Effect of Curing Age on Tensile Properties of Fly Ash Based Engineered Geopolymer Composites(FA-EGC)by Uniaxial Tensile Test and Ultrasonic Pulse Velocity Method

Tensile properties of fly ash based engineered geopolymer composites(FA-EGC)at different curing ages were studied by uniaxial tensile test and ultrasonic pulse velocity(UPV)methods,which included uniaxial tensile properties,the correlation between ultrasonic pulse velocity and tensile properties,and characteristic parameters of microcracks.The experimental results show that obvious strain hardening behavior can be found in FA-EGC at different curing ages.With the increase of curing age,the tensile strength increases,the tensile strain decreases and the toughness becomes worse.The UPV of FA-EGC increases with curing age,and a strong correlation can be found between tensile strength and UPV.With the increase of curing age,the average crack width of FA-EGC decreases and the total number of cracks increases.This is because the strength of geopolymer increases fast at early age,thus the later strength development of FA-EGC tend to be stable.At the same time,the bond strength between fiber and matrix,and the friction of fiber/matrix interface continue to increase with curing age,thus the bridging effect of fiber is gradually strengthened.In conclusion,the increase of curing age is beneficial to the development of tensile properties of FA-EGC.

Chloride Corrosion of Reinforced Calcium Aluminate Cement Mortar

This paper describes a study on the corrosion behavior of steel reinforcement in CAC mortars via electrochemical methods including corrosion potential,electrochemical impedance,and linear polarization evaluation.Results indicate that there is a non-linear relationship between the corrosion degree of steel reinforcement in CAC mortar and the concentration of NaCl solution.The electrochemical parameters of specimens immersed in 3%NaCl solution suddenly drop at 40 days,earlier than 60 days of the reference.And the charge transfer resistivity of the specimen has decreased by 11 orders of magnitude at 40 days,showing an evident corrosion on steel reinforcement.However,it is interesting to notice that the corrosion is delayed by high external chloride concentration.The specimens immersed in 9%and 15%NaCl solutions remain in a relatively stable state within 120 days with slight pitting.The great corrosion protection of CAC concrete to embedded steel bars enables its wide application in marine.

Calcium Carbonate and Ettringite Induced Efflorescence in CAC-Anhydrite Binary Systems

We focused on the efflorescence induced microstructural evolution of ettringite-rich systems prepared with calcium aluminate cement(CAC)and anhydrite.The effects of anhydrite on the visible efflorescence,and the corresponding capillary absorption of CAC-anhydrite mortars were revealed.The composition and microstructure of efflorescence-causing substances were investigated by optical microscope,in-situ Raman spectroscopy,scanning electron microscope,energy dispersive spectrometer,thermogravimetric analysis,and differential scanning calorimetry,at multi-scales.Results indicate that,besides the calcium carbonate,ettringite is another main component of efflorescence-causing substances.Compared with the neat CAC mortars,the addition of anhydrite has a significant effect on the degree of efflorescence by acting on the composition of hydration products and pore structure.In addition,methods are proposed for the prevention of efflorescence of CAC-anhydrite binary system.

MIL-100(V) derived porous vanadium oxide/carbon microspheres with oxygen defects and intercalated water molecules as high-performance cathode for aqueous zinc ion battery

The development of aqueous zinc ion battery cathode materials with high capacity and high magnification is still a challenge.Herein,porous vanadium oxide/carbon(p-VO_(x)@C,mainly VO_(2) with a small amount of V_(2)O_(3)) core/shell microspheres with oxygen vacancies are facilely fabricated by using a vanadium-based metal-organic framework(MIL-100(V)) as a sacrificial template.This unique structure can improve the conductivity of the VO_(x),accelerate electrolyte diffusion,and suppress structural collapse during circulation.Subsequently,H_(2)O molecules are introduced into the interlayer of VO_(x) through a highly efficient in-situ electrochemical activation process,facilitating the intercalation and diffusion of zinc ions.After the activation,an optimal sample exhibits a high specific capacity of 464.3 mA h g^(-1) at0.2 A g^(-1) and 395.2 mA h g^(-1) at 10 A g^(-1),indicating excellent rate performance.Moreover,the optimal sample maintains a capacity retention of about 89.3% after 2500 cycles at 10 A g^(-1).Density functional theory calculation demonstrates that the presence of oxygen vacancies and intercalated water molecules can significantly reduce the diffusion barrier for zinc ions.In addition,it is proved that the storage of zinc ions in the cathode is achieved by reversible intercalation/extraction during the charge and discharge process through various ex-situ analysis technologies.This work demonstrates that the p-VO_(x)@C has great potential for applications in aqueous ZIBs after electrochemical activation.

Evolution of distribution and content of water in cement paste by low field nuclear magnetic resonance

The low field nuclear magnetic resonance (NMR), as a nondestructive and noninvasive technique, was employed to investigate the water distribution and content in cement paste with different water-to-cement ratio (w/c ratio) during early and later hydration stages. From the water distribution spectrum deduced from relaxation time distribution in paste, it is suggested that the water fills in the capillary pores at initial period, and then diffuses to the mesopores and gel pores in hydration products with the hydration proceeding. The decrease of peak area in water distribution spectrum reflects the transformation from physically bound water to chemically bound water. In addition, based on the connection between relaxation time and pore size, the relative content changes of water in various states and constrained in different types of pores were also measured. The results demonstrate that it is influenced by the formation of pore system and the original water-to-cement ratio in the paste. Consequently, the relative content of capillary water is dropped to less than 2% in the paste with low w/c ratio of 0.3 when being hydrated for 1 d, while the contents are still 16% and 36% in the pastes with w/c ratios of 0.4 and 0.5, respectively.

SEM-backscattered Electron Imaging and Image Processing for Evaluation of Unhydrated Cement Volume Fraction in Slag Blended Portland Cement Pastes

Proper parameters for image taking and minimum field number for image processing were investigated to evaluate volume fraction of unhydrated cement（UHC） in both neat cement paste and slag blended cement paste. Our research suggested that magnification 250x was sufficient for the two pastes, and accelerating voltage should be set as 15 kV and 20 kV for BSE image taking of neat cement paste and slag blended cement paste respectively; the minimum field number increased while the total imaging area stayed the same as the magnification increased within certain statistical bias.

Effect of the Entrained Air Void on Strength and Interfacial Transition Zone of Air-Entrained Mortar

In order to facilitate the development and application of air entraining agents (AEA) in the high performance concrete, entrained air void structure parameters (air void size range from 10 to 1 600 mu m) of 28 d sifted mortar were measured by image analysis method. The relationship between the air void size distribution and strength of mortar was studied by methods of grey connection analysis and multiple linear regression analysis. The multiple linear regression equation was established with a correlation coefficient of 0.966. The weight of the affection of hierarchical porosity on the compressive strength ratio was also obtained. In addition, the effect of air voids on the paste-aggregate interfacial transition zone (ITZ) was analyzed by microhardness. The results show that the correlation between different pore size range and the compressive strength is negative. The effect of air void size distribution on 28 days compressive strength is different: under the condition of similar total porosity, with the increase of the porosity of the air void size, ranging from 10 to 200 mu m, and the decrease of the porosity, ranging from 200 to 1 600 mu m, the average air void diameter and mean free spacing are decreased; as well as the width of ITZ. On the contrary, the microhardness of the ITZ is increased while the compressive strength loss is decreased.

Effects of Surface-activated Coal Gangue Aggregates on Properties of Cement-based Materials

Effects of calcined coal gangue （CG） aggregates treated by the surface thermal activation on the flowability and strength, and paste-CG aggregate interfaces of the cement-based material were investigated. The experimental results show that the compressive and flexural strength of the cement-based material with the calcined CG aggregates is much higher than that of the material with the natural CG aggregates, but the flowability of the material with calcined CG is significantly reduced with the calcined time. The strength of the material with the calcined CG aggregates only increases little with the calcined time at the same w/c ratio, but is reduced with the calcined time at the same flowability. The CG aggregates calcined by the surface thermal activation obviously overcomes the disadvantages of fully calcined CG.

Effects of Cr3+, Cu2+, and Pb2+ on Fly Ash based Geopolymer

The effects of Cr^3+, Cu^2+, and Pb^2+ on compressive strength, reaction products, and pore structures of fly ash based geopolymer were studied. In addition, the immobilization and bonding interaction between heavy metal and fly ash based geopolymers were investigated by X-ray photoelectron spectroscopic(XPS) and environmental scanning electron microscope(ESEM) techniques. The experimental results showed that the incorporation of Cr^3+, Cu^2+, and Pb^2+ had a great effect on the later compressive strength and resulted in producing reinhardbraunsite in the solidified body. Moreover, the Pb^2+ reduced the total pore volume of the solidified body, while Cr^3+ and Cu^2+ increased it. The XPS results indicated that O(1s), Si(2p), and Al(2p)bind energy increased due to Cr^3+ and Cu^2+ addition, but it did not change significantly due to Pb^2+ addition.The microstructure of calcium silicate hydrate(C-S-H) gel and sodium silicoaluminate hydrate(N-A-S-H) gel changed in different degree according to the ESEM results. The immobilization of Cr^3+, Cu^2+, and Pb^2+ using fly ash based geopolymer is attributed not only to the physical encapsulation, but also to the chemical bonding interaction.

Static and Dynamic Leaching Experiments of Heavy Metals from Fly Ash-Based Geopolymers

The feasibility of high calcium fly ash （CFA）-based geopolymers to fix heavy metals were studied. The CFA-based geopolymers were prepared from CFA, flue gas desulfurization gypsum （FGDG）, and water treatment residual （WTR）. The static leaching showed that heavy metals concentrations from CFA- based geopolymers were lower than their maximum concentration limits according to the U.S. environmental protection law. And the encapsulated and fixed ratios of heavy metals by the CFA-based geopolymers were 96.02%-99.88%. The dynamic real-time leaching experiment showed that concentration of Pb （II） was less than 1.μg / L, Cr （VI） less than 3.25 mg / L, while Hg （II） less than 4.0 μg / L. Additionally, dynamic accumulated leaching concentrations were increased at the beginning of leaching process then kept stable. During the dynamic leaching process, heavy metals migrated and accumulated in an area near to the solid-solution interface. When small part of heavy metals in ＂the accumulated area＂ breached through the threshold value of physical encapsulation and chemical fixation they migrated into solution. The dynamic leaching ratios and effective diffusion coefficients of heavy metals from CFA-based geopolymer were very low and the long-term security of heavy metals in CFA-based geopolymer was safe.

Utilization of Thermally Treated Flue Gas Desulfurization (FGD) Gypsum and Class-C Fly Ash (CFA) to Prepare CFA-Based Geopolymer

The feasibility of utilization of flue gas desulfurization （FGD） gypsum and Class-C fly ash （CFA） to prepare CFA-based geopolymer were studied. The results showed that geopolymer made from 90% CFA and 10% FGD gypsum （FGDG） which was thermally treated at 800 ℃ for 1 h obtained the better compressive strength of 37.0 MPa. The micro characteristics and structures of the geopolymer samples of CFA and CFA-FGDG were tested by XRD, FT-IR, and SEM-EDXA after these samples cured at 75 ℃ for 8 h followed by 23 ℃ for 28 d. Both the geopolymer samples of CFA and CFA-FGDG have significant asymmetric stretching of A1-O/Si-O bonds and Si-O-Si / Si-O-A1 bending band. In geopolymer sample of CFA-FGDG, a small quantity of lathy products probably being the ettringite wrapped over the spherical fly ash particle, and the concentration of sulfur is much more than that in geopolymer sample of CFA. It is indicated that FGD gypsum may react during alkali-activated and geopolymeric process.

Preparation of Bentonite Supported Nano Titanium Dioxide Photocatalysts by Electrostatic Self-assembly Method

Electrostatic self-assembly method （ESAM） was used to prepare bentonite supported-nano titanium dioxide photocatalysts. The materials were characterized by X-ray diffraction （XRD）, fourier transform infrared spectroscopy （FT-IR） and scanning electron microscopy （SEM）. Methyl orange was used to estimate the photocatalytic activity of the materials. The effects of the calcination temperature and silane dosage on the photocatalytic activity of the samples were investigated. The experimental results show that the bentonite facilitates the formation of anatase and restrains the transformation of anatase to rutile. Part of nano-size TiO2 particles insert into the galleries of bentonite. The photocatalysts exhibit a synergistic effect of adsorption and photocatalysis on methyl orange. Photocatalysts prepared by ESAM method exhibit higher photocatalytic activity and better recycle ability than those of the traditional method.

Effect of PCEs with Different Functional Groups on the Performance of Cement Paste

The adsorption behaviors and dispersing properties of polycarboxylate superplasticizer(PCE) with different functional groups were systematically analyzed to reveal the theory and methods of modifying PCE molecular structures and regulating PCE performances. By substituting carboxylic groups with sulfonic groups, ester groups or acylamino groups, respectively, modified PCEs with different functional groups were synthesized. Results show that introducing low amount of ester groups or sulfonic groups into the PCE molecules has no negative effects on the fluidity of cement paste, while introducing acylamino groups into PCE molecules significantly weakens the fluidity of cement paste. At low amount(when the molar ratio of sodium methallyl sulfonate to TPEG is lower than 0.4), the rapid adsorption of sulfonic groups onto the cement particles contributes to the high dispersing performance of the sulfonic group modified PCEs. When the substitution ratio of acrylic acid by sulfonic acid is higher than 0.4, the viscosity and the yield stress of cement paste increases sharply. Redundant sulfonic groups lead to the excessive charge density of the PCE, which contributes to the inhomogeneous adsorption on the cement grains and hence results in the decline of the dispersing performance. Substitution of carboxylic group by acylamino group or ester group slightly changes the viscosity as well as the yield stress of cement paste. Introducing sulfonic group into PCE molecule improves the adsorption behavior of PCEs, while introducing ester group or acylamino group into PCE depresses the adsorption properties.

Self-healing of Cracks in Concrete with Various Crystalline Mineral Additives in Underground Environment

Cracks can deteriorate mechanical properties and/or durability of concrete. A few studies have shown that, cracks can autogenously heal under a certain conditions besides the traditional passive repair with a deliberate external intervention. For underground concrete structures, the presence of water, as a necessity for chemical reactions of the healing additives, is beneficial to healing concrete. In this paper, a natural healing method by mineral additives was developed according to the chemical and physical characteristics of underground environment. The healing capacity of three different crystalline mineral materials classified namely, carbonate, calcium sulphoaluminate expansive agent and natural metakaolin due to permeation- crystallization, expansion and pozzolanic reaction, has been assessed from the mechanical properties, referring to the relative elastic modulus, the strength restoration, and the water permeability of the healed specimens. In addition, the morphology of the healing products in the vicinity of the crack was observed. The results indicate that the specimens incorporated with the three mineral additives show different healing capacity according to the improved mechanical properties and permeability. The permeability of the host matrix decreased a lot after crack healing by natural metakaolin followed by carbonate whereas no noticeable improvement of water permeability has been observed for the specimens mixed with expansive agent. The specimens incorporated with carbonate show the best mechanical restoration in terms of relative elastic modulus and compressive strength. Although the dominate element is CaCO3 by reaction of CO32-, either from the dissolved CO2 or from the additives, and Ca2＋ in the cementitious system to fill the cracks, the healing capacity depends greatly on the morphology and the properties of the newly formed products.

Influence of Thermally Treated Flue Gas Desulfurization(FGD) Gypsum on Performance of the Slag Powder Concrete

The feasibility of flue gas desulphurization （FGD） as concrete admixture was studied. A combined concrete admixture of the thermally-treated FGD gypsum and slag powder was explored. The FGD gypsum was roasted at 200℃ for 60 min and then mixed with the slag powder to form FGD gypsum-slag powder combined admixture in which the SO3 content was 3.5wt%. Cement was partially and equivalently replaced by slag powder alone or FGD gypsum-slag powder, at concentration of 25wt%, 40wt%, and 50wt%, respectively. The setting times, hydration products, total porosity and pore size distributions of the paste were determined. The compressive strength and drying shrinkage of cement mortar and concrete were also tested. The experimental results show that, in the presence of FGD gypsum, the setting times are much slower than those of pastes in the absence of FGD gypsum. The combination of FGD gypsum and slag powder provides synergistic benefits above that of slag powder alone. The addition of FGD gypsum provides benefit by promoting ettringite formation and forms a compact microstructure, increasing the compressive strength and reduces the drying shrinkage of cement mortar and concrete.

Healing Effectiveness of Cracks Rehabilitation in Reinforced Concrete Using Electrodeposition Method

An electrodeposition method and its experimental device for rehabilitation of cracks in reinforced concrete were proposed. Porous concrete is proposed to simulate cracked concrete, and mass increment, permeation coefficient and sound velocity of ultrasonic wave were used to be evaluating indicators of healing effectiveness of crack rehabilitation in this method. Effect of currency density, concentration of electrolyte solution on healing effectiveness of porous reinforced concretes with different total void ratio was studied. The experimental results indicate that the simulation of porous concrete for cracks can reflect the healing effectiveness of electrodeposition method effectively, Total void ratio of porous concrete has little effect on healing effectiveness of electrodeposition at early ages. The higher the currency density or concentration of electrolyte solution is, the higher the electrodeposition rate and sound velocity in porous concrete are, and the lower the permeation coefficient of porous concrete will be. Mg（OH）2 crystals produced in high current density are large, thin sheet-shaped and arranged loosely.

Anti-cracking Property of EVA-modified Polypropylene Fiber-reinforced Concrete Under Thermal-cooling Cycling Curing

In order to investigate the synergistic effect of re-dispersible powder-ethylene-vinyl acetate copolymer(EVA) and polypropylene fiber on the crack resistance of concrete under thermal fatigue loading, the compressive strength, ultimate tensile strength, ultimate tensile strain and tensile modulus of elasticity were tested. In addition, ultrasonic method and scanning electron microscope analysis were used to explain the microstructure mechanism. The results show that polypropylene fiberreinforced concrete presents a better performance on crack resistance than ordinary concrete, and the synergism of EVA and polypropylene fiber can improve the anti-cracking ability of concrete further.

Engineering Sodium Metal Anode with Sodiophilic Bismuthide Penetration for Dendrite-Free and High-Rate Sodium-Ion Battery

Sodium(Na)metal batteries with a high volumetric energy density that can be operated at high rates are highly desirable.However,an uneven Na-ion migration in bulk Na anodes leads to localized deposition/dissolution of sodium during high-rate plating/stripping behaviors,followed by severe dendrite growth and loose stacking.Herein,we engineer the Na hybrid anode with sodiophilic Na_(3)Bi-penetration to develop the abundant phase-boundary ionic transport channels.Compared to intrinsic Na,the reduced adsorption energy and ion-diffusion barrier on Na_(3)Bi ensure even Na^(+)nucleation and rapid Na^(+)migration within the hybrid electrode,leading to uniform deposition and dissolution at high current densities.Furthermore,the bismuthide enables compact Na deposition within the sodiophilic framework during cycling,thus favoring a high volumetric capacity.Consequently,the obtained anode was endowed with a high current density(up to 5 mA∙cm^(−2)),high areal capacity(up to 5 mA∙h∙cm^(−2)),and long-term cycling stability(up to 2800 h at 2 mA∙cm^(−2)).

Influence of Polycarboxylate Superplasticizer on Rheological Behavior in Cement Paste

Molecular structures of polycarboxylate（PCE） superplasticizer significantly affect the rheological properties of cement paste. Consequently, we employed self-synthesized PCE copolymers with different carboxylic densities to investigate their influence on the rheological behavior of cement paste. Three typical rheological models were applied to analyze the rheological properties, including Power-law model, Bingham model as well as Herschel-Buikley model. In addition, the thixotropical performances of cement paste in the presence of PCE with different carboxylic densities were investigated. The results show that the carboxylic density of PCE greatly influences the dispersing performance of PCE superplasticizers. As carboxylic density increases, the dispersing capability of PCE improves, and P（PEG1-AA6） possesses the strongest dispersing capability, the initial fluidity and 1 h fluidity of cement paste are both the highest, and cement paste has the lowest viscosity and the smallest hysteresis loop.

In-situ Monitoring of Hydration Kinetics of Cement Pastes by Low-field NMR

Low field NMR technique was applied to investigate the hydration of cement pastes with different water to cement ratios or addition of superplasticizer. As a nondestructive method, this technique can be used to monitor the hydration kinetics process by following the changes of longitudinal relaxation time （T1） of water constrained in the pastes. The experimental results indicate that the T1 distributions of water in the fresh paste normally exhibite bimodal distribution, where the large peak is corresponding to the free water while the small one is contributed by the water stored in the flocculations. Time dependence of the weighted average T1 has a good agreement with the hydration process and could be divided into four stages, i e, initial period, dormant period, accelerated period and steady period. The hydration mechanism of each stage was described based on the theory of cement chemistry. In addition, the total signal intensity, which is proportional to the content of the physically bound water in the samples, decrease successively during the hydration reflecting the consumption of physically bound water by hydration reactions.