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.

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.

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 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.

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.

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.

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.

矿用电缆护套热降解动力学与火灾危险性探究

针对矿用电缆护套的燃烧性能,为电缆安全设计和合理选用提供依据,通过TGA/DSC和CONE探究了MYQ、MHYV和MKVV型电缆护套热降解特性和火灾危险性。结果表明:3种护套的热降解过程均可分为3个阶段,热失重主要发生在前2个阶段,且第一阶段的失重率最大;MYQ护套受温度影响最大,但是热解过程最缓慢;MHYV和MKVV护套受温度影响较小,但是热解反应最剧烈,且2种护套热解过程相似。MYQ护套的火灾危险性远大于MHYV和MKVV护套。根据计算得出的3种电缆护套的热解活化能,采用广义主图法确定了每种护套各个阶段的热解反应模型。研究结果可为电缆护套材料热解和火灾危险性研究以及电缆护套安全设计提供参考。

全混流反应器异常操作工况下反应温度预测方法及危害分析

采用数学拟合方法,根据不同温度下反应物含量变化的实验数据获取釜式反应器中主反应的动力学参数,根据加速量热仪法测定二次反应温度随时间的关系确定二次反应的动力学参数,并基于热量衡算和反应动力学研究建立全混流反应器(CSTR)的温度预测模型,研究了CSTR异常操作工况下反应温度的预测方法,并进行了危害分析。模拟结果显示,对常规n级放热反应,该模型可简单准确模拟不同操作条件下CSTR内操作参数随时间的变化关系,在换热失效条件下,反应温度最高可达130℃;所建立的模型可定量模拟异常工况下反应温度、组分含量及热负荷的变化,可为反应器异常操作工况下的反应危害分析提供数据支持,对反应工艺和反应器设计及本质安全的实现具有指导意义。

融合危险度模糊分级的UAV动态避障方法

针对无人机(UAV)在多障碍环境中面对运动障碍的反应式避障问题,为了在反应避障决策时能够朝向周围障碍更远、更少的方向进行避障,提出了一种融合障碍危险度模糊分级的三维速度障碍避障方法。通过三维速度障碍法,给出探测域内各运动障碍的碰撞预测。选取坐标系三轴方向作为相互独立的可用避障加速度方向,在速度及加速度限制下求解三轴方向上避障加速度方向以及数值区间。通过模糊算法,给出了周围其他静止障碍的危险分级方法,提出优化评价函数对计算各方向上的最优加速度,给出优化避障指令。仿真结果表明,针对复杂环境,UAV在反应避障的同时考虑了其他障碍的影响,相比原算法拥有了更高的避障成功率和更少的避障次数。

化工工艺氯化反应的重点监管与分类探讨

文章从化工生产企业精细化管理要求及国家政策对危化品行业监管的角度出发,对当前国家重点监管的化工工艺中的氯化反应放热类型未加以细化分类、给企业投资带来影响等问题进行了探讨。从氯化反应危险特性角度通过反应物料量热实验验证氯化工艺中有一类氯化反应类型为吸热反应,并结合典型氯化反应类别进行比较对比,发现这类特殊的氯化反应类型为甲酰化反应。因此,建议国家相关部门对此类吸热氯化反应工艺应从现有政策危险反应工艺中加以区分,并对重点危险化工工艺监管的合理性及规范性进行调整,以减少企业建设过程中的不必要投资,为国家优化出台涉及重点监管化工反应工艺的管理控制提供更合理的参考依据。

2,6-二苦氨基-3,5-二硝基吡啶合成过程硝化反应安全风险分析

为了分析2,6-二苦氨基-3,5-二硝基吡啶(PYX)合成过程硝化反应的热危险性,以2,6-双(苦氨基)吡啶(PAP)为原料,经硝化反应制备得到了PYX,利用反应量热仪(RC1)测定了该硝化反应热数据,利用差示扫描量热仪和绝热量热仪分别对PAP、PYX和硝化液的热分解过程进行了测试,并计算了硝化液的分解反应动力学参数。结果表明,硝化反应的摩尔生成焓Δm H r为-686.8 kJ/mol,绝热温升ΔT ad为76.8 K;硝化反应的最大累积度为48.7%,发生冷却失效时,体系所能达到的最高温度MTSR为86.6℃;DSC测得PAP和PYX的分解峰温分别为312.74℃和377.77℃;利用绝热加速度量热仪(ARC)测得绝热条件下,硝化液的T D24为221.3℃;综合反应量热数据和绝热量热数据得出,该硝化反应发生冷却失效后有可能引起冲料,但触发其二次分解反应风险较低。因此,需设置加料、搅拌与温度的联锁和蒸发冷却装置。

Alkali-Silica Reactivity and Strength of Mortars with Expanded Slate, Expanded Glass or Perlite

Lightweight aggregates are increasingly used in concrete construction. They reduce concrete selfweight furnishing a structural advantage. In contrast, the mechanical properties and durability of lightweight concrete can become the governing factor on lightweight aggregate replacement ratios. Alkali-Silica Reactison (ASR) and compressive strength of mortar samples with expanded slate, expanded glass or perlite, covering the spectrum of internal porosity and weight of lightweight aggregates, were evaluated. Scanning electron microscopy was utilized to evaluate the contribution of the aggregates’ porosity and chemical composition in inhibiting ASR. Perlite, owing to its highly porous microstructure and lower matter excelled in ASR expansion while chemical composition and denser microstructure of the heavier expanded slate resulted in more signified late ASR expansion and higher compressive strength. An attempt in visual inspection of ASR attack of alkali metal ions on silica-rich expanded glass using an ultra-accelerated exposure to sodium hydroxide solution was made.

丁酮肟盐酸盐热分解反应动力学及危险性研究

为探究丁酮肟盐酸盐的热危险性,利用差示扫描量热仪(Differential Scanning Calorimeter,DSC)获得热分解特性与分解反应类型;并利用Kissinger、KAS(Kissinger Akahira Sunose)线性回归法和非线性回归法求解动力学模型及参数;利用所得动力学参数推算其最大反应速率到达时间(Time to Maximun Rate,TMR)、转换限制时间(Conversion Limit Time,TCL)和自加速分解温度(Self-Accelerating Decomposition Temperature,SADT)。结果表明:随升温速率提高,初始分解温度和分解的峰值温度提高,平均比放热量为749.01 kJ/kg;丁酮肟盐酸盐的热分解具有自催化特征,包含两个自催化反阶段,且第1阶段产生的热量诱导第2阶段的发生,第1阶段的Ea为99.02 kJ/mol,第2阶段的Ea为93.46 kJ/mol;丁酮肟盐酸盐的SADT为39.51℃,控制温度为29.51℃,因此在生产、运输和储存过程中应加强温度的监控。

绝热加速量热仪在反应安全风险评估应用中的常见问题

绝热加速量热仪(ARC)目前已被广泛运用于反应安全风险评估中。本文在总结ARC在反应安全风险评估中应用的基础上,指出在进行ARC测试时一些常见问题一直被人忽略,这些问题中一部分是可以通过更好地设计实验方法来避免,如进样量过少、样品池的不兼容性和样品低温反应等问题;另外一部分是仪器自身的问题,需要了解其根本原因从而避免使用错误的数据得出错误的结论,如绝热炉最大温升速率限制、压力链接接头的热损失、压力链接管道中的蒸气冷凝和温升速率较大时ARC样品温度测量准确性等问题。本文就这些问题作系统性分析,旨在提醒科研学者可以更好地设计实验和解读数据。文中分析得出结论:推荐ARC进样量为4g左右,选择与测试样品兼容的样品池,尽量使用新制备的样品做测试,且能分辨当样品的最大温升速率大于ARC绝热炉的最大温升速率时的非绝热数据。文章总结以上几种方法为在工艺反应安全风险评估中更准确地使用ARC数据提供参考。

3,4-二氯苯甲醛肟化反应热危险性研究

为研究3,4-二氯苯甲醛肟化反应过程热危险性,分别采用差示扫描量热仪(DSC)、绝热加速量热仪(ARC)、Gaussian 09软件和反应量热仪(RC1e),对原料、产物的热分解情况以及肟化反应过程的热效应进行研究。结果表明:原料3,4-二氯苯甲醛吸热量为157.08 kJ/kg,盐酸羟胺放热量为2561.63 kJ/kg,反应后混合物料放热量为462.52 kJ/kg;反应失控情况下,最大反应速率到达时间为24 h时所对应的温度T D24为501.78 K;反应过程体系理论计算所得反应热为153.36 kJ/kg,实验测得放热量为139.47 kJ/kg。综合考虑以实测数据对工艺危险度等级进行评估,可知工艺存在冲料及分解风险,并给出了相应的建议措施。

长链脂肪醇酯化工艺热安全风险研究与安全工艺优化

以长链脂肪醇和氨基磺酸酯化反应为研究对象,使用反应量热仪(RC1mx)和绝热加速量热仪(ARC)获得工艺一的绝热温升、失控体系可能达到的最高温度等热数据,风险评估工艺一反应风险等级为4级。利用实时原位红外光谱仪(ReactIR)对比了不同加料方式和反应温度,获得改进工艺,改进工艺的反应温度提高至130℃,氨基磺酸一次性改为分四次等量投料。改进工艺的反应风险等级为2级,安全性显著提高,可投入工业化生产。