Effect of Anti-freezing Admixtures on Alkali-silica Reaction in Mortars

The influence of anti-freezing admixture on the alkali aggregate reaction in mortar was analyzed with accelerated methods. It is confirmed that the addition of sodium salt ingredients of anti-freezing admixture accelerates the alkali silica reaction to some extent, whereas calcium salt ingredient of anti-freezing admixture reduces the expansion of alkali silica reaction caused by high alkali cement. It is found that the addition of the fly ash considerably suppresses the expansion of alkali silica reaction induced by the anti-freezing admixtures.

Effect of Pozzolanic Reaction Products on Alkali-silica Reaction

The effect of fly ash on controlling alkail-silica rection （ASR） in simudated alkali solution was studied. The expausion of mortar bars and the content of Ca（ OH）2 in cement paste cured at 80 °G for 91 d were measured. Traasmission electron microscopy （TEM） and high-resolution transmission electron microscot9 （HRTEM） were employed to study the microstructure of C-S-H. TEM/ energy dispersive spectroscopy （EDS） leas then used to determine the composition of C-S-H. The pore structure of the paste was analyzed by mercury intntsion porosimetry （MIP）. The results show that the contents of fly ash of 30% and 45% can well inhibit ASR. And the content of Ca（OH） 2 decreases with the increase of fly ash. That fly ash reacted with Ca（OH）2 to produce C-S-H with a low Ca/Si molar ratio could bind more Na^＋ and K^＋ ious, and produce a reduction in the amount of soluble alkali available for ASR. At the same time, the C- S- H produced by pozzolanic reaction converted large pores to snudler ones （ gel pores smaller than 10 nm ） to deusify the pore structure. Perhaps that could inhibit alkali trausport to aggregate for ASR.

Effect of Mineral Admixtures on Alkali-Silica Reaction

The influence of silica fume, slag and fly ash on alkali-silica reaction under the condition of 70 ℃ is studied. The results show that silica, slag and fly ash may inhibit alkali-silica reaction only under suitable content. When the content is less than 10%, silica fume does not markedly influence the expansion of alkali- silica reaction. When the content is 15%-20%, silica fume only may delay the expansion of alkali-silica reaction. When the content is 30%-70%, slag may only delay the expansion of alkali-silica reaction, but cannot inhibit the expansion of alkali-silica reaction. When the content is 10%, fly ash does not markedly influence the expansion of alkali-silica reaction. When the content is 20%-30%, fly ash may only delay the expansion of alkali-silica reaction, but cannot inhibit the expansion of alkali-silica reaction. When the content is over 50%, it is possible that fly ash can inhibit effectively alkali-silica reaction.

Effect of the Composite of Natural Zeolite and Fly Ash on Alkali-Silica Reaction

The effect of the composite of natural zeolite and fly ash on alkali-silica reaction (ASR) was studied with natural alkali-reactive aggregate and quartz glass aggregate respectively.The expansive experiment of mortar bar and concrete prism was completed.The results show that ASR can be suppressed effectively by the composite of natural zeolite and fly ash.

The Mechanism of the Eeffect of Mineral Admixtures on the Expansion of Aalkali-silica Reaction

On the base of the influence rule of silica fume, slag and fly ash on alkali-silica reaction under the condition of 70 ℃, the mechanism of the effect of mineral admixtures on alkali-silica reaction is studied further in the paper. The results show that the effects of mineral admixtures on alkali-silica reaction are mainly chemistry effect and surface physichemistry effect. Under suitable condition, the chemistry effect may make alkali-silica reaction to be inhibited effectively, but the physichemistry effect only make alkali-silica reaction to be delayed. The chemistry effect and the physichemistry effect of minerals admixture are relative to the content of Ca（OH）2 in system. Under the condition that there is a large quantity of Ca（OH）2, mineral admixture cannot inhibit alkali-silica reaction effectively. Only when Ca（OH）2 in the system is very less, it is possible that mineral admixture inhibits alkali-silica reaction effectively.

Alkali-Silica Reaction Inhibited by LiOH and Its Mechanism

A high alkali reactive aggregate zeolitization perlite was used to test the long term effectiveness of LiOH in inhibiting alkali silica reaction.In this paper,the rigorous conditions were designed that the mortar bars had been cured at 80℃ for 3 years after autoclaved 24 hours at 150℃.Under this condition,LiOH was able to inhibit the alkali silica reaction long term effectiveness.Not only the relationship between the molar ratio of n(Li)/(Na) and the alkali contents in systems was established, but also the governing mechanism of such effects was also studied by SEM.

Efficacy of Aluminum Hydroxides as Inhibitors of Alkali-Silica Reactions

A comparative study of amorphous and crystalline forms of commercial aluminum hydroxides as inhibitors of alkalisilica reactions in Portland cement mortars has been performed. It was found that at dosages of 1% to 3%, amorphous aluminum hydroxide can efficiently inhibit alkali-silica expansion of Portland cement compositions. High inhibiting activity of amorphous Al(OH)3 additives may be explained by their ability to actively bind Ca(OH)2 formed by the hydration of silicate phases of cement, to form ettringite (with participation of gypsum). Crystalline Al(OH)3 additives that do not possess the ability to interact with Ca(OH)2 even after additional grinding, however, demonstrate week properties to inhibit alkali-silica expansion. This may indicate that the inhibitory effect of Al(OH)3 at least—partly, may be given by its influence on the concentration of Al3+ ions in the pore solution. Some expansion of the samples with admixtures of Al(OH)3 observed during the alkaline expansion accelerated test procedure is not associated with the formation of ettringite and is only due to alkali-silicate reactions.

The Impact of Aluminum- and Iron-Bearing Admixtures on the Resistance of Portland Cement Mortars to Alkali-Silica Reaction and Sulfate Attack

Study of sulfate resistance of mortars with aluminum- and iron-bearing admixtures (Al(OH)3, Al2(SO4)3, FeSO4, Fe2(SO4)3) in conditions close to those established in ASTM C 1012, and the study of the mitigation effect of these admixtures on alkali-silica reaction in accordance with accelerated “mortar bar” test ( GOST 8269.0, ASTM C 1260) were performed. Iron (II) and (III) sulfates show ability for mitigation alkali-silica reaction, while also, in contrast with Al-bearing substances, do not induce the drastic reducing of the initial setting time and do not promote the progress of sulfate corrosion. Compared with FeSO4, iron (III) sulfate has moderate deleterious impact on the early strength of cement paste and can be of interest alone as an inhibitor of ASR. Iron (II) sulfate may be used together with aluminum sulfate to offset the accelerating effect of the latter on the setting of cement paste and to reduce a risk of sulfate corrosion. During prolonged water storage, the mortar elongation and secondary ettringite formation do not occur, even when Al2(SO4)3 is available. Therefore, the investigated admixtures cannot act as agents of internal sulfate attack, however, Al2(SO4)3 can enhance the outer sulfate attack.

Calcined Clay Pozzolan as an Admixture to Mitigate the Alkali-Silica Reaction in Concrete

Calcined clay pozzolan has been used to replace varying portions of high alkali Portland limestone cement in order to study its effect on the alkali-silica reaction (ASR). Portland limestone cement used for the study had a total Na2Oeq of 4.32. Mortar-bar expansion decreased as pozzolan content in the cement increased. The highest expansion was recorded for reference bars with no pozzolan, reaching a maximum of 0.35% at 42 days whilst the expansion was reduced by between 42.5% and 107.8% at 14 days and between 9.4% and 16.4% at 84 days with increasing calcined clay pozzolan content. Mortar bars with 25% pozzolan were the least expansive recording expansion less than 0.1% at all test ages. X-ray diffractometry of the hydrated blended cement paste powders showed the formation of stable calcium silicates in increasing quantities whilst the presence of expansive alkali-silica gel, responsible for ASR expansion, decreased as pozzolan content increased. The study confirms that calcined clay pozzolan has an influence on ASR in mortar bars and causes a significant reduction in expansion at a replacement level of 25%.

Ultrafine Silica Additives Behavior during Alkali-Silica Reaction Long-Term Expansion Test

A silica fume, precipitated silica, metakaolin and siliceous fly ash behavior as constituents of mortars was studied, while mortar samples have been tested for long-term alkali-silica reaction expansion in accordance to the GOST 8269.0 specification. Solid-state 29Si-MAS NMR spectroscopy and thermogravimetric analysis were used to describe Portland cement hydration, supplementary cementitious material pozzolanic reaction and to establish a structure of products of those processes. It was found that long-term test conditions, in contrast to the accelerated test, do not affect the composition of products formed too much, compared to normal conditions. This allows results obtained with long-term test to be expected as more relevant in terms of predicting of supplementary cementitious materials inhibiting properties.

The Mitigation of Alkali-Silica Reactions by Aluminum-Bearing Substances

An ability of aluminum-bearing substances-amorphous aluminum hydroxide, aluminum sulphate and basic aluminum sulphate to mitigate alkali-silica reactions in Portland cement mortars has been studied. At equivalent dosages in terms of Al2O3, these substances are ranged in the following order in respect of inhibiting effect: Al(OH)1.78(SO4)0.61 ≥ Al2(SO4)3 > Al(OH)3. It is found that the plasticizing agents of the main types used in cement compositions have no influence on the inhibiting effect of aluminum-bearing admixtures. To control the setting time of cement paste, iron(II) sulphate may be used for partial substitution of Al2SO4·18H2O, and this operation is not influence on the results of ASR expansion test.

Reaction视频中用户弹幕信息交互行为的情感反应生成机理研究

深入挖掘Reaction视频中弹幕信息交互行为的情感反应机理有助于理解用户弹幕创作背后的情感生成原因及情感变化过程。本文基于情感反应模型,利用定向内容分析法对哔哩哔哩网站中11个热门视频的弹幕信息资源、视频内容以及reactor反应情况展开编码研究,构建了Reaction视频中用户弹幕信息交互行为的情感反应生成机理模型。研究发现,Reaction视频弹幕信息交互行为中的情感反应生成机理总体上遵循“信息刺激-情感反应”的路径,信息刺激有时会独立唤醒情绪或特定情感态度,有时也会通过唤醒特定情感态度进而影响情绪或内化情感态度的生成。该模型有助于提升情感反应理论在计算机协助交流中的情境化探索,也将为社交媒体中用户与信息交互提供优化建议。

Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

Deformable Catalytic Material Derived from Mechanical Flexibility for Hydrogen Evolution Reaction

Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.

“Buckets effect”in the kinetics of electrocatalytic reactions

In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.

Metal-organic-framework-derived copper-based catalyst for multicomponent C-S coupling reaction

Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.

The reaction mechanism and interfacial crystallization of Al nanoparticle-embedded Ni under shock loading

The shock-induced reaction mechanism and characteristics of Ni/Al system,considering an Al nanoparticle-embedded Ni single crystal,are investigated through molecular dynamics simulation.For the shock melting of Al nanoparticle,interfacial crystallization and dissolution are the main characteristics.The reaction degree of Al particle first increases linearly and then logarithmically with time driven by rapid mechanical mixing and following dissolution.The reaction rate increases with the decrease of particle diameter,however,the reaction is seriously hindered by interfacial crystallization when the diameter is lower than 9 nm in our simulations.Meanwhile,we found a negative exponential growth in the fraction of crystallized Al atoms,and the crystallinity of B2-NiAl(up to 20%)is positively correlated with the specific surface area of Al particle.This can be attributed to the formation mechanism of B2-NiAl by structural evolution of finite mixing layer near the collapsed interface.For shock melting of both Al particle and Ni matrix,the liquid-liquid phase inter-diffusion is the main reaction mechanism that can be enhanced by the formation of internal jet.In addition,the enhanced diffusion is manifested in the logarithmic growth law of mean square displacement,which results in an almost constant reaction rate similar to the mechanical mixing process.

Approaching Ultimate Synthesis Reaction Rate of Ni-Rich Layered Cathodes for Lithium-Ion Batteries

Nickel-rich layered oxide LiNi_(x)Co_(y)MnzO_(2)(NCM,x+y+z=1)is the most promising cathode material for high-energy lithium-ion batteries.However,conventional synthesis methods are limited by the slow heating rate,sluggish reaction dynamics,high energy consumption,and long reaction time.To overcome these chal-lenges,we first employed a high-temperature shock(HTS)strategy for fast synthesis of the NCM,and the approaching ultimate reaction rate of solid phase transition is deeply investigated for the first time.In the HTS process,ultrafast average reaction rate of phase transition from Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_(2) to Li-containing oxides is 66.7(%s^(-1)),that is,taking only 1.5 s.An ultrahigh heating rate leads to fast reaction kinetics,which induces the rapid phase transition of NCM cathodes.The HTS-synthesized nickel-rich layered oxides perform good cycling performances(94%for NCM523,94%for NCM622,and 80%for NCM811 after 200 cycles at 4.3 V).These findings might also assist to pave the way for preparing effectively Ni-rich layered oxides for lithium-ion batteries.

Exciting lattice oxygen of nickel–iron bi-metal alkoxide for efficient electrochemical oxygen evolution reaction

High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.

Solvent effects on Diels-Alder reaction in ionic liquids:A reaction density functional study

Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.