Investigation of stress-induced progressive failure of mine pillars using a Voronoi grain-based breakable block model

The Voronoi grain-based breakable block model(VGBBM)based on the combined finite-discrete element method(FDEM)was proposed to explicitly characterize the failure mechanism and predict the deformation behavior of hard-rock mine pillars.The influence of the microscopic parameters on the macroscopic mechanical behavior was investigated using laboratory-scale models.The field-scale pillar models(width-to-height,W/H=1,2 and 3)were calibrated based on the empirically predicted stress-strain curves of Creighton mine pillars.The results indicated that as the W/H ratios increased,the VGBBM effectively predicted the transition from strain-softening to pseudo-ductile behavior in pillars,and explicitly captured the separated rock slabs and the V-shaped damage zones on both sides of pillars and conjugate shear bands in core zones of pillars.The volumetric strain field revealed significant compressional deformation in core zones of pillars.While the peak strains of W/H=1 and 2 pillars were relatively consistent,there were significant differences in the strain energy storage and release mechanism.W/H was the primary factor influencing the deformation and strain energy in the pillar core.The friction coefficient of the structural plane was also an important factor affecting the pillar strength and the weakest discontinuity angle.The fracture surface was controlled by the discontinuity angle and the friction coefficient.This study demonstrated the capability of the VGBBM in predicting the strengths and deformation behavior of hard-rock pillars in deep mine design.

Pillar effect induced by ultrahigh phosphorous/nitrogen doping enables graphene/MXene film with excellent cycling stability for alkali metal ion storage

Graphene's large theoretical surface area and high conductivity make it an attractive anode material for potassium-ion batteries(PIBs).However,its practical application is hindered by small interlayer distance and long ion transfer distance.Herein,this paper aims to address the issue by introducing MXene through a simple and scalable method for assembling graphene and realizing ultrahigh P doping content.The findings reveal that MXene and P-C bonds have a "pillar effect" on the structure of graphene,and the P-C bond plays a primary role.In addition,N/P co-doping introduces abundant defects,providing more active sites for K^(+) storage and facilitating K^(+) adsorption.As expected,the developed ultrahigh phosphorous/nitrogen co-doped flexible reduced graphene oxide/MXene(NPrGM) electrode exhibits remarkable reversible discharge capacity(554 mA hg^(-1) at 0.05 A g^(-1)),impressive rate capability(178 mA h g^(-1) at 2 A g^(-1)),and robust cyclic stability(0.0005% decay per cycle after 10,000 cycles at 2 A g^(-1)).Furthermore,the assembled activated carbon‖NPrGM potassium-ion hybrid capacitor(PIHC) can deliver an impressive energy density of 131 W h kg^(-1) and stable cycling performance with 98.1% capacitance retention after5000 cycles at 1 A g^(-1).Such a new strategy will effectively promote the practical application of graphene materials in PIBs/PIHCs and open new avenues for the scalable development of flexible films based on two-dimensional materials for potential applications in energy storage,thermal interface,and electromagnetic shielding.

Estimating shear strength of high-level pillars supported with cemented backfilling using the HoekeBrown strength criterion

Deep metal mines are often mined using the high-level pillars with subsequent cementation backfilling(HLSCB)mining method.At the design stage,it is therefore important to have a reasonable method for determining the shear strength of the high-level pillars(i.e.cohesion and internal friction angle)when they are supported by cemented backfilling.In this study,a formula was derived for the upper limit of the confining pressure σ3max on a high-level pillar supported by cemented backfilling in a deep metal mine.A new method of estimating the shear strength of such pillars was then proposed based on the Hoek eBrown failure criterion.Our analysis indicates that the horizontal stress σhh acting on the cemented backfill pillar can be simplified by expressing it as a constant value.A reasonable and effective value for σ3max can then be determined.The value of s3max predicted using the proposed method is generally less than 3 MPa.Within this range,the shear strength of the high-level pillar is accurately calculated using the equivalent MohreCoulomb theory.The proposed method can effectively avoid the calculation of inaccurate shear strength values for the high-level pillars when the original HoekeBrown criterion is used in the presence of large confining pressures,i.e.the situation in which the cohesion value is too large and the friction angle is too small can effectively be avoided.The proposed method is applied to a deep metal mine in China that is being excavated using the HLSCB method.The shear strength parameters of the high-level pillars obtained using the proposed method were input in the numerical simulations.The numerical results show that the recommended level heights and sizes of the high-level pillars and rooms in the mine are rational.

POROUS MEMBRANE TEMPLATED SYNTHESIS OF POLYMER PILLARED LAYER

The anodic porous alumina membranes with a definite pore diameter and aspect ratio were used as templates tosynthesize polymer pillared layer structures. The pillared polymer was produced in the template membrane pores, and thelayer on the template surfaces. Rigid cured epoxy resin, polystyrene and soft hydrogel were chosen to confirm themethodology. The pillars were in the form of either tubes or fibers, which were controlled by the alumina membrane pore surface wettability. The structural features were confirmed by scanning electron microscopy results.

Preparation and Microstructure of Al-pillared Interlayered Montmorillonite

Al-pillared interlayered montmorillonite (Al-PILM) was prepared using the artificial Na-montmorillonite from the Qingfengshan bentonite mine as a starting material mixed with Al-pillaring solutions.The microstructure of the materials was studied by an X-ray powder diffractometer and a Fourier transform infrared (FTIR) spectrometer.The results indicated that the basal spacing [d(001) value] of the materials was increased significantly to 1.9194 nm relative to Na-montmorillonite (1.2182 nm).After calcined for 2 h at 300℃,the basal spacing was stabilized at 1.8394 nm and the layered structure of the materials was not destroyed.Thermal analysis was conducted by a thermal gravimetry and differential thermal analysis (TG-DTA) instrument,it showed that Al-PILM lost physically adsorbed water below 230.6℃ and water formed by dehydroxylation of the pillars at around 497.1℃, with a peak of the phase transformation at 903.0℃.

First Synthesis of Zirconia-pillared Layered Lanthanum Niobate

A zirconia-pillared layered lanthanum niobate was prepared by first preswelling layered HLaNb2O7 with n-hexadecylamine(n-C16H33NH2), then further reacting with zirconyl chloride aqueous solution, and finally calcining the resultant solid product in air. The obtained new material has an interlayer spacing of 1.36nm, and a high thermal stability above 700 degrees C.

Partial Atomic Tin Nanocomplex Pillared Few-Layered Ti_(3)C_(2)Tx MXenes for Superior Lithium-Ion Storage

MXenes have attracted great interest in various fields,and pillared MXenes open a new path with larger interlayer spacing.However,the further study of pillared MXenes is blocked at multilayered state due to serious restacking phenomenon of few-layered MXene nanosheets.In this work,for the first time,we designed a facile NH4+method to fundamentally solve the restacking issues of MXene nanosheets and succeeded in achieving pillared few-layered MXene.Sn nanocomplex pillared few-layered Ti3C2Tx(STCT)composites were synthesized by introducing atomic Sn nanocomplex into interlayer of pillared few-layered Ti3C2Tx MXenes via pillaring technique.The MXene matrix can inhibit Sn nanocomplex particles agglomeration and serve as conductive network.Meanwhile,the Sn nanocomplex particles can further open the interlayer spacing of Ti3C2Tx during lithiation/delithiation processes and therefore generate extra capacity.Benefiting from the“pillar effect,”the STCT composites can maintain 1016 mAh g^?1 after 1200 cycles at 2000 mA g^?1 and deliver a stable capacity of 680 mAh g^?1 at 5 A g^?1,showing one of the best performances among MXene-based composites.This work will provide a new way for the development of pillared MXenes and their energy storage due to significant breakthrough from multilayered state to few-layered one.

Modification of pillared MFI zeolite nanosheets by nitridation with tailored activity in benzylation of mesitylene and benzyl alcohol

The modification of pillared MFI zeolites was performed by nitridation of silica pillared MFI zeolite nanosheets under NH3 atmosphere with different time. The resultant zeolites were characterized by a complementary combination of X-ray power diffraction(XRD), scanning electron microscopy(SEM),transmission electron microscopy(TEM), pyridine-IR spectroscopy and N2 adsorption–desorption isotherms. The analyses showed that the nitridation didn’t destroy the crystallinity and specific surface area of zeolites, and the acidity of zeolites can be tailored by tuning the time of nitridation, resulting in the different concentration ratios of Br?nsted-to-Lewis(B/L) acid sites. Moreover, the nitrided zeolites exhibited high selectivity to 2-benzyl-1,3,5-trimethylbenzene than parent silica pillared MFI zeolite nanosheets in benzylation of mesitylene with benzyl alcohol. A balance between Br?nsted acid sites and Lewis acid sites can inhibit the self-etherification of benzyl alcohol and enhance the selectivity of alkylated product. These experimental data implied that nitridation was an effective method to modulate the acidity of zeolites and the synergy between Br?nsted acid sites and Lewis acid sites was a decisive factor to determine the selectivity.

Synthesis and Characterization of Al-Cr-Pillared Montmorillonite with High Thermal Stability and Adsorption Capacity*

Al-Cr-pillared montmorillonite was synthesized by using bentonite and Al-Cr pillaring solutions as starting materials.The basal spacing and specific surface areas of the materials were significantly increased relative to those of untreated clays.When the Al/Cr molar ratio(R) was 0.10,the d(001) value and specific surface area of pillared montmorillonite were 1.9194 nm and 165.7 m2 g -1,respectively.Thermal stability of the materials was determined using calcined tests and X-ray diffraction (XRD) analysis.The materials formed at different R(0.05;0.10;0.15;0.25) exhibit a high thermal stability at 300℃,especially at initial R=0.10,the basal interlayer spacing of materials is stabilized at 1.7313 nm after calcined at 500℃ for 2 h.Adsorption behavior of the materials was studied by adsorption experiments.The results show that the Al-Cr-pillared montmorillonites exhibit much stronger adsorption capacity on Cr 6+ in aqueous solution than untreated clays do.

Construction of TiO_(2)-pillared multilayer graphene nanocomposites as efficient photocatalysts for ciprofloxacin degradation

We successfully constructed TiO_(2)-pillared multilayer graphene nanocomposites(T-MLGs)via a facile method as follows:dodecanediamine pre-pillaring,ion exchange(Ti4+pillaring),and interlayer in-situ formation of TiO_(2) by hydrothermal method.TiO_(2) nanoparticles were distributed uniformly on the graphene interlayer.The special structure combined the advantages of graphene and TiO_(2) nanoparticles.As a result,T-MLGs with 64.3wt%TiO_(2) showed the optimum photodegradation rate and adsorption capabilities toward ciprofloxacin.The photodegradation rate of T-MLGs with 64.3wt%TiO_(2) was 78%under light-emitting diode light irradiation for 150 min.Meanwhile,the pseudofirst-order rate constant of T-MLGs with 64.3wt%TiO_(2) was 3.89 times than that of pristine TiO_(2).The composites also exhibited high stability and reusability after five consecutive photocatalytic tests.This work provides a facile method to synthesize semiconductor-pillared graphene nanocomposites by replacing TiO_(2) nanoparticles with other nanoparticles and a feasible means for sustainable utilization of photocatalysts in wastewater control.

Synthesis and Photocatalytic Property of the ZrO_2/TiO_2 Pillared Laponite

The ZrO2/TiO2 pillared laponite （Ti-Zr-lap） photocatalysts were prepared with intercalation reaction by supercritical fluid drying （SCFD）,and characterized by XRD,TEM,SEM and BET surface area analysis,and the photocatalytic properties of Ti-Zr-lap were investigated by degradation of azo dye acid red B （ARB）.The results showed that the ZrO2/TiO2 pillared structures in laponite could be formed,with the mass fraction of （Zr4＋＋Ti4＋）/laponite （Xm） increasing,the basal spacing and the BET surface area of Ti-Zr-lap significantly increased.The Ti-Zr-lap used as photocatalyst had the advantages of stable and porous layered structure,large surface area with the anatase type TiO2.Compared with the Ti-Zr-lap dried by air drying,the Ti-Zr-lap dried by SCFD showed better photocatalytic property which was very close to that of P25 TiO2.Using the Ti-Zr-lap as photocatalyst with the optimum Xm of 0.16 and the calcination temperature of 500 ℃,under the conditions of the initial concentration of ARB 20 mg/L,photocatalyst concentration of 1.5 g/L and irradiation time 60 min,the decoloring rate of ARB could achieve 98.3%,indicating that the Ti-Zr-lap had excellent photocatalytic property.

Atomic insights into synergistic effect of pillared graphene by carbon nanotube on the mechanical properties of polymer nanocomposites

Molecular dynamics simulations have been performed to explore the underlying synergistic mechanism of pillared graphene or non-covalent connected graphene and carbon nanotubes(CNTs) on the mechanical properties of polyethylene(PE) nanocomposites. By constructing the pillared graphene model and CNTs/graphene model, the effect of the structure, arrangement and dispersion of hybrid fillers on the tensile mechanical properties of PE nanocomposites was studied. The results show that the pillared graphene/PE nanocomposites exhibit higher Young’s modulus, tensile strength and elongation at break than non-covalent connected CNTs/graphene/PE nanocomposites. The pull-out simulations show that pillared graphene by CNTs has both large interfacial load and long displacement due to the mixed modes of shear separation and normal separation. Additionally, pillared graphene can not only inhibit agglomeration but also form a compact effective thickness(stiff layer), consistent with the adsorption behavior and improved interfacial energy between pillared graphene and PE matrix.

Synthesis of Magnetically Modified Fe-Al Pillared Bentonite and Heterogeneous Fenton-like Degradation of Orange II

Magnetically modified Fe-Al pillared bentonite（Fe3O4/ Fe-Al-Bent） was prepared via chemical co-precipitation method and characterized by powder X-ray diffraction（XRD）, Brunauer-EmmettTeller（BET）, Fourier transform infrared spectroscopy（FTIR） and scanning electron microscopy（SEM）. A series of experiments were carried out to investigate the degradation of Orange II by the obtained heterogeneous catalysts in the presence of H2O2. The experimental result indicated that the synthetic materials had a high catalytic activity and good reusability.

Adsorption of Environmental Pollutants on Pillared Montmorillonite

Both inorganic and organic pillared montmorillonites were used to adsorb phenol. Batch kinetics and isotherm studies were carried out to evaluate the effect of equilibrium time and pH on adsorption of phe- nol by montmorillonites and re-adsorbing characteristics of pillared montmorillonites. The adsorption of phenol increased with increasing solution pH values. The elimination ratio of phenol from the solution by the absorption of organic modified pillared montmorillonite (OrPMt) reached equilibrium quickly after vibrating for 5 minutes. Meanwhile for organic montmorillonite (OrMt), pillared montmorillonite (PMt) and montmorillonite (Mt), the time to reach phenol-absorption equilibrium were 20, 30 and 90 minutes, respectively. The adsorbing capacity of the pillared montmorillonite modified with surfactant improved greatly. The phenol-adsorbing capacity of pillared molltmorillonites mainly depended on microporous structure and surface component of the modified clays. After calcination at 500 ℃, the pillar structure and the basal spacing (1.83 um) were still stable. So the pillared montmorillonite could be recycled, and it was a potential material for adsorbing environmental pollutants.

Sorption of wastewater containing reactive red X-3B on inorgano-organo pillared bentonite

Bentonite is a kind of natural clay with good exchanging ability. By exchanging its interlamellar cations with various soluble cations, such as quaternary ammonium cations and inorganic metal ions, the properties of natural bentonite can be greatly improved. In this study, hexadecyltrimethylammonium bromide (HDTMA), CaCl2, MgCl2, FeCl3, AlCl3 were used as organic and inorganic pillared materials respectively to produce several kinds of Ca-, Mg-, Fe-, Al-organo pillared bentonites. Sorption of reactive red X-3B on them was studied to determine their potential application as sorbents in wastewater treatment. The results showed that these pillared bentonites had much improved sorption properties, and that the dye solutions’ pH value had some effect on the performance of these inorgano-organo pillared bentonites. Isotherms of reactive X-3B on these pillared bentonites sug-gested a Langmuir-type sorption mechanism.

Comparison of Conventional and Microwave-assisted Synthesis and Characteristics of Aluminum-pillared Rectorite

The synthesis and characterization of aluminum-pillared rectorite were studied. The synthesis was conducted with both conventional heating and microwave irradiation. Microwave irradiation was found to enhance the intercalation and ion-exchange during synthesis, and to be able to produce the rectorite with a larger d_(001) and a better uniformity. The specific surface area is 180 m^2/g and basal spacing is 3.2 nm. The texture change and thermal and hydrothermal stability of cross-linked rectorite were examined using XRD, FTIR, nitrogen-adsorption and TGA. The experimental results show that the aluminum-pillared rectorite, after calcined at 800 ℃ for 3 hours, can keep the basal aluminum-silicate texture and would not disperse in water at room or an elevated temperature. The aluminum-pillared rectorite shows a high specific surface area, good thermal and hydrothermal stability, and is promising in applications as catalyst carriers and adsorbents for waste treatment.

Study on structural characteristics of pillared clay modified phosphate fertilizers and its increase efficiency mechanism

Three types of new high-efficiency phosphate fertilizers were made when pillared clays at certain proportions were added into ground phosphate rock. Chemical analyses showed that their soluble phosphorus content decreased more than that of superphosphate. Pot experiment showed that, under equal weights, the new fertilizers increased their efficiency by a large margin over that of superphosphate. Researches on their structures by means of XRD, IR and EPR spectrum revealed that their crystal structures changed considerably, improving their activity and preventing the fixation of available phosphorus in the soil, and consequently, greatly improved the bioavailability and became the main cause of the increase of biomass.

Two Pillared-layer Co(Ⅱ) Metalorganic Frameworks Displaying Pore Modulation by Rodlike Ligands

Two novel compounds, {[Co2（epda）2（4,4＇-bpy）（H20）z]＇3H20}n 1 and {[Co2（epda）2（bpe）（HzO）z]＇3HzO}n 2 （H2epda = 5-ethyl-pyridine-2,3-dicarboxylic acid, 4,4＇-bpy = 4,4＇-bipyridine and bpe = 1,2-di（4-pyridyl）ethylene） were solvothermally synthesized and charac- terized by elemental analysis, IR spectroscopy, thermogravimetric analysis （TGA）, and single- crystal X-ray diffraction. Complex 1 is ofmonoclinic system, space group P21/c with a = 13.344（5）, b = 14.724（5）, c = 8.267（3） A, fl = 105.840（4）~, V= 1562.5（10） A3, Dc = 1.480 g/cm3, Mr = 375.19, Z = 4, F（000） = 712, gl = 1.121 mm-1, the final R = 0.0512 and wR = 0.1260 for 2890 observed reflections with I 〉 2σ（I）. 2 belongs to the monoclinic system, space group P21/c with a = 14.224（4）, b = 14.726（4）, c = 8.287（2） A,β = 99.696（4）°, V= 1711.1（9） A3, Dc = 1.402 g/cm3, Mr = 388.21, Z = 4, F（000） = 740, kt = 1.027 mm-1, the final R = 0.0354 and wR = 0.0862 for 12237 observed reflections with I 〉 2a（/）. Both complexes present intimately related structures featuring infinite Co-carboxylate layers of [Con（epda）（H20）]n pillared by 4,4＇-bpy （or bpe） molecule to produce the microporous frameworks, Unambiguously indicating that pore dimensions of the framework are regulated by the N,N＇-donor pillars.

Synthesis and Photocatalytic Activity of Ti-pillared Bentonite

Ti-pillared bentonite has been successfully prepared using a modified method that can induce the transformation of TiO2 pillar from amorphous to anatase phase at a low temperature （150℃）. The value of d0.01 =1.94 nm obtained by Ti-pillared bentonite is larger than that of corresponding raw clay （1.56 nm）. Due to large numbers of Ti-pillars formed, the Ti-pillared bentonite shows an excellent ability in adsorbing Rhodamine B （RB）. The photocatalytic activity and kinetic equation are investigated by decomposing RB solution under the UV irradiation. It is found that the Ti- pillared bentonite shows super photocatalytic activity for the degradation of RB solution compared with the untreated bentonite and pure TiO2, and the kinetic equation of the degradation of RB solution is a 1.5-oder equation.