Micromechanics of ITZ–Aggregate Interaction in Concrete Part I: Stress Concentration

At the macroscopic scale, concrete appears as a composite made of a cement paste matrix with embedded aggregates. The latter are covered by interfacial transition zones (ITZs) of reduced stiffness and strength. Cracking in the ITZs is probably the key to the nonlinear stress–strain behavior in the prepeak regime. For a deeper understanding of this effect triggered by tensile microstress peaks, we here employ and extend the framework of continuum micromechanics, as to develop analytical solutions relating the macroscopic stresses acting on a piece of concrete, to microtractions at the aggregates' surfaces and to three‐dimensional stress states within the ITZs. In the latter context, a new aggregate‐to‐ITZ stress concentration tensor is derived based on the separation‐of‐scale principle, which implies that ITZs may be modeled as two‐dimensional interfaces at the concrete scale, but as three‐dimensional bulk phases at the scale of a few micrometers. Microtensile peaks occur both under uniaxial macroscopic tension and compression. To describe the respective microtraction and microstress fields, it is suitable to define aggregate's “poles” and “equator” by an “axis” through the aggregate center, directed in the uniaxial macroscopic loading direction. Accordingly, tensile microtraction peaks, induced by macro‐tension and macro‐compression, respectively, occur at the “poles” and at the “equator”, respectively. The largest tensile ITZ‐microstresses occur at an offset of about π/8 from the “poles” and the “equator”, respectively. These fields of microtractions and ITZ microstresses are prerequisites for upscaling ITZ‐related strength to the macroscopic concrete level, as presented in the companion paper (Part II).     

Properties of electrolyte solutions relevant to high concentration chloride leaching. II. Density, viscosity and heat capacity of mixed aqueous solutions of magnesium chloride and nickel chloride measured to 90 °C

Results of density and viscosity measurements for aqueous solutions of MgCl₂ (0.5–3.5 mol L^− 1) and MgCl₂ + 10% NiCl₂ (0.5–3.5 mol L^− 1) at temperatures of 25, 60 and 90 °C show an almost linear increase in density with total concentration, while low nickel contents and temperature have comparatively small effects. Viscosities of MgCl₂ solutions rise sharply at 25 °C but are significantly lower at 90 °C. The viscosity of 3–4 mol kg^− 1 MgCl₂ at 90 °C is similar to water at 25 °C. Nickel has no significant effect on the viscosity of these solutions.Results of heat capacity measurements for aqueous solutions of MgCl₂ (0.5–3.5 mol L^− 1) and MgCl₂ + 10% NiCl₂ (0.5–3.5 mol L^− 1) at temperatures of 60 and 90 °C show that the heat capacities of these solution decrease significantly with total concentration, while the effects of low nickel contents and temperature are again comparatively small.     

Micromechanics of ITZ‐Aggregate Interaction in Concrete Part II: Strength Upscaling

Cracking in concrete typically starts in the immediate vicinity around the aggregates, i.e., in the region of the so‐called interfacial transition zones (ITZs), but the process is still not fully understood. Notably, crushing of concrete in compression results in fragments with interesting aggregate surface textures. Part of the aggregate surfaces is cleanly separated from the ITZ, while another part of the aggregate surfaces remains covered with a thin layer of cement paste. This suggests two different types of failure: ITZ‐aggregate separation and ITZ failure; which we here study based on the continuum micromechanics approach of the companion paper (part I). It provides access to both traction vectors acting on aggregate surfaces and three‐dimensional stress states within representative ITZ volumes for loading states below the elastic limit of concrete. When inserting these microtractions and microstresses into Rankine‐type strength criteria for the aggregate‐ITZ interface and for the ITZ, respectively, the micromechanics model allows for upscaling this microscopic failure behavior to concrete‐level criteria for crack onset. Comparing the latter to corresponding experimental results, reveals that under tension‐dominated loading both ITZ failure and ITZ‐aggregate separation appear to be realistic, while under compression‐dominated loading ITZ failure appears as the more likely mechanism. Also, comparing model and experiments shows that the ITZ‐aggregate separation strength amounts to at least half of the internal ITZ cohesion strength, but may be much larger than the latter.     

Properties of electrolyte solutions relevant to high concentration chloride leaching. III. Solubility of pertinent solids and iron(III)/iron(II) redox potential measured in concentrated magnesium chloride solutions

Results of solubility measurements of nickel chloride, manganese chloride, iron(II) chloride, hematite and akaganeite in aqueous solutions of MgCl₂ (0.5–3.5 mol L^− 1) at temperatures of 60 and 90 °C are reported. Solubilities of metal(II) chlorides decrease almost linearly with MgCl₂ concentration due to the common ion effect. Nickel chloride and iron(II) chloride solubilities are very similar, while manganese chloride is about 30% more soluble.Hematite is more stable (i.e. less soluble) than akaganeite under all conditions investigated in this study, while ferrihydrite is considerably less stable. In other words, there is no change in the relative stabilities of these phases effected by the presence of high magnesium chloride concentrations. The solubility of all of these phases decreases with temperature and, for each temperature, the solubility constants increase linearly with the MgCl₂ concentration. The present results allow the prediction of the iron concentration as a function of the H⁺ and MgCl₂ molality at equilibrium with hematite or akaganeite.The Fe(III)/Fe(II) redox behaviour has been characterized in concentrated aqueous solutions of MgCl₂ (1.5–3.5 mol L^− 1) at a temperature of 25 °C. Standard redox potentials are ca. 100 mV lower than at infinite dilution and change linearly by only 13 mV in the range 2–4 mol L^− 1 MgCl₂.     

Calculation of indifferent phase equilibria

A straightforward iterative search for indifferent equilibria is described. It is applied to systems relevant to separation and production processes such as fractional distillation or crystallization and sintering. The respective G functions were taken from literature or obtained with the help of the optimization routine of ChemSage. The calculations for the localization of indifferent phase equilibria were also carried out with ChemSage, however, the new method operates independently of the computer software used.     

Properties of electrolyte solutions relevant to high concentration chloride leaching I. Mixed aqueous solutions of hydrochloric acid and magnesium chloride

A computer code based on a Pitzer model has been developed for the comprehensive prediction of the thermodynamic properties of MgCl₂–HCl aqueous solutions over a wide range of conditions from 25 to 120 °C and from 0–350 g L^− 1 chloride. This code was applied to the calculation of (i) water activities and mean ionic activity coefficients for mixed aqueous solutions of hydrochloric acid and magnesium chloride over a wide range of concentrations and to 100 °C, (ii) solubilities of MgCl₂·6H₂O in MgCl₂–HCl solutions to 80 °C, (iii) partial pressures of HCl(g) and H₂O(g) over MgCl₂–HCl aqueous solutions at various temperatures and (iv) partial pressures of HCl(g) at the normal boiling point of these mixed electrolyte solutions. The model predictions are in excellent agreement with available experimental data and confirm evidence from the literature that MgCl₂(aq) and HCl(aq) mix almost ideally at constant water activity.     

Computer-assisted optimization of cobalt-base alloy compositions

Cobalt-base hard metals are known for their wear and corrosion resistance and also for their ability to retain hardness at elevated temperatures.

Considering the matrix of these alloys it can be predicted that (a) the performance against corrosive media will improve when the Cr content is increased, (b) a higher W content will be advantageous because of its solid solution strengthening effect, and (c) care has to be taken in the course of liquid phase sintering to avoid unwished-for carbides and/or intermetallic phases, because these would be detrimental with respect to mechanical properties of the alloys.

To locate ranges for optimal matrix and carbide compositions thermodynamic calculations with were carried out on the basis of recently published data which were improved by a new optimization routine.

A series of phase diagrams was calculated and the optimal compositions of alloys were derived. Furthermore, calculated transition temperatures and phase compositions of some selected alloys compare reasonably with published experimental results.