Quantitative analysis of microstructure evolution,stress partitioning and thermodynamics in the dynamic transformation of Fe-14Ni alloy

Dynamic transformation(DT)of austenite(γ)to ferrite(α)in the hot deformation of various carbon steels was widely investigated.However,the nature of DT remains unclear due to the lack of quantitative analysis of stress partitioning between two phases and the uncertainty of local distribution of substitu-tional elements at the interface in multi-component carbon steels used in the previous studies.Therefore,in the present study,a binary Fe-Ni alloy withα+γduplex microstructure in equilibrium was prepared and isothermally compressed inα+γtwo-phase region to achieve a quantitative analysis of microstruc-ture evolution,stress partitioning,and thermodynamics during DT.γtoαDT during isothermal compres-sion andαtoγreverse transformation on isothermal annealing under unloaded condition after deforma-tion were accompanied by Ni partitioning.The lattice strains during thermomechanical processing were obtained via in-situ neutron diffraction measurement,based on which the stress partitioning behavior betweenγandαwas discussed by using the generalized Hooke’s law.A thermodynamic framework for the isothermal deformation in solids was established based on the basic laws of thermodynamics,and it was shown that the total Helmholtz free energy change in the deformable material during the isothermal process should be smaller than the work done to the deformable material.Under the present thermody-namic framework,the microstructure evolution in the isothermal compression of Fe-14Ni alloy was well explained by considering the changes in chemical free energy,plastic and elastic energies,and the work done to the material.In addition,the stabilization of the softαphase in Fe-14Ni alloy by deformation was rationalized since theγtoαtransformation decreased the total Helmholtz free energy by decreasing the elastic and dislocation energies.

Dialectical Thermodynamics’Solution to the Conceptual Imbroglio That Is the Reversible Path

According to the second law of thermodynamics, as currently understood, any given transit of a system along the reversible path proceeds with a total entropy change equal to zero. The fact that this condition is also the identifier of thermodynamic equilibrium, makes each and every point along the reversible path a state of equilibrium, and the reversible path, as expressed by a noted thermodynamic author, “a dense succession of equilibrium states”. The difficulties with these notions are plural. The fact, for example, that systems need to be forced out of equilibrium via the expenditure of work, would make any spontaneous reversible process a consumer of work, this in opposition to common thermodynamic wisdom that makes spontaneous reversible processes the most efficient transformers of work-producing-potential into actual work. The solution to this and other related impasses is provided by Dialectical Thermodynamics via its previously proved notion assigning a negative entropy change to the energy upgrading process represented by the transformation of heat into work. The said solution is here exemplified with the ideal-gas phase isomerization of butane into isobutane.

A thermodynamics-consistent spatiotemporally-nonlocal model for microstructure-dependent heat conduction

The spatiotemporally-nonlocal phenomena in heat conduction become significant but challenging for metamaterials with artificial microstructures.However,the microstructure-dependent heat conduction phenomena are captured under the hypothesis of spatiotemporally local equilibrium.To capture the microstructure-dependent heat conduction phenomena,a generalized nonlocal irreversible thermodynamics is proposed by removing both the temporally-local and spatially-local equilibrium hypotheses from the classical irreversible thermodynamics.The generalized nonlocal irreversible thermodynamics has intrinsic length and time parameters and thus can provide a thermodynamics basis for the spatiotemporally-nonlocal law of heat conduction.To remove the temporallylocal equilibrium hypothesis,the generalized entropy is assumed to depend not only on the internal energy but also on its first-order and high-order time derivatives.To remove the spatially local equilibrium hypothesis,the thermodynamics flux field in the dissipation function is assumed to relate not only to the thermodynamics force at the reference point but also to the thermodynamics force of the neighboring points.With the developed theoretical framework,the thermodynamics-consistent spatiotemporally-nonlocal models can then be developed for heat transfer problems.Two examples are provided to illustrate the applications of steady-state and transient heat conduction problems.

Improving hydrogen storage thermodynamics and kinetics of Ce-Mg-Ni-based alloy by mechanical milling with TiF_(3)

Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocomposite materials of Mg and additives.In this experiment,TiF_(3)was selected as an additive,and the mechanical milling method was employed to prepare the experimental alloys.The alloys used in this experiment were the as-cast Ce_(5)Mg_(85)Ni_(10),as-milled Ce_(5)Mg_(85)Ni_(10)and Ce_(5)Mg_(85)Ni_(10)+3 wt.%TiF3.The phase transformation,structural evolution,isothermal and non-isothermal hydrogenation and dehydrogenation performances of the alloys were inspected by XRD,SEM,TEM,Sievert apparatus,DSC and TGA.It revealed that nanocrystalline appeared in the as-milled samples.Compared with the as-cast alloy,ball milling made the particle dimension and grain size decrease dramatically and the defect density increase significantly.The addition of TiF_(3)made the surface of ball milling alloy particles markedly coarser and more irregular.Ball milling and adding TiF_(3)distinctly improved the activation and kinetics of the alloys.Moreover,ball milling along with TiF_(3)can decrease the onset dehydrogenation temperature of Mg-based hydrides and slightly ameliorate their thermodynamics.

Thermodynamics-directed bulk/grain-boundary engineering for superior electrochemical durability of Ni-rich cathode

Introducing high-valence Ta element is an essential strategy for addressing the structu ral deterioration of the Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM)cathode,but the enlarged Li/Ni cation mixing leads to the inferior rate capability originating from the hindered Li~+migration.Note that the non-magnetic Ti~(4+)ion can suppress Li/Ni disorder by removing the magnetic frustration in the transition metal layer.However,it is still challenging to directionally design expected Ta/Ti dual-modification,resulting from the complexity of the elemental distribution and the uncertainty of in-situ formed coating compounds by introducing foreign elements.Herein,a LiTaO_3 grain boundary(GB)coating and bulk Ti-doping have been successfully achieved in LiNi_(0.834)Co_(0.11)Mn_(0.056)O_(2) cathode by thermodynamic guidance,in which the structural formation energy and interfacial binding energy are employed to predict the elemental diffusion discrepancy and thermodynamically stable coating compounds.Thanks to the coupling effect of strengthened structural/interfacial stability and improved Li~+diffusion kinetics by simultaneous bulk/GB engineering,the Ta/Ti-NCM cathode exhibits outstanding capacity retention,reaching 91.1%after 400 cycles at 1 C.This elaborate work contributes valuable insights into rational dual-modification engineering from a thermodynamic perspective for maximizing the electrochemical performances of NCM cathodes.

Thermodynamics in a quantum corrected Reissner-Nordstr?m-AdS black hole and its GUP-corrections

We calculate the thermodynamic quantities in the quantum corrected Reissner-Nordstr?m-AdS(RN-AdS)black hole,and examine their quantum corrections.By analyzing the mass and heat capacity,we give the critical state and the remnant state,respectively,and discuss their consistency.Then,we investigate the quantum tunneling from the event horizon of massless scalar particle by using the null geodesic method,and charged massive boson W^(±)and fermions by using the Hamilton-Jacob method.It is shown that the same Hawking temperature can be obtained from these tunneling processes of different particles and methods.Next,by using the generalized uncertainty principle(GUP),we study the quantum corrections to the tunneling and the temperature.Then the logarithmic correction to the black hole entropy is obtained.

Heart failure with preserved ejection fraction and the first law of thermodynamics

In heart failure with preserved ejection fraction,significant left ventricular diastolic abnormalities are present,despite a normal systolic ejection fraction.This article will consider whether this is consistent with the law of conservation of energy,also know as the first law of thermodynamics.

Two innovative equivalent statements of the third law of thermodynamics

It is found from textbooks and literature that there are three different statements for the third law of thermodynamics,i.e., the Nernst theorem, the unattainability statement of absolute zero temperature, and the heat capacity statement. It is pointed out that such three statements correspond to three thermodynamic parameters, which are, respectively, the entropy,temperature, and heat capacity, and can be obtained by extrapolating the experimental results of different parameters at ultralow temperatures to absolute zero. It is expounded that because there is no need for additional assumptions in the derivation of the Nernst equation, the Nernst theorem should be renamed as the Nernst statement. Moreover, it is proved that both the Nernst statement and the heat capacity statement are mutually deducible and equivalent, while the unattainability of absolute zero temperature is only a corollary of the Nernst statement or the heat capacity statement so that it is unsuitably referred to as one statement of the third law of thermodynamics. The conclusion is that the Nernst statement and the heat capacity statement are two equivalent statements of the third law of thermodynamics.

Elimination, Kinetics and Thermodynamics of Fe(II) Ions by Adsorption in Static and Dynamic Conditions on Activated Carbons in Aqueous Media

This work investigated the removal, kinetics and thermodynamics of iron(II) ions (Fe(II)) by adsorption in static and dynamic conditions in aqueous media on activated carbons (AC-i30min, AC-i1h, and AC-i24h), prepared from palm nut shells collected in the city of Franceville to Gabon, using potassium hydroxide (KOH) as the activating agent. Results on the elimination of Fe(II) in static and dynamic adsorption on prepared activated carbons (ACs) showed that the AC-i24h adsorbent has the best Fe(II) adsorption capacities at saturation (Qsat). The Qsat obtained on AC-i24h in static and dynamic conditions (17.87 and 10.38 mg/g, respectively) were higher than those of AC-i30min (13.89 and 5.54 mg/g respectively) and AC-i1h (14.92 and 8.64 mg/g respectively). Moreover, the static adsorption was more effective in the removal of Fe(II) ions in aqueous media in our experimental conditions. The percentage removal (%E) of Fe(II) obtained on prepared activated carbons in static conditions was better than those obtained in dynamic conditions, especially on AC-i24h, where the %E was 89.27% in static and 61.56% in dynamic. In kinetics, results showed that the pseudo-second-order kinetic model best described the adsorption mechanisms of Fe(II) on prepared activated carbons in static adsorption, with mainly of chemisorption on the solid surfaces. However, in dynamic conditions, the pseudo-first-order kinetic model was more suitable. In addition to the weak interactions between Fe(II) and the activated carbon surfaces, strong interactions (chemisorption) were also observed. Also, thermodynamic data obtained on AC-i24h in static adsorption indicated that the adsorption of Fe(II) was spontaneous and increased with temperature (ΔG˚ H˚ = 503.54 KJ/mol).

高精度流体PVTx性质测量实验系统的研制

在对国内外现有流体PVTx性质实验系统分析研究的基础上,结合一些最新的温度、压力及计算机自动测量等技术,研制了一套新的高精度流体PVTx性质实验系统.通过对系统的误差分析表明:新实验系统的温度测量不确定度小于±2mK,压力测量不确定度小于±0 7kPa.利用新的实验系统,对294～353K温度区间的HFC152a饱和蒸气压进行了研究.实验结果表明,HFC152a的测量值与公认文献值的平均偏差小于0 011%,最大偏差小于0 037%.

应用储层流体包裹体PVTX模拟研究油气成藏期次——以塔里木盆地托甫台地区为例

储层流体包裹体PVTX模拟被广泛用来确定包裹体的捕获温度与压力,进而精确恢复油气运移/成藏的时间/深度。应用该VTFlinc模拟方法,选择塔里木盆地塔河油田外围托甫台地区的TP2井,对其奥陶系碳酸盐岩储层中的流体包裹体开展了研究,根据包裹体的岩相学、显微测温、激光拉曼光谱、激光共聚焦显微镜等分析,研究了包裹体的形成期次、成份及热力学特征,并模拟计算了包裹体形成的古温度和古压力,进而推断了油气充注的时间和成藏期次。结果表明,TP2井区主要存在两期油气充注,第一期大致在加里东晚期,时间距今420～405Ma,第二期大致在喜山晚期,时间距今8～2Ma。以往研究认为塔河油田主体部位的后期喜山期油气充注成藏事件并未影响到这一地区,而通过本文应用的新方法研究,证明了该期油气成藏事件存在,这为区域油气勘探提供了新的参考信息,也充分展示出本研究方法所具有的潜在重要推广应用意义。

近共沸制冷剂R290/R134a PVTx性质的实验研究

为了获得混合制冷剂R134a/R290的热物性数据,搭建了高精度PVTx实验系统。以Burnett法为基础,测定了R134a/R290质量分数为50%/50%、55%/45%和60%/40%在温度为252 K^320 K的PVT性质,并且拟合了三种不同配比的混合工质的气态维里方程。实验数据与方程的平均误差为1%左右,具有较好的重合度。

基于包裹体PVTx数值模拟恢复油藏古温压---存在的问题、对策及应用实例

包裹体PVTx数值模拟是恢复油藏古温压的重要手段。由于无法精确地确定油包裹体的组成,以及油包裹体成分在地质演化过程中可能发生不可逆的次生变化,现有方法恢复的古温压存在不确定性。一般而言,与油包裹体伴生的盐水包裹体成分相对简单,且遭受次生蚀变影响的概率较低。因此,尝试将伴生的盐水包裹体作为独立的地质压力计在塔里木盆地顺南地区SN1井进行了应用研究。包裹体岩相学研究显示,SN1井高角度裂缝充填的方解石中,发育大量遭受过次生蚀变的含沥青烃包裹体及伴生的盐水包裹体。包裹体古温压恢复显示,伴生的盐水包裹体呈现异常高的均一温度(超过170℃),均一压力波动范围大,且存在异常高压(39.1 MPa起,甚至超过165.8 MPa)。上述现象可能与热流体活动和原油充注后所经历的裂解增压过程有关。基于盐水包裹体均一压力的最低值,结合该地区埋藏史和热演化史分析,推测热液活动时间为海西期。上述认识与该地区NE向走滑断裂活动具有较好的时空匹配关系。综上所述,油包裹体伴生的盐水包裹体作为独立的地质压力计,可以用来恢复油藏古温压的演化轨迹,并限定古流体活动的时间,能够在一定程度上弥补现有方法的不足。

多元混合工质及纯质的PVTx实验研究

多元混合工质及纯质的ＰＶＴｘ实验研究王怀信，高志明，马一太，刘靖，赵凤亭（天津大学热能研究所天津３０００７２）关键词代用工质，ＰＶＴｘ特性以ＨＣＦＣ２２、ＨＣＦＣ１２４及ＨＦＣ１５２ａ为组元的混合工质是ＣＦＣ１２有希望的灌注式替代物。其中ＨＣＦＣ１２...

碳氢化合物/HFC227ea二元系的PVTx实验研究

对定容式 ＰＶＴｘ实验装置的恒温、测温和测压系统进行了改进，温度和压力基本测量精度提高到±５ｍＫ和±０．４ ｋＰａ．对 ＨＣ１２７０／ＨＦＣ２２７ｅａ、ＨＣ２９０／ＨＦＣ２２７ｅａ和 ＨＣ１７０／ＨＦＣ２２７ｅａ二元物系进行了 ＰＶＴｘ实验研究．

流体包裹体PVTx模拟研究油气充注期次和古压力恢复:以西湖凹陷平湖构造带为例

传统流体包裹体PVTx模拟应用包裹体组分、气液比和均一温度,结合模拟软件可以恢复包裹体被捕获时的古流体压力,然而组分参数受多因素影响而难以确定,导致精度有限。介绍了Ping等2011年提出的一种改进PVTx模拟法,以西湖凹陷平湖构造带为例,应用显微荧光、显微测温和激光共聚焦扫描显微镜等分析,划分了油气充注期次并恢复了古压力,简化了依靠传统模拟软件获取捕获压力的步骤。研究结果表明：平湖构造带存在两期油气充注,第一期距今16.8~13.2 Ma,即中新世早期,主要充注发橙黄色荧光的原油,古流体压力为25.00~28.86MPa;第二期为主成藏期,距今10.0~0Ma,即中新世中后期至今,主要充注天然气和发蓝绿色、蓝白色多种荧光颜色的原油,古流体压力为38.60~44.31 MPa。研究结果有助于深化勘探区油气成藏规律的认识。

Thermodynamics and kinetics of adsorption of molybdenum blue with D301 ion exchange resin

The adsorption behavior of D301 for molybdenum blue was investigated.The thermodynamics parameters in adsorption process were calculated and the adsorption kinetics was studied.The experimental results show that the adsorption characteristic of D301 for molybdenum blue fits well with the Freundlich adsorption isotherm equation.In the adsorption process of D301 for molybdenum blue,both the enthalpy change ΔH and entropy change ΔS are positive,while the free energy change ΔG is negative when temperatures are in the range of 303-333 K.It is indicated that the adsorption is a spontaneous and endothermic process,and the elevated temperatures benefit to the adsorption.Kinetic studies show that the kinetic data are well described by double driving-force model,and the adsorption rate of molybdenum blue on D301 is controlled by the intraparticle diffusion during the adsorption process.The total kinetic equation is determined.

新型环保制冷剂R1234ze/R600a PVTx性质

在Burnett原理基础上搭建了高精度PVT实验台,对新型环保混合制冷剂R1234ze/R600a进行了热物性测试。在温度范围为280.15~330.15 K时,测量了质量分数为80%/20%和75%/25%的R1234ze/R600a混合制冷剂的PVT性质,同时拟合出了相应温度与压力下该混合工质的密度与气体维里方程,为进一步研究该混合制冷剂作为新型替代制冷剂的性能提供了热物性参数。

Thermodynamics of removing impurities from crude lead by vacuum distillation refining

A novel technique was developed to remove impurities from crude lead by vacuum distillation.The thermodynamics on vacuum distillation refining process of crude lead was studied by means of saturated vapor pressure of main components of crude lead,separation coefficients and vapor-liquid equilibrium composition of Pb-i（i stands for an impurity） system at different temperatures.The behaviors of impurities in the vacuum distillation refining process were investigated.The results show that the vacuum distillation should be taken to obtain lead from crude lead,in which Zn,As and partial Sb are volatilized at lower temperature of 923-1023 K.Lead is distilled from the residue containing Cu,Sn,Ag and Bi at higher temperature of 1323-1423 K,but the impurity Bi is also volatilized along with lead and cannot be separated from lead.

利用包裹体PVTx和PetroMod盆地模拟系统反演鄂尔多斯盆地上古生界古流体压力

包裹体捕获压力反映了油气藏形成时的流体压力,对于成藏过程具有重要的指示意义。本文尝试结合包裹体PVTx相态模拟及Petro Mod盆地模拟两种方法反演鄂尔多斯盆地上古生界古流体压力。以鄂尔多斯盆地天环凹陷地区布1井为例,利用包裹体PVTx相态模拟得到布1井2个包裹体样品均一温度及捕获压力分别为98.2℃,34.38MPa和121℃,30.01MPa。由Petro Mod盆地模拟生成布1井的热演化史及古流体压力史,将二者结果结合推导出包裹体形成时间。结果表明,鄂尔多斯盆地天环凹陷地区主要成藏时间为122-100Ma（晚白垩世）。结合烃源岩生烃史,推测包裹体流体形成于上古生界烃源岩快速生烃阶段,对应成熟度范围约为Ro≈0.68%-0.76%。