 10 kN and the frequency is 5 Hz. The damage process of the specimens was detected by the acoustic emission (AE) detection system. The results imply that the shear failure process of coal-like rock materials under constant normal load can be divided into four stages. The normal disturbance decreased the shear strength of the specimens and increased the shear modulus of the specimens. With the increase in normal load, the influence of disturbance on the shear strength of the specimen decreased. By analyzing the AE parameters, it was found that the dynamic load made the internal damage of the specimen more severe during the shear failure process. The damage variable was calculated by AE cumulative energy, and the damage evolution was divided into three stages. The shear failure mechanism of the specimen was judged by RA (rise time/amplitude) and AF (average frequency). It was found that from the elastic deformation stage to the unstable development fracture stage, the proportion of shear fracture increased. When the dynamic normal load was 10 kN and 30 kN, the fracture was mainly shear fracture; When the dynamic normal load was 50 kN, the fracture was mainly tensile or mixed fracture. The dynamic normal load affects the shear strength and failure mechanism. Therefore, the influence of disturbance load on coal-rock mass strength cannot be ignored in underground engineering.

Study on Mechanical Properties and Weakening Mechanism of Acid Corrosion Lamprophyre.

In order to study the weakening mechanism and mechanical behaviors of hard lamprophyre of Carboniferous Permian coal-bearing strata in China's mining area, lamprophyre samples were subjected to static rock dissolution experiments with pH values of 0, 2, and 4. The acid corrosion mechanism of lamprophyre was revealed from the weight changes of samples, characteristics of solution ion concentration, and macro-mechanical properties. The experimental results show that reaction occurred between lamprophyre and acid solution. With the increasing concentration of H+, the reaction was more intense, the degree of acid etching was higher, and the weight loss was greater. The internal damage induced by acid etching results in the slow extension of the compaction stage of stress-strain curve of uniaxial compression, and the obvious deterioration of mechanical properties of the lamprophyre. The uniaxial compressive strength of the lamprophyre in the dry state is 132 MPa, which decreased to 39 MPa under the acid etching condition, showing significant mudding characteristics. Dolomite (CaMg(CO3)2 with 19.63%) and orthoclase (KAlSi3O8 with 31.4%) in lamprophyre are the major minerals constituents involved in acidification reaction. Photomicrograph recorded from SEM studies reveals that the dissolution effect was directly related to the concentration of H+ in the solution. The dissolution effect was from the surface to the inside. The small dissolution pores became larger and continuously expanded, then finally formed a skeleton structure dominated by quartz. The content of K+, Ca2+, and Mg2+ in the solution after acid etching reaction indicates that the acidified product of orthoclase is colloidal H2SiO3, which adhered to the surface of samples during acid etching and hinders the further acidification of minerals. The dissolution of dolomite and orthoclase under acidic conditions directly leads to the damage of their structure and further promotes the water-rock interaction, which is the fundamental reason for the weakening of the mechanical properties of lamprophyre.

Failure properties and stability monitoring of strip and column cemented gangue backfill bodies under uniaxial compression in constructional backfill mining.

The strip and column cemented gangue backfill bodies (CGBBs) are the main supporting components in the design of constructional backfill mining for coal mining, which determines the stability of goaf. Previous researches have mostly focused on the mechanical properties of column CGBB, but the mechanical properties of strip CGBB are still unclear. Herein, the uniaxial compression experiments for strip and column CGBBs were conducted to compare the failure properties. The acoustic emission (AE) and two types of resistivity monitoring were used to monitor the damage evolution. The effect of the length-height ratio on the mechanical characteristic of strip CGBB was analyzed by discrete element simulation. The results show that the strength and peak strain of strip CGBB under uniaxial compression is higher than those of column CGBB and the strip CGBB shows better ductility. The stress of column CGBB decreases significantly faster than that of strip CGBB at the post-peak stage. The strength and ductility of strip CGBB increase with the increase of length-height ratio. The strip CGBB is destroyed from both ends to the middle under uniaxial compression, and the core bearing area is reduced correspondingly. The AE signal evolution of CGBBs under uniaxial compression before the peak stress contains three stages, and the AE signals of strip CGBB at the peak stress will not rise sharply compared with column CGBB. The resistivity monitoring effect of the horizontally symmetrical conductive mesh is better than that of the axial. The horizontal resistivity increases gradually with the increase of stress under uniaxial compression, and increases sharply at the peak stress, and then drops after the peak stress. The damage constitutive models and the stability monitoring models of the CGBBs are established based on the experimental results. This work would be instructive for the design and stability monitoring of CGBB.

Deformation and instability properties of cemented gangue backfill column under step-by-step load in constructional backfill mining.

Constructional backfill mining with cemented gangue backfill column can solve the environmental issues caused by mining activities and the accumulation of waste gangue at a low cost. To study the deformation and instability properties of cemented gangue backfill columns during the advancement of coal mining face, five step-by-step loading paths were adapted to mimic the different loading processes of the roof. The lateral deformation at different heights and axial deformation of the sample were monitored. The results show that the deformation and instability of the backfill column have the properties of loading paths and are affected by the step-by-step loading path. When stress-strength ratio (SSR) is less than 0.6, the lateral of backfill column shrinks during the creeping process. In high-stress levels, lateral creep strain develops faster than axial creep strain. The backfill column has characteristics of axial creep hardening and lateral creep softening during the step-by-step loading process. The instantaneous deformation modulus and instantaneous Poisson's ratio show an upward trend. The strength of backfill column under the step-by-step load is related to loading paths and is no less than uniaxial compressive strength. The non-uniformity of the lateral deformation of backfill column leads to excessive localized deformation that mainly occurs in the middle, causing the overall instability. The development of cracks of backfill column under step-by-step load could be divided into 4 stages according to SSR. Under different step-by-step loading paths, the axial creep strain rate is nearly a constant before entering the accelerated creep stage. A nonlinear creep constitutive model with a creep strain rate trigger was proposed to depict the development of axial strain under step-by-step load. This research could provide a scientific reference for the design of the advancing distance and cycle for the hydraulic support, and reinforcement of the backfill column.

Semi-Supervised Structured Subspace Learning for Multi-View Clustering.

Multi-view clustering aims at simultaneously obtaining a consensus underlying subspace across multiple views and conducting clustering on the learned consensus subspace, which has gained a variety of interest in image processing. In this paper, we propose the Semi-supervised Structured Subspace Learning algorithm for clustering data points from Multiple sources (SSSL-M). We explicitly extend the traditional multi-view clustering with a semi-supervised manner and then build an anti-block-diagonal indicator matrix with small amount of supervisory information to pursue the block-diagonal structure of the shared affinity matrix. SSSL-M regularizes multiple view-specific affinity matrices into a shared affinity matrix based on reconstruction through a unified framework consisting of backward encoding networks and the self-expressive mapping. The shared affinity matrix is comprehensive and can flexibly encode complementary information from multiple view-specific affinity matrices. An enhanced structural consistency of affinity matrices from different views can be achieved and the intrinsic relationships among affinity matrices from multiple views can be effectively reflected in this manner. Technically, we formulate the proposed model as an optimization problem, which can be solved by an alternating optimization scheme. Experimental results over seven different benchmark datasets demonstrate that better clustering results can be obtained by our method compared with the state-of-the-art approaches.

NIM-Nets: Noise-aware Incomplete Multi-view Learning Networks.

Data in real world are usually characterized in multiple views, including different types of features or different modalities. Multi-view learning has been popular in the past decades and achieved significant improvements. In this paper, we investigate three challenging problems in the field of incomplete multi-view representation learning, namely, i) how to reduce the influences produced by missing views in multi-view dataset, ii) how to learn a consistent and informative representation among different views and iii) how to alleviate the impacts of the inherent noise in multi-view data caused by high-dimensional features or varied quality for different data points. To address these challenges, we integrate these three tasks into a problem and propose a novel framework termed Noise-aware Incomplete Multi-view Learning Networks (NIM-Nets). NIM-Nets fully utilize incomplete data from different views to produce a multi-view shared representation which is consistent, informative and robust to noise. We model the inherent noise in data by defining the distribution Γ and assuming that each observation in the incomplete dataset is sampled from the distribution Γ. To the best of our knowledge, this is the first work to unify learning the consistent and informative representation, alleviating the impacts of noise in data and handling the view-missing patterns in multi-view learning into a framework. We also first give a definition of robustness and completeness for incomplete multi-view representation learning. Based on NIM-Nets, we present joint optimization models for classification and clustering, respectively. Extensive experiments on different datasets demonstrate the effectiveness of our method over the existing work based on classification and clustering tasks in terms of different metrics.

In situ study on interactions between hydroxyl groups in kaolinite and re-adsorption water.

The interactions between O-H groups in kaolinite and re-adsorption water is an important aspect that should be considered in the hydraulic fracturing method for the production of shale gas, because the external water adsorbed by kaolinite in shale would significantly affect the desorption of methane. In this study, the interactions were investigated via changing the amount of O-H groups and re-adsorption water in kaolinite by heating treatment and water re-adsorption. To overcome the overlap of IR vibration bands of the O-H functional groups in H2O and those in parent kaolinite, kaolinite samples with D2O re-adsorption were prepared by drying the H2O from raw kaolinite and soaking the dried kaolinite in D2O. The interactions between O-H groups in kaolinite and D2O molecules were investigated by in situ DRIFT and TG-MS. The results demonstrated that the vibration at 3670 ± 4 cm-1 in the DRIFT spectra could be due to the outer O-H groups of the octahedral sheet on the upper surface of the kaolinite microcrystal structure, rather than a type of inner-surface O-H group. All types of O-H groups, including the inner O-H groups in kaolinite, could be transformed into O-D groups after D2O re-adsorption at room temperature. The inner-surface O-H groups in kaolinite are the most preferred sites for D2O re-adsorption; thus, they would be the key factor for studying the effect of re-adsorption water on methane desorption. When the temperature increased from 100 °C to 300 °C, two layers of kaolinite slipped away from each other, resulting in the transformation of inner-surface O-H groups into outer O-H groups. Thus, the temperature range of 100 to 300 °C was suggested for the heat treatment of kaolinite to decrease the content of inner-surface O-H groups; thereby, the amount of re-adsorption water was reduced. However, to thoroughly remove the re-adsorption water, a temperature higher than 650 °C should be used.

Magnetic natural composite Fe3O4-chitosan@bentonite for removal of heavy metals from acid mine drainage.

Magnetic Fe3O4-chitosan@bentonite (Fe3O4-CS@BT) composites using natural materials were synthesized and used to remediate acid mine drainage (AMD) for heavy metal removal. It was found that the composites had a good magnetism, high stability and good performance in removal of Cr(VI) in the synthetic aqueous solutions. The thermodynamic parameters showed that Cr(VI) adsorption onto Fe3O4-CS@BT was an exothermic and spontaneous process. The adsorption kinetics was well described by a pseudo-second-order model, and the adsorption isotherms fit the Langmuir model with a maximum adsorption capacity of 62.1 mg/g at 25 °C. Solution pH was a key factor for adsorption and the optimized pH was 2.0. Fe3O4-CS@BT could be easily recycled through an external magnetic field and the adsorption capacity reduced by only 3% after five consecutive adsorption-desorption processes. In addition, Fe3O4-CS@BT was found to be an excellent adsorbent for actual AMD remediation containing Cd, Cr, Cu, Fe Zn, Ni and Pb, suggesting that the Fe3O4-CS@BT was an effective and economical adsorbent for the treatment of AMD.