Effect of lanthanum-modified magnesium silicate on isotactic polypropylene crystallization in composite materials during shear flow

The activity of isotactic polypropylene (iPP) nucleating additives during shear flow of composite materials is still not entirely explained. In current work the sol-gel method was employed to synthesize MgO·SiO₂ filler, surface-modified with trivalent lanthanum. The crystallization of commercial iPP in the presence of 0.5% by weight La³⁺ modified or unmodified silicates was analyzed. The wide angle X-ray scattering analysis proved that the presence of even small amount of filler influences significantly on supermolecular structure of iPP. The results of microscope observations confirmed that the lanthanum-modified filler shows the nucleating ability for iPP. In that case a significant reduction of crystallization induction time was noticed. The investigation of iPP crystallization in composites after shear treatment confirmed that the increase of shear rate reduces the nucleating ability of additives. Moreover, the flow of filler particles during shearing may impede the shear-induced crystallization phenomenon.     

Influence of size-classified and slightly soluble mineral additives on hydration of tricalcium silicate

Early-age hydration of cement is enhanced by slightly soluble mineral additives (ie, fillers, such as quartz and limestone). However, few studies have attempted to systematically compare the effects of different fillers on cementitious hydration rates, and none have quantified such effects using fillers with comparable, size-classified particle size distributions (PSDs). This study examines the influence of size-classified fillers [ie, limestone (CaCO₃), quartz (SiO₂), corundum (Al₂O₃), and rutile (TiO₂)] on early-age hydration kinetics of tricalcium silicate (C₃S) using a combination of experimental methods, while also employing a modified phase boundary and nucleation and growth model. In prior studies, wherein fillers with broad PSDs were used, it has been reported that between quartz and limestone, the latter is a superior filler due to its ability to partake in anion-exchange reactions with C-S-H. Contrary to prior investigations, this study shows that when size-classified and area matched fillers are used—which, essentially, eliminate degrees of freedom associated with surface area and agglomeration of filler particulates—the filler effect of quartz is broadly similar to that of limestone as well as rutile. Results also show that unlike quartz, limestone, and rutile—which enhance C₃S hydration kinetics—corundum suppresses hydration of C₃S during the first several hours after mixing. Such deceleration in C₃S hydration kinetics is attributed to the adsorption of aluminate anions—released from corundum's dissolution—onto anhydrous particulates’ surfaces, which impedes both the dissolution of C₃S and heterogeneous nucleation of C-S-H.     

TiS夹杂物对D6AC超高强度钢强韧性的影响

一般钢中加Ti可使晶粒细化,从而提高钢的强韧性。但D6AC超高强度铟中可否加Ti的问题,一直存在争论。因为加Ti后,可能生成含Ti夹杂物而使韧性降低。为了改善D6AC钢的韧性,首先需要弄清这一问题。本文系统研究了含Ti夹杂物对D6AC钢强韧性的影响,并与同一钢种中,含有常见的MnS夹杂物进行比较,得出: 1.TiS夹杂物对强度和延伸率的影响不明显; 2.TiS夹杂物对面缩率、冲击韧性和断裂韧性稍有影响; 3.TiS开裂％随应变增大而增加,但在同一应变下却低于MnS; 4.TiS夹杂物使K_(1C)值降低的幅度低于MnS,因此,D6AC钢中加Ti可以改善强韧性。     

Thiol-ene emulsion polymerization using a semi-continuous approach

The thermally initiated thiol-ene emulsion polymerization of diallyl phthalate (DAP) diene and ethylenedioxy diethanthiol (EDDT) dithiol monomers in batch and semibatch emulsion polymerization is investigated. The batch process leads to larger and broader particle sizes than when the polymerization is carried out in semibatch. The evolution of the particle size and the final particle size distribution indicate that the stability of the latexes is limited and, hence, aggregation phenomena occurred in both processes. In particular, the evolution of the particle size distribution (PSD) in the semibatch process indicates nucleation, growth, and aggregation occurring simultaneously that produced a bimodal particle size. When the diene monomer was changed to diallyl terephthalate (DATP), the semibatch polymerization yielded smaller particles and narrow distribution without any indication of aggregation. The partial substitution of the dithiol by a trithiol monomer that is substantially more water insoluble affected nucleation of the particles, yielding for both systems smaller particles. The polythioether polymers synthesized present low glass transition temperatures (~ −30/−40°C) and those containing the therephthalate yield crystalline films. The potential application of the polymers as pressure sensitive adhesives (PSAs) was preliminarily assessed.     

Understanding the role of seeds in reactive magnesia cement (RMC) formulations

Nucleation effects of seeds in reactive magnesia cement (RMC) systems have been reported, but this process has never been directly observed. In this study, different types and contents of seeds were introduced in RMC formulations. Results show that seeded RMC samples revealed accelerated hydration/carbonation that led to their more rapid strength development, and the use of magnesite outperformed other seeds given their overall performances, as explained by their more homogenous microstructures. Further, in the model solution, the amount of Mg2+ ions adsorbed onto seeds particles continuously increased with the increment of Mg2+ concentrations, confirming the nucleation effects of seeds in RMC formulations directly, and seeds surfaces revealed a much higher affinity for Mg2+ ions than other ions due to their acid-base interactions. Therefore, the use of seeds could act as accelerators that shorten the curing period of RMC-based concrete products on a large scale.     

Unusual crystallization pathways revealed in six barium disilicate (BaSi2O5) glasses

Due to the unusual crystallization of (nominally) stoichiometric BaSi₂O₅ (BS2) glass, which shows unexpected and diverse crystal phases, a series of six glasses with different chemicals and melting procedures were prepared in three laboratories and characterized before and after crystallization by differential scanning calorimetry, density measurements, X-ray diffraction, FTIR, and Raman spectroscopy. The aim of this study was to assess whether there is systematic behavior in the crystallization pathways in relation to precursor chemicals, impurities, and hydroxyl content of this glass. Small glass monoliths were treated at the first DSC crystallization peak and quenched to determine which phases formed in the early-stages of crystallization. The glass transition temperatures (T_g) divide these six glasses between those with a T_g near 690 °C versus those near 700 °C. The DSC peak crystallization temperatures varied even more; from 855 to 917 °C. In these six glasses, our results are best explained by a combination of metastable high-BaSi₂O₅ and Ba₆Si₁₀O₂₆. Monotonic trends in crystallization show that the DSC signal from the Ba-rich phases increases as the T_g and the crystallization temperatures increase. The BS2 glasses with both the lowest T_g and lowest DSC crystallization temperatures show the most barium disilicate crystal. This leads to the conclusion that the metastable monoclinic high-BaSi₂O₅ is favored in these conditions. The small differences in glass synthesis conditions and chemicals used strongly influence the relative proportions of phases which crystallize and their kinetics. In-situ and ex-situ diffraction measurements confirm the conclusions above. The structural distinctions between the barium silicate crystals and the BS2 supercooled liquid, and the implications for the role of structural polymerization are discussed. We conclude that high-BaSi₂O₅ or Ba₆Si₁₀O₂₆ are the predominant phases in the earliest stages of crystallization. This study highlights the extreme sensitivity of BS2 glass crystallization kinetics and pathways to minor differences in composition and synthesis conditions and explains the different conclusions reached by distinct authors that worked on the crystallization of BS2 glasses.     

Study on the electrochemical behaviour of Al3+ in LiCl-KCl-AlCl3 melt

The electrochemical behaviour of Al³⁺ reduction on a tungsten electrode in LiCl-KCl-AlCl₃ molten salt was investigated by electrochemical techniques. Using cyclic voltammetry (CV) and square wave voltammetry (SWV), Al³⁺ was reduced to Al in one step, and Li was deposited on Al to form Al-Li alloys of different compositions. According to chronoamperometry (CA), co-deposition of Li-Al alloys can be obtained at cathode current densities greater than 0.045 A cm⁻² or cathode potentials lower than −2.28 V (vs. Ag/AgCl). The apparent standard potential was calculated using the equilibrium electrode potential obtained from the open-circuit chronopotentiometry. Al³⁺ diffusion coefficient calculated by CV at 703 K is 0.82 × 10⁻⁵ cm²/s. In addition, the diffusion activation energy of Al³⁺ in LiCl-KCl-AlCl₃ molten salt was also obtained using the Arrhenius equation. The linear polarization was used to calculate exchange current density at different temperatures. Based on the theoretical model of metal nucleation deposition developed by Scharifker and Hills, the nucleation process of Al³⁺ involves instantaneous nucleation in the range of 673~763 K.     

Holistic Analysis of the Tribological Interfaces of an Axial Piston Pump – Focusing on the Pump Efficiency

Research work performed on an axial piston pump is shown in a holistic manner, analyzing each lubricating interface by linking their gap height and temperature behavior to the overall pump efficiency. The temperature field and dynamic fluid film height were measured in two of the three lubricating interfaces. This is the first time that the temperature fields and gap heights were simultaneously measured in two of the main three interfaces of an axial piston machine. For a deeper analysis of the measurement data, all gaps were simulated with a numerical tool which takes solid body deformation due to temperature and pressure loads into account. This unique combination of both extensive measurement data and sophisticated simulation resulted in novel trends that clarify the complex phenomena occurring in these hydrostatic fluid films.     

The effect of specific β‐nucleation on morphology and mechanical behavior of isotactic polypropylene

The commercial grade of isotactic polypropylene was modified by a specific β‐nucleating agent in a broad concentration range. The supermolecular structure of the specimens prepared by injection molding was characterized by X‐ray scattering and correlated with mechanical behavior. It was found that at a critical nucleant concentration of 0.03 wt % the content of the β‐modification virtually reaches a saturation level. With further addition of the nucleant, the β‐phase content increases only slightly. The long period passes through a distinct maximum at the same nucleant concentration. This singularity in structure remarkably correlates with a minimum of the yield stress and maxima of strain at break and fracture toughness. Such general behavior is also reflected in the correlation between the β‐phase concentration and fracture toughness profiles along the injection‐molded bars. It is suggested that in the critically nucleated material an optimum thickness of the amorphous interlayer with connecting chains between the β‐crystallites is established, rendering the material the highest possible ductility and toughness. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1174–1184, 2002