Preparation, Crystallization and Mechanical Properties of Potassium Aluminosilicate Glass-ceramics

In this study,transparent K_(2)O-Al_(2)O_(3)-SiO_(2)(KAS)glass-ceramics with leucite as the main crystalline phase were prepared by melting-quench method and two-step heat treatment.The effects of SiO_(2)/Al_(2)O_(3) ratio and heat treatment on crystallization and mechanical properties were studied.The crystallization kinetics and X-Ray Diffraction(XRD)results showed that SiO_(2)/Al_(2)O_(3) ratio and heat treatment system had a direct impact on the crystallization behavior of potassium aluminosilicate glass-ceramics.When heat-treated at 680℃/2 h and 780℃/1 h,cracks generated on the surface of the sample with the addition of SiO_(2)/Al_(2)O_(3)=4.8(in mol)due to the huge difference in the coefficient of thermal expansion between glass matrix and surface.When the addition of SiO_(2)/Al_(2)O_(3)(in mol)was 4,the sample with leucite as the main crystalline phase showed an excellent fracture toughness(1.46 MPa·m^(0.5))after the heat treatment of 680℃/2 h and 780℃/5 h.And there was a phase transformation from kaliophilite to leucite.The crystalline phases of the sample heat-treated at 680℃/8 h and 780℃/1 h were leucite and kaliophilite,which resulted in the visible light transmittance of 63%and the fracture toughness of 0.91 MPa·m^(0.5).Furthermore,after the heat treatment of 680℃/2 h and 780℃/5 h,the main crystalline phase of the sample with SiO_(2)/Al_(2)O_(3)=3.2(in mol)was still kaliophilite.Because leucite only grows on the surface of the sample and is hard to grow inward,it is hard to achieve the bulk crystallization of leucite in the sample with SiO_(2)/Al_(2)O_(3)=3.2(in mol).

Carbonation of Dicalcium Silicate Enhanced by Ammonia Bicarbonate and Its Mechanism

The strength development law of γ-type dicalcium silicate (γ-C_(2)S) under different carbonation processes was investigated,and the carbonation mechanism of γ-C_(2)S under the action of NH_(4)HCO_(3) was clarified by using a wide range of test methods,including XRD and SEM.A method of saturated NH_(4)HCO_(3) solution as a curing agent was identified to improve the carbonation efficiency and enhance the carbonation degree of γ-C_(2)S,and then a high-strength carbonated specimen was obtained.Microhardness analysis and SEM morphology analysis were conducted on the carbonised specimens obtained under atmospheric pressure carbonisation conditions using the curing agent.It was found that γ-C_(2)S could perform carbonisation well under atmospheric pressure,which promoted the carbonisation efficiency and decreased the carbonisation cost simultaneously.Therefore,a new carbonisation process solution was proposed for the rapid carbonisation of γ-C_(2)S.

The Fabrication and Detection Performance of High Sensitivity Au-Ag Alloy Nanostar/Paper Flexible Surface Enhanced Raman Spectroscopy Sensors

Au-Ag alloy nanostars based flexible paper surface enhanced Raman spectroscopy sensors were fabricated through simple nanostar coating on regular office paper,and the surface enhanced Raman spectroscopy detection performances were investigated using crystal violet dye analyte.Au-Ag nanostars with sharp tips were synthesized via metal ions reduction method.Transmission electron microscope images,X-Ray diffraction pattern and energy dispersive spectroscopy elemental mapping confirmed the nanostar geometry and Au/Ag components of the nanostructure.UV-Vis-NIR absorption spectrum shows wide local surface plasmon resonance induced optical extinction.In addition,finite-difference time-domain simulation shows much stronger electromagnetic field from nanostars than from sphere nanoparticle.The effect of coating layer on Raman signal intensities was discussed,and optimized 5-layer coating with best Raman signal was obtained.The Au-Ag nanostatrs homogeneously distribute on paper fiber surface.The detection limit is 10-10 M,and the relationship between analyte concentrations and Raman signal intensities shows well linear,for potential quantitative analysis.The calculated enhancement factor is 4.795×10^(6).The flexible paper surface enhanced Raman spectroscopy sensors could be applied for trace chemical and biology molecule detection.

Versatile Surface Modification of Ceramsite Via Honeycomb Calcium-aluminum-silicate-hydrate and Its Functionalization by 3-thiocyanatopropyltriethoxysilane for Enhanced Cadmium(Ⅱ) Removal

A low-cost and efficient filter medium for Cd(Ⅱ) removal was prepared by anchoring-SCN functional groups(by 3-thiocyanatopropyltriethoxysilane, TCPS) on ceramsite via the approach of synthesizing a honeycomb calciumaluminum-silicate-hydrate(C-A-S-H) layer as intermediate. The specific surface area of ceramsite was increased enormously by more than 50 times because of the modification of honeycomb layer. Moreover, the abundant Si-OH bonds existing in the structure of CAS-H can serve as active sites for TCPS. The combined effects ensure that the hybrid filter medium(named ceramsite/C-A-S-H/TCPS) demonstrated a high Cd(Ⅱ) adsorption capacity of 18.27 mg·g^-1 for particle size of 0.1-0.6 mm, 12.63 mg·g^-1 for 0.6-1.25 mm and 8.64 mg·g^-1 for 1.25-2.35 mm. The Cd(Ⅱ) adsorption capacity per unit area of ceramsite/C-A-S-H/TCPS(0.1-0.6 mm) is up to 4.07 mg·m^-2, which is much higher than that of many nano-adsorbents. In addition, ceramsite/C-AS-H/TCPS could maintain a high removal efficiency(> 85%) in a wide range of p H 3-11 and showed excellent selectivity in the presence of competing ions. Furthermore, Cd(Ⅱ) could be desorbed from ceramsite/C-A-S-H/TCPS composites with nearly 100%, suggesting the potential application in recycling of heavy metal ions.

Density Functional Theory for Battery Materials

Batteries are the most widely used energy storage devices, and the lithiumion battery is the most heavily commercialized and most widely used battery type in the industry. However, the current rapid development of society requires a major advancement in battery materials to achieve high capacity,long life cycle, low cost, and reliable safety. Therefore, many new efficient energy storage materials and battery systems are being developed and explored, and their working mechanisms must be clearly understood before industrial application. In recent years, density functional theory (DFT) has been employed in the energy storage field and has made significant contributions to the understanding of electrochemical reaction mechanisms and to virtual screening of promising energy storage materials. In this review,the applications of DFT to battery materials are summarized and exemplified by some representative and up-to-date studies in the literature. The main focuses in this review include the following:1) structural stability estimation by cohesive energy, formation energy, Gibbs free energy, and phonon dispersion spectra calculations;2) the Gibbs free energy calculations for electrochemical reactions, corresponding open-circuit voltage, and theoretical capacity predictions of batteries;3) the analyses of molecule orbitals, band structures, density of states (DOS), and charge distribution of battery materials;4) ion transport kinetics in battery materials;5) simulations of adsorption processes. We conclude the review with the discussion of the assessments and validation of the popular functionals against several benchmarks, and a few suggestions have been given for the selection of density functionals for battery material systems.

Use of Different Barium Salts to Inhibit the Thaumasite Form of Sulfate Attack in Cement-based Materials

We investigated the effects of different barium compounds on the thaumasite form of sulphate attack（TSA）resistance of cement-based materials when they were used as admixtures in mortars.Moreover,we analyzed the inhibition mechanisms within different types of barium salts,namely BaCO_3 and Ba（OH）_2,on the thaumasite formation.The controlcement mortar and mortars with barium salts to cement and limestone weight ratios of 0.5%,1.0%,and 1.5% were immersed in 5%（by weight）MgSO_4 solution at 5 ℃ to mimic TSA.Appearance,mass,and compressive strength of the mortar samples were monitored and measured to assess the generaldegradation extent of these samples.The products of sulphate attack were further analyzed by XRD,FTIR,and SEM,respectively.Experimentalresults show that different degradation extent is evident in allmortars cured in MgSO_4 solution.However,barium salts can greatly inhibit such degradation.Barium in hydroxide form has better effectiveness in protection against TSA than carbonate form,which may be due to their solubility difference in alkaline cement pore solution,and the presence of these barium compounds can reduce the degree of TSA by comparison with the almost completely decomposed controlsamples.

Degradation of Formaldehyde and Benzene by TiO2 Photocatalytic Cement Based Materials

A novel photocatalytic cement based material was prepared. The distribution of TiO2 on the surface of cement was characterized by scanning electron microscope（SEM） and X-ray diffraction（XRD）, which showed the relationship of photocatalysis and presence of TiO2. TiO2 also had an impact on cement hydration, which was studied by thermal analysis. With 300 W UV illuminations, formaldehyde and benzene were degraded efficiently by the prepared photocatalytic cement based materials. 15wt% TiO2/cement showed the highest degradation efficiency and capability. The results show that formaldehyde and benzene can be degraded within 4 and 9 hours, respectively. Besides, inorganic ions can induce TiO2 agglomeration. As a result, the presence of inorganic ions in cement is unfavorable for degradation. The photocatalytic cement based materials were fabricated and the degradation efficiency of formaldehyde was measured on building roof under sunlight illumination. Formaldehyde in glass chamber can be degraded thoroughly within 10 days.

Effect of Silica Fume on the Thaumasite Form of Sulfate Attack on Cement-based Materials

Thaumasite form of sulfate attack（TSA） can be observed in cement containing limestone under sulfate condition at low temperature. Mixing with suitable mineral admixture could be a good choice to improve the TSA resistance performance of cement-based materials. We investigated the durability performance of limestone-cement mortars reinforced with silica fume（SF） in 5% MgSO_4 solution at 5 ℃. The mortars, which were immersed in aggressive condition, were prepared with 2%, 4%, 6%, 8%, and 10% cement replacement by SF at a fixed water-to-binder ratio. Appearance, compressive strength, change of length and mass and corrosion products were investigated to evaluate the TSA resistance performance of SF based specimens. The results showed that specimens in the absence of SF almost disintegrated. Increasing SF dosage can reduce the degree of deterioration of SF mortars in TSA environment. Mortar mixtures with more than 6% SF merely show slight degeneration in relation to macroscopic and microscopic tests and characterizations.

Research on the Low-carbon Cementitious Materials:Effect of Triisopropanolamine on the Hydration of Phosphorous Slag and Steel Slag

Cement,phosphorous slag(PS),and steel slag(SS)were used to prepare low-carbon cementitious materials,and triisopropanolamine(TIPA)was used to improve the mechanical properties by controlling the hydration process.The experimental results show that,by using 0.06%TIPA,the compressive strength of cement containing 60%PS or 60%SS could be enhanced by 12%or 18%at 28 d.The presence of TIPA significantly affected the hydration process of PS and SS in cement.In the early stage,TIPA accelerated the dissolution of Al in PS,and the formation of carboaluminate hydrate was facilitated,which could induce the hydration;TIPA promoted the dissolution of Fe in SS,and the formation of Fe-monocarbonate,which was precipitated on the surface of SS,resulting in the postponement of hydration,especially for the high SS content.In the later stage,under the continuous solubilization effect of TIPA,the hydration of PS and SS could refine the pore structure.It was noted that compared with portland cement,the carbon emissions of cement-PS-TIPA and cement-SS-TIPA was reduced by 52%and 49%,respectively.

Polymorph Transformation of Tricalcium Silicate Doped with Heavy Metal

The aim of the present study was to investigate the influence of heavy metals on the polymorph transformation of tricalcium silicate.Heavy metal（0.1wt% to 3.0wt%） of Cr,Zn,Cu,Ni and Pb（in oxides form） was added into the raw mixtures and then sintered together three times at 1450 ℃ for 2 h.The f-CaO content of doped C3S was determined by the glycerol-ethanol method,and their polymorph transformation was investigated by means of XRD and FTIR.Thermal analysis（DTA/DTG） was conducted to determine the reaction temperatures and mass losses during the sintering process of raw mixtures.The concentration of heavy metal in C3S after sintering was determined by ICP-AES.The experimental results indicate that heavy metal doping contributes to a higher symmetry of C3S except for Pb.Addition of up to 3.0wt%,Cr will lead to a decomposition of C3S into C2S and CaO;Zn will cause a transformation from T1 to M2 polymorph,and then to R polymorph;Cu and Ni cause a gradual transformation from T1 to T2 and then to M1 and/or M2 polymorph.During the sintering process,all the Pb releases into atmosphere because of evaporation.

Effects of Co_(2)O_(3)Addition on Microstructure and Properties of SiC Composite Ceramics for Solar Absorber and Storage

SiC composite ceramics for solar absorber and storage integration are new concentrating solar power materials.SiC composite ceramics for solar absorber and storage integration were fabricated using SiC,black corundum and kaolin as the raw materials,Co_(2)O_(3)as the additive via pressureless graphite-buried sintering method in this study.Influences of Co_(2)O_(3)on the microstructure and properties of SiC composite ceramics for solar absorber and storage integration were studied.The results indicate that sample D2(5wt%Co_(2)O_(3))sintered at 1480℃exhibits optimal performances for 119.91 MPa bending strength,93%solar absorption,981.5 kJ/kg(25-800℃)thermal storage density.The weight gain ratio is 12.58 mg/cm2after 100 h oxidation at 1000℃.The Co_(2)O_(3)can decrease the liquid phase formation temperature and reduce the viscosity of liquid phase during sintering.The liquid with low viscosity not only promotes the elimination of pores to achieve densification,but also increases bending strength,solar absorption,thermal storage density and oxidation resistance.A dense SiO_(2) layer was formed on the surface of SiC after 100 h oxidation at 1000℃,which protects the sample from further oxidation.However,excessive Co_(2)O_(3)will make the microstructure loose,which is disadvantageous to the performances of samples.

Ferro-vanadium Slag in Improving Inner Chloride Solidification Rate of Cement Materials

We investigated the effects of ferro-vanadium slag(FVS)as a supplemental cementing material which can dissolve a large amount of active aluminum phases without excessive pretreatment or excitation to enhance the inner chloride solidified rate(CSR)of cement-based materials.Cement-FVS pastes with 0-30%content of FVS was designed,and the CSR was examined.Hydrates at different curing ages were studied by X-ray diffraction(XRD)and thermo-gravimetric analysis(TGA);hydration heat and^(29)Si nuclear magnetic resonance(^(29)Si-NMR)were tested to analyze the hydration degree of the system;mechanical properties in cement-FVS system were evaluated by compressive strength test,pore structure and the fractal regression.Results revealed that the incorporation of FVS could greatly promote the CSR of cement-FVS system.Compared with the control groups,30%dosage of FVS could increase the CSR by 69%at 3 d,47%at 7d,36%at 28 d and 34%at 60 d.It was demonstrated that the incorporation of FVS could enhance the chemical solidifying ability of chloride,and the main reason was the promoted generation of Kuzel’s salt and the Friedel’s salt in hydrate products,and the enhanced chloride migration resistance capacity by increasing the volume of gel pores in the cement-FVS system.Considering the influence of FVS on strength performance,this paper suggested that the suitable dosage of FVS as a supplemental cementing material was around 10%.The study in this paper might provide one efficient path to promote the chloride solidifying capacity of cement-based material and meanwhile the comprehensive utilization of FVS.

Preparation and Thermal Shock Resistance of Mullite Ceramics for High Temperature Solar Thermal Storage

Mullite thermal storage ceramics were prepared by low-cost calcined bauxite and kaolin.The phase composition,microstructure,high temperature resistance and thermophysical properties were characterized by modern testing techniques.The experimental results indicate that sample A3(bauxite/kaolin ratio of 5:5)sintered at 1620℃has the optimum comprehensive properties,with bulk density of 2.83 g·cm^(-3)and bending strength of 155.44 MPa.After 30 thermal shocks(1000℃-room temperature,air cooling),the bending strength of sample A3 increases to 166.15 MPa with an enhancement rate of 6.89%,the corresponding thermal conductivity and specific heat capacity are 3.54 W·(m·K)^(-1)and 1.39 kJ·(kg·K)^(-1)at 800℃,and the thermal storage density is 1096 kJ·kg^(-1)(25-800 mullite ceramics;sintering properties;high-temperature thermal storage;thermal shock resistance).Mullite forms a dense and continuous interlaced network microstructure,which endows the samples high thermal storage density and high bending strength,but the decrease of bauxite/kaolin ratio leads to the decrease of mullite content,which reduces the properties of the samples.

Au@Ag Core-shell Nanorods Self-assembled on Polyelectrolyte Multilayers for Ultra-High Sensitivity SERS Fiber Probes

We demonstrated a chemical process in the fabrication of a SERS fiber probe with an ultrahigh sensitivity.The synthesis was carried out by preparing Au@Ag core-shell nanorods (Au@Ag-NRs) selfassembled on polyelectrolyte (PE) multilayers,for which Au@Ag-NRs were controlled by adjusting the silver layer thickness.The effect of silver layer thickness of Au@Ag-NRs on the SERS performance of the fiber probe was investigated.The SERS fiber probe shows the best performance when the silver layer thickness is controlled at 8.57 nm.Under the condition of optimizing silver layer thickness,the fiber probe exhibits ultra-high sensitivity (i e,10^(-10) M crystalline violet,CV),good reproducibility (i e,RSD of 3.5%) and stability.Besides,electromagnetic field distribution of the SERS fiber probe was also investigated.The strongest enhancement is found within the core of fiber,whereas a weakened electromagnetic field exists in the fiber cladding layer.The SERS fiber probe can be a good candidate in ultra-trace detection for biomedical and environmental areas.

Mixed-Alkali Effect on Thermal Property and Elastic Behavior in Borosilicate Glasses

We investigated the mixed alkali effect on the thermal properties and elastic response to temperature in the borosilicate glasses system with the composition of 70.65Si O_(2)·21.09B_(2)O_(3)·1.88Al_(2)O_(3)·(6.38-x)Li_(2)O·x Na_(2)O glasses,where x=0.00,1.595,3.19,4.785,and 6.38.Except for the expected positive and negative deviations from linearity for the coefficients of thermal expansion,room temperature E and G,we observed a new mixed alkali efiect on the response of elastic moduli to temperature.Fourier transform infrared spectra were obtained to elucidate the possible structural origin of the mixed alkali efiects.This work provides a valuable insight into the structural and mechanical properties of mixed-alkali borosilicate glasses.

Influence Mechanism of Curing Regimes on Interfacial Transition Zone of Lightweight Ultra-High Performance Concrete

This study aims to clarify the effects of curing regimes and lightweight aggregate(LWA)on the morphology, width and mechanical properties of the interfacial transition zone(ITZ) of ultra-high performance concrete(UHPC), and provide reference for the selection of lightweight ultra-high performance concrete(L-UHPC) curing regimes and the pre-wetting degree LWA. The results show that, under the three curing regimes(standard curing, steam curing and autoclaved curing), LWA is tightly bound to the matrix without obvious boundaries. ITZ width increases with the water absorption of LWA and decreases with increasing curing temperature. The ITZ microhardness is the highest when water absorption is 3%, and the microhardness value is more stable with the distance from LWA. Steam and autoclaved curing increase ITZ microhardness compared to standard curing. As LWA pre-wetting and curing temperatures increase, the degree of hydration at the ITZ increases, generating high-density CSH(HD CSH) and ultra-high-density CSH(UHD CSH), and reducing unhydrated particles in ITZ. ITZ micro-mechanical properties are optimized due to hydration products being denser.

The Fabrication and SERS Performance of Multi-layer Hollow Au-Ag Alloy Nano Urchins Structure-based SERS Fiber Probe

Novel hollow Au Ag alloy nano urchins were synthesized via Ag seeds growth method,and self-assembly coated on the wall and end-tip of silica fiber for fiber probe fabrication.The nano urchins homogeneously distributed on fiber surface because of fiber silanization.The sizes and tip sharpness of the nano-urchins could be controlled by Ag seeds.The elements distribution analysis indicated there was high Ag content in tip-top for better surface enhance Raman scattering performance.The detectable concentration could be as low as 10-8 M using crystal violet molecules as analyte.Moreover,the fiber probes were stable in air,due to Au in the alloy.This fiber probe could be used for low content single molecular analysis.

Numerical Simulation of a Viscoelastic Thinning Process for Preparing Flexible Glasses by Redrawing Method

The forming process of the flexible ultrathin glasses(UTG)prepared by the redrawing method was numerically simulated using ANSYS Polyflow software.In the forming process by the redrawing method,temperature,viscosity,transverse and longitudinal velocity distribution of the glasses with different compositions were studied.Furthermore,the influence of these factors on the width and thickness of the flexible glass plate was investigated.It is found that the internal and external heat exchange of glass has a dominant influence on the viscosity variation during the UTG forming process,which is inconsistent with the general viscosity-temperature dependence.The glass that first reaches the lower limit of forming viscosity can significantly resist the shrinking effect caused by surface tension,making the glass wider during the forming.If the original glass width remains unchanged,the glass thickness or feeding speed is reduced,wider and thinner flexible glasses can be produced.

Effect of High Content Limestone Powder on Microstructure and Mechanical Properties of Cement-based Materials

Compared with the control sample without limestone powder(LP), the mechanical properties of the sample with 30% LP can be significantly improved by using a small amount of water reducer to reduce the water-cement ratio, without significantly affecting the fluidity of the fresh mixture and increasing the economic cost. In addition, compared with the sole addition of limestone powder, dual addition of metakaolin and limestone powder can effectively improve the strengths. The reason of this phenomenon was investigated by means of XRD, TG-DTG, SEM, LF-NMR and isothermal calorimetry, etc. The reactive aluminum-rich phases in metakaolin react with limestone powder in the hydration process, and the formed calcium carboaluminate reduces the porosity and makes the hardened paste denser. The addition of ground granulated blast furnace slag can also improve the strength of the specimen added with limestone powder, whereas, the effect is inferior to that of metakaolin, for the ground granulated blast furnace slag contains less reactive aluminate phases, and accordingly, the amount of calcium carboaluminate generated is lower than that of metakaolin.

Interfacial and Vacancies Engineering of Copper Nickel Sulfide for Enhanced Oxygen Reduction and Alcohols Oxidation Activity

Rational design and construction of highly efficient nonprecious electrocatalysts for oxygen reduction and alcohols oxidation reactions(ORR,AOR)are extremely vital for the development of direct oxidation alkaline fuel cells,metal-air batteries,and water electrolysis system involving hydrogen and value-added organic products generation,but they remain a great challenge.Herein,a bifunctional electrocatalyst is prepared by anchoring CuS/NiS_(2)nanoparticles with abundant heterointerfaces and sulfur vacancies on graphene(Cu_(1)Ni_(2)-S/G)for ORR and AOR.Benefiting from the synergistic effects between strong interfacial coupling and regulation of the sulfur vacancies,Cu_(1)Ni_(2)-S/G achieves dramatically enhanced ORR activity with long term stability.Meanwhile,when ethanol is utilized as an oxidant for AOR,an ultralow potential(1.37 V)at a current density of 10 mA cm-2 is achieved,simultaneously delivering a high Faradaic efficiency of 96%for ethyl acetate production.Cu_(1)Ni_(2)-S/G also exhibits catalytic activity for other alcohols electrooxidation process,indicating its multifunctionality.This work not only highlights a viable strategy for tailoring catalytic activity through the synergetic combination of interfacial and vacancies engineering,but also opens up new avenues for the construction of a self-driven biomass electrocatalysis system for the generation of value-added organic products and hydrogen under ambient conditions.