A Model for Temperature Infl uence on Concrete Hydration Exothermic Rate (Part one: Theory and Experiment)

Recent achievements in concrete hydration exothermic models based on Arrhenius equation have improved computation accuracy for mass concrete temperature field. But the properties of the activation energy and the gas constant （Ea/R） have not been well studied yet. From the latest experiments it is shown that Ea/R obviously changes with the hydration degree without fixed form. In this paper, the relationship between hydration degree and Ea/R is studied and a new hydration exothermic model is proposed. With those achievements, the mass concrete temperature field with arbitrary boundary condition can be calculated more precisely.

In-depth investigation of the exothermic reactions between lithiated graphite and electrolyte in lithium-ion battery

Thermal runaway is a critical issue for the large application of lithium-ion batteries.Exothermic reactions between lithiated graphite and electrolyte play a crucial role in the thermal runaway of lithium-ion batteries.However,the role of each component in the electrolyte during the exothermic reactions with lithiated graphite has not been fully understood.In this paper,the exothermic reactions between lithiated graphite and electrolyte of lithium-ion battery are investigated through differential scanning calorimetry(DSC) and evolved gas analysis.The lithiated graphite in the presence of electrolyte exhibit three exothermic peaks during DSC test.The reactions between lithiated graphite and LiPF_(6) and ethylene carbonate are found to be responsible for the first two exothermic peaks,while the third exothermic peak is attributed to the reaction between lithiated graphite and binder.In contrast,diethylene carbonate and ethyl methyl carbonate contribute little to the total heat generation of graphite-electrolyte reactions.The reaction mechanism between lithiated graphite and electrolyte,including the major reaction equations and gas products,are summarized.Finally,DSC tests on samples with various amounts of electrolyte are performed to clarify the quantitative relationship between lithiated graphite and electrolyte during the exothermic reactions.2.5 mg of lithiated graphite (Li_(0.8627)C_(6)) can fully react with around 7.2 mg electrolyte,releasing a heat generation of 2491 J g^(-1).The results presented in this study can provide useful guidance for the safety improvement of lithium-ion batteries.

The Dynamic Flexibility of Batch Exothermic Reaction System： Take into Account the Effect of the Initial Operational Temperature

It is shown in this article that by changing the initial operation condition of the batch processes, the dynamic performance of the system can be varied largely, especially for the initial operational temperature of the exothermic reaction. The initial operation condition is often ignored in the designing batch processes for flexibility against disturbances or parameter variations. When the initial condition is not rigid as in the case of a batch reactor, where the initial reaction temperature is quite arbitrary, optimization can also be applied to determine the ＂best＂ initial condition to use. Problems for dynamic flexibility analysis of exothermic reaction including initial temperature and process operation can be formulated as dynamic optimization problems. Formulations are derived when the initial conditions are considered or not. When the initial conditions are considered, the initial condition can be transferred into control variables in the first optimal step. The solution of the dynamic optimization is on the basis of Rugge-Kutta integration algorithm and decomposition search algorithm. This method, as illustrated and tested with two highly nonlinear process problems, enables the determination of the optimal level. The dynamic performance is improved by the proposed method in the two exothermic reaction examples.

Effect of Top Slag Basicity on Quality of Steel Treated by Exothermic Agent SiFe and SiCaBa during Chemical Heating

The effect of top slag basicity on quality of steel treated with SiFe and SiCaBa alloy as exothermic agent in chemical heating was studied.These experiments were carried out in MoSi_2 laboratory furnace with 0.2 kg molten steel for equilibrium test and 2 kg molten steel for simulation test respectively.These results showed that the adjusting basicity of top slag with CaO is effective to prevent rephosphorization and resulphurization,and it is possible to dephosphorize and desulphurize and remove the inclusions from molten steel when basicity R of the top slag is adjusted to 2.0 — 3.10,and SiCaBa alloy is better than SiFe alloy in this relation.

Studies on Relationship Between Low Temperature Exotherms and Freezing Injury in Stem Tissues and Flower Buds of Mei Flower and David's Peach

Differential thermal analysis was utilized to determine midwinter hardiness of stem tissues and flower buds of mei flower (Prunus mume) and David’s peach (Prunus davidiana). Low temperature freezing exotherms were found to occur at -35℃ in Green Calyxs’ David’s peach and -18℃ in mei flower. A Low temperature exotherm was produced by the freezing of deep supercooling water which was detected in the wood tissues but not in the bark. Freezing processes of the wood and those of the bark appeared to be independent. Deep supercooling points of both species were found to be closely related to freezing injury and to their respective distributions.

Convenient design of anti-wetting nano-Al/WO_(3)metastable intermolecular composites(MICs)with an enhanced exothermic life-span

For solving the dilemma of the short exothermic life-span of WO_(3)based metastable interstitial composites(MICs)with extensive application prospect,this paper has firstly designed the promising antiwetting Al/WO_(3)MICs via electrophoresis assembly of nano-Al and WO_(3)particles fabricated by hydrothermal synthesis method,followed by the subsequent fluorination treatment.A combination of X ray diffraction(XRD),field emission scanning electron microscope(FESEM),energy dispersive X-ray spectroscopy(EDX),and Fourier transform infrared spectroscopy(FT-IR)techniques were utilized in order to characterize the crystal structure,microstructure,and elemental composition distribution of target films after different natural exposure tests.The product with uniform distribution and high purity possesses a high contact angle of~170°and a minute sliding angle of~1°,and displays the outstanding anti-wetting property using droplets with different surface tensions.It also shows great moisture stability in high relative-humidity circumstances after one year of the natural exposure experiment.Notably,the heat output of a fresh sample can reach up to 2.3 kJ/g and retain 96%after the whole exposure test,showing outstanding thermo-stability for at least one year.This work further proposed the mechanism of antiwetting Al/WO_(3)MICs considering the variation tendency of their DSC curve,providing a valuable theoretical reference for designing other self-protected MICs with a long exothermic life-span applied in wide fields of national defense,military industry,etc.

An efficient light-to-heat conversion coupling photothermal effect and exothermic chemical reaction in Au NRs/V_(2)C MXene membranes for high-performance laser ignition

MXene,a new type of two-dimensional materials,have been demonstrated as one of the best photothermal materials owing to their strong light-matter interaction and high photothermal conversion efficiency in recent years.Herein,we report the intriguing light-to-heat conversion property of vanadium carbide(V_(2)C)MXene under irradiation of millisecond laser pulse.Unlike the typical photothermal materials,the V_(2)C MXene not only converts the incident laser energy to heat by the physical photothermal effect,but also triggers the exothermic oxidation of the V_(2)C MXene.The oxidation could be greatly promoted with addition of plasmonic Au nanorods(Au NRs)for light absorption enhancement.Owing to the unique light-to-heat conversion property,the Au NRs/V_(2)C MXene membrane could serve as high temperature pulse(HTP)generators that is proposed for numerous applications with high demand for immediacy.As a proof-of concept application,Au NRs/V_(2)C MXene membrane was applied for laser ignition of the high energy density materials,such as 2,4,6,8,10,12-(hexanitrohexaaza)cyclododecane(HNIW or CL-20).An improved ignition performance,in terms of lowered laser threshold,is achieved as compared to the state-of-the-art light-to-heat conversion materials.

Relationship between the Standard Enthalpy of Formation and the Ratio of Standard Enthalpy of Formation and Exothermic Denitration Decomposition Peak Temperature of M(NTO)_n

A relationship is established, using the least squares method, between the standard enthalpy of formation and the standard enthalpy of formation divided by the exothermic denitration decomposition peak absolute temperature corresponding to β →0.

Formation of composites fabricated by exothermic dispersion reaction in Al-TiO_2-B_2O_3 system

The formation of aluminum matrix composites fabricated by exothermic dispersion reaction in Al-TiO2-B2O3 system was investigated. The thermal analysis results show that the reactions are spontaneous and exothermic. The Gibbs free energy of α-Al2O3 is the lowest among all the combustion products, followed by TiB2 and Al3Ti. It is noted that when the B2O3/TiO2 mole ratio is below 1, the reaction products are composed of particle-like α-Al2O3, TiB2 and rod-like Al3Ti. The α-Al2O3 crystallites, resulting from the reaction between Al and TiO2 or B2O3, are segregated at the grain boundaries due to a lower wettability with the matrix. SEM micrographs show that rod-like Al3Ti phase distributes uniformly in the matrix. When the B2O3/TiO2 mole ratio is around 1, the Al3Ti phase almost disappears in the composites, and the distribution of α-Al2O3 particulates is improved evidently.

An extended numerical model of the first exothermic peak for three dimensional printed cement-based materials

The first exothermic peak of cement-based material occurs a few minutes after mixing,and the properties of three dimensional(3D)printed concrete,such as setting time,are very sensitive to this.Against this background,based on the classical Park cement exothermic model of hydration,we propose and construct a numerical model of the first exothermic peak,taking into account the proportions of C_(3)S,C_(3)A and quicklime in particular.The calculated parameters are calibrated by means of relevant published exothermic test data.It is found that this developed model offers a good simulation of the first exothermic peak of hydration for C_(3)S and C_(3)A proportions from 0 to 100% of cement clinker and reflects the effect of quicklime content at 8%-10%.The unique value of this research is provision of an important computational tool for applications that are sensitive to the first exothermic peak of hydration,such as 3D printing.

Exothermic Performance of the Calcined Limestone Determined by Exothermic Temperature under Fluidization during CaCO_(3)/CaO Energy Storage Cycles

Thermochemical energy storage based on CaO/CaCO_(3)cycles has obtained significant attention as an alternative energy storage solution for concentrated solar power plants.In view of the applicability of fluidized bed reactors for CaO/CaCO_(3)heat storage,it is imperative to study the factors related to the heat release performance of CaO.This work presents an exothermic experiment on calcined limestone under fluidization,exploring the impact of initial temperature,CO_(2)concentration,particle size,superficial gas velocity,and number of cycles on the exothermic performance of CaO.The result indicates that CaO with high initial temperature leads to higher exothermic temperature,with better exothermic stability under cycles.An optimal initial temperature range of 600℃-650℃exists with an actual CaO conversion rate deviating merely 2%from theoretical conversion.Higher CO_(2)concentration augments the exothermic temperature and rate of CaO,while also improves the effective conversion of CaO.Nevertheless,high CO_(2)concentrations exacerbate the sintering and deactivation of CaO.High superficial gas velocity and small particle size shorten the exothermic time by increasing heat dissipation,but has minimal effect on the exothermic properties.Finally,the exothermic properties of CaO under fluidized and static conditions are studied.The result shows that exothermic temperature and exothermic rate of CaO under fluidization are enhanced,displaying higher heat storage performance than that under static state.This study provides valuable insights for optimizing the exothermic performance of CaO in fluidized bed reactors,contributing to advanced thermochemical energy storage for concentrated solar power plants.

喷油正时对氨/柴油双燃料发动机燃烧放热规律和部分排放的影响

以船用单缸柴油机为研究对象,采用氨气预混、柴油直喷的燃烧模式,通过试验方式探讨喷油正时对氨/柴油双燃料发动机燃烧与排放特性的影响。结果表明,与纯柴油模式相比,喷入氨气后,发动机缸压峰值P_(max)降低,着火时刻推迟,燃烧持续期增加,最大压力升高率R_(max)减少,CO_(2)和NO_(x)的排放下降,未燃氨和N_(2)O的排放显著增加。在双燃料模式下,随着柴油喷射时刻的提前,缸内燃烧情况改善,P_(max)和R_(max)增大,未燃氨和N_(2)O排放下降,NO_(x)排放上升,碳烟排放先减后增,CO_(2)排放无显著变化;随着负荷的增加,P_(max)和R_(max)增大,但氨气喷射量的增加降低了缸内空气充量,使得着火时刻推迟,燃烧持续期增加,CO_(2)、碳烟和NOx的排放增加,未燃氨和N_(2)O的排放降低。如果优先考虑燃烧平稳性,25%和75%负荷率下的喷油正时最佳值为-5°CA;若以降低温室气体排放为首要目标,25%负荷率下的喷油正时最佳值为-15°CA,75%负荷率下的喷油正时最佳值为-10°CA;若以降低NOx排放为首要目标,25%和75%负荷率下的喷油正时均为-5°CA。

Exothermic process of cast-in-place pile foundation and its thermal agitation of the frozen ground under a long dry bridge on the Qinghai-Tibet Railway

A number of dry bridges have been built to substitute for the roadbed on the Qinghai-Tibet Railway,China.The aim of this study was to investigate the exothermic process of cast-in-place (CIP) pile foundation of a dry bridge and its harm to the stability of nearby frozen ground.We present 3D heat conduction functions of a concrete pile and of frozen ground with related boundaries.Our analysis is based on the theory of heat conduction and the exponent law describing the adiabatic temperature rise caused by hydration heat.Results under continuous and initial conditions were combined to establish a finite element model of a CIP pile-frozen ground system for a dry bridge under actual field conditions in cold regions.Numerical results indicated that the process could effectively simulate the exothermic process of CIP pile foundation.Thermal disturbance to frozen ground under a long dry bridge caused by the casting temperature and hydration heat of CIP piles was substantial and long-lasting.The simulated thermal analysis results agreed with field measurements and some significant rules relating to the problem were deduced and conclusions reached.

不同预氧化程度下煤自燃特性研究

煤自燃是影响煤矿安全生产的主要灾害之一。为研究氧化煤的自燃特性,利用程序升温试验系统对预氧化不同氧化程度为40℃、70℃、100℃、120℃、150℃和170℃煤样在低温氧化阶段的耗氧速率、CO和CO_(2)产生率、放热强度进行了计算,得出不同氧化程度煤在不同氧化温度下的自燃特性。结果表明:随着温度的升高,预氧化程度为40℃、70℃、100℃、120℃、150℃和170℃煤样的耗氧速率、CO及CO_(2)产生率、放热强度均超过了原煤,预氧化程度为170℃的煤样与原煤基本持平,对氧化煤应该进行有效防治,分析结果对采空区煤自燃防治具有一定的指导意义。

Co-Harvest Phase-Change Enthalpy and Isomerization Energy for High-Energy Heat Output by Controlling Crystallization of Alkyl-Grafted Azobenzene Molecules

Photoisomerization-induced phase change are important for co-harvesting the latent heat and isomerization energy of azobenzene molecules.Chemically optimizing heat output and energy delivery at alternating temperatures are challenging because of the differences in crystallizability and isomerization.This article reports two series of asymmetrically alkyl-grafted azobenzene(Azo-g),with and without a methyl group,that have an optically triggered phase change.Three exothermic modes were designed to utilize crystallization enthalpy(△H_(c))and photothermal(isomerization)energy(△H_(p))at different temperatures determined by the crystallization.Azo-g has high heat output(275-303 J g^(-1))by synchronously releasing△H_(c)and△H_(p)over a wide temperature range(-79℃to 25℃).We fabricated a new distributed energy utilization and delivery system to realize a temperature increase of 6.6℃at a temperature of-8℃.The findings offer insight into selective utilization of latent heat and isomerization energy by molecular optimization of crystallization and isomerization processes.

大中型球墨铸铁件冒口发热保温覆盖剂的补缩效率试验研究

简述了大中型球墨铸铁冒口覆盖剂的性能要求,提出了新的冒口补缩效率表征和测试方法,通过实际生产试用对新型大中型球墨铸铁件冒口发热保温覆盖剂和国内外2家著名公司同类产品进行了系统的对比研究。结果表明:大中型球墨铸铁件冒口新型发热保温冒口覆盖剂的发热反应起燃温度、起燃时间、发热速度、发热量和生产成本等得到综合平衡,具有低成本和环境友好的特点;新型覆盖剂中氟盐含量低,冒口根部未见石墨球粗大或球化不良缺陷,对球铁铸件表层的石墨球形态影响很小;新型覆盖剂可使大中型球墨铸铁件的冒口相对补缩效率高达50%,优于对比测试的国内外2家著名公司的同类产品,能较好地满足高端装备大中型球墨铸铁件生产要求;新建立的“冒口相对补缩效率”新指标反映了冒口缩沉总体积和形状(即冒口安全高度)的综合影响,比传统的“冒口补缩效率”更能准确地表征冒口的实际补缩能力和效果。

深层环境下固井水泥水化放热特性及井周温度场演化规律研究

塔里木盆地已建成我国最大的超深层油气生产基地,深层环境会对水泥水化放热特性产生一定的影响,研究深层环境下水泥水化放热及传热特性对明确井周温度场演化规律至关重要。文章首先根据现场实测资料建立了塔里木油田近井和远井地层温度方程,根据不同地层深度的温度分布情况,开展了不同温度下G级水泥水化放热实验,基于Krstulovic-Dabic(K-D)经典水化动力学模型,结合水泥成核结晶与晶体生长、相边界反应以及扩散三过程反应特征推导了不同温度下水泥水化放热预测曲线,进一步推导了套管-水泥环-地层热传导模型,并将放热曲线作为热源代入到有限元模型中,得到了不同井深的套管与水泥在水化放热与高温地层的共同作用下温度场的变化情况。研究结果可为下一步分析有限局部空间的温度场变化对地层压力和套管变形影响提供技术支持。

鄂尔多斯长7段油页岩不同阶段热解反应特征

针对原位热采开发油页岩矿藏中热解反应变化复杂、控温困难等问题,通过热重分析实验对鄂尔多斯盆地长7油页岩热解过程进行阶段划分;通过X射线衍射测试、气相色谱-质谱联用等实验重点检测有机质裂解放热阶段的产物成分,分析不同阶段演化的主要化学反应,进一步验证阶段划分。结果表明,油页岩在氮气氛围下的热解可以划分为3个阶段:脱水阶段(<300℃)、有机质裂解放热阶段(300~720℃)、矿物吸热分解阶段(>720℃)。在有机质裂解放热阶段,油页岩的失重约为总失重的74%,无机矿物未发生热裂解。有机质裂解放热阶段可进一步划分为3个阶段:300℃≤T<450℃的低温初始段、450℃≤T<600℃的中温热解段、600℃≤T≤720℃的高温热解完成段。有机质的热解主要发生在中温热解段。随温度升高,烷烃脱氢反应、酯化反应变为以酯类化合物热裂解反应、烷烃断链生成小分子烃类反应为主;温度升至600~720℃时,会促使化合物发生聚合向油页岩半焦转化;当温度控制在中温热解段时,油页岩油成分最好,含27.70%酯类、29.89%脂肪烃、14.49%醇类、12.66%芳香烃等。研究结果为油页岩热解机理分析、油页岩数值模拟模型的建立和提高现场采收率提供理论指导,并对控制有机质的反应温度范围提供依据,保证较高的转化率。

天下冷暖,知于化学——化学能与热能的转化

冷热现象是人类最早观察和认识的自然现象之一。在自然界的能量转化现象中,化学能与热能的转化是常见形式之一。现代社会中,有很多相关应用给大众生活带来了极大的便利。本科普实验秉承着“应用化学,安全至上,造福社会”的理念,旨在通过简单的实验,激发普通大众对化学的兴趣,帮助他们正确认识化学,了解化学反应可能存在的安全风险,并培养其正确的安全意识。实验围绕化学反应中两个特征鲜明的反应:吸热反应(氯化铵与氢氧化钡反应)和放热反应(发热包与水反应),针对不同知识背景的受众,设计了不同的呈现形式(如趣味实验——气球捏捏冰、情景剧——碘-淀抱抱乐),在幼儿园、中学和社区开展了多场主题科普教育活动。实验通过这些活动向大众展示了化学能与热能之间相互转化的奇妙现象,普及了相关安全常识,使不同的受众真切地感受到了化学的无穷魅力,同时也提高了他们的安全意识。

月桂酸-棕榈酸-十四醇复合相变混凝土的制备与分析

用月桂酸-棕榈酸-十四醇与膨胀珍珠岩制备三元复合相变材料(LA-PA-TD/EP),采用湿裹水泥法将其进行封装,并对其基本性能及热工性能进行研究。结果表明:湿裹水泥的封装方式可将LA-PA-TD/EP泄漏率降至1.94%,随着相变骨料替代率的增加,LA-PA-TD/EP复合相变混凝土的力学性能出现下降趋势,但其蓄放热性能增强。当相变骨料替代率为20%时,相变混凝土抗压强度、抗拉强度分别为22.8、2.53 MPa,较普通混凝土分别降低了42.7%、47.0%,复合相变混凝土的蓄放热性能良好,可满足混凝土基本要求。