Scaling Effects in Perovskite Ferroelectrics: Fundamental Limits and Process‐Structure‐Property Relations

Ferroelectric materials are well‐suited for a variety of applications because they can offer a combination of high performance and scaled integration. Examples of note include piezoelectrics to transform between electrical and mechanical energies, capacitors used to store charge, electro‐optic devices, and nonvolatile memory storage. Accordingly, they are widely used as sensors, actuators, energy storage, and memory components, ultrasonic devices, and in consumer electronics products. Because these functional properties arise from a noncentrosymmetric crystal structure with spontaneous strain and a permanent electric dipole, the properties depend upon physical and electrical boundary conditions, and consequently, physical dimension. The change in properties with decreasing physical dimension is commonly referred to as a size effect. In thin films, size effects are widely observed, whereas in bulk ceramics, changes in properties from the values of large‐grained specimens is most notable in samples with grain sizes below several micrometers. It is important to note that ferroelectricity typically persists to length scales of about 10 nm, but below this point is often absent. Despite the stability of ferroelectricity for dimensions greater than ~10 nm, the dielectric and piezoelectric coefficients of scaled ferroelectrics are suppressed relative to their bulk counterparts, in some cases by changes up to 80%. The loss of extrinsic contributions (domain and phase boundary motion) to the electromechanical response accounts for much of this suppression. In this article, the current understanding of the underlying mechanisms for this behavior in perovskite ferroelectrics is reviewed. We focus on the intrinsic limits of ferroelectric response, the roles of electrical and mechanical boundary conditions, grain size and thickness effects, and extraneous effects related to processing. In many cases, multiple mechanisms combine to produce the observed scaling effects.     

Current Understanding of Structure–Processing–Property Relationships in BaTiO3–Bi(M)O3 Dielectrics

As part of a continued push for high permittivity dielectrics suitable for use at elevated operating temperatures and/or large electric fields, modifications of BaTiO₃ with Bi(M)O₃, where M represents a net‐trivalent B‐site occupied by one or more species, have received a great deal of recent attention. Materials in this composition family exhibit weakly coupled relaxor behavior that is not only remarkably stable at high temperatures and under large electric fields, but is also quite similar across various identities of M. Moderate levels of Bi content (as much as 50 mol%) appear to be crucial to the stability of the dielectric response. In addition, the presence of significant Bi reduces the processing temperatures required for densification and increases the required oxygen content in processing atmospheres relative to traditional X7R‐type BaTiO₃‐based dielectrics. Although detailed understanding of the structure–processing–property relationships in this class of materials is still in its infancy, this article reviews the current state of understanding of the mechanisms underlying the high and stable values of both relative permittivity and resistivity that are characteristic of BaTiO₃‐Bi(M)O₃ dielectrics as well as the processing challenges and opportunities associated with these materials.     

Low temperature ferroelectric behavior in morphotropic Pb (Zr1−xTix)O3

We provide an insight into the switching of near‐morphotropic composition of PZT, using molecular dynamics simulations and electrical measurements. The simulations and experiments exhibit qualitatively similar hysteretic behavior of the polarization for different temperatures showing widening of the P‐E loops and the decrease in the coercive field toward high temperatures. Remarkably, we have shown that polarization switching at low temperatures occurs via polarization rotation, that is a fundamentally different mechanism from high‐temperature switching, which is nucleation driven.     

Techniques for monitoring protein misfolding and aggregation in vitro and in living cells

Protein misfolding and aggregation have been considered important in understanding many neurodegenerative diseases and recombinant biopharmaceutical production. Various traditional and modern techniques have been utilized to monitor protein aggregation in vitro and in living cells. Fibril formation, morphology and secondary structure content of amyloidogenic proteins in vitro have been monitored by molecular probes, TEM/AFM, and CD/FTIR analyses, respectively. Protein aggregation in living cells has been qualitatively or quantitatively monitored by numerous molecular folding reporters based on either fluorescent protein or enzyme. Aggregation of a target protein is directly correlated to the changes in fluorescence or enzyme activity of the folding reporter fused to the target protein, which allows non-invasive monitoring aggregation of the target protein in living cells. Advances in the techniques used to monitor protein aggregation in vitro and in living cells have greatly facilitated the understanding of the molecular mechanism of amyloidogenic protein aggregation associated with neurodegenerative diseases, optimizing culture conditions to reduce aggregation of biopharmaceuticals expressed in living cells, and screening of small molecule libraries in the search for protein aggregation inhibitors.     

Cytotoxic salan-titanium(IV) complexes: high activity toward a range of sensitive and drug-resistant cell lines, and mechanistic insights

The cytotoxicities of highly efficient salan-Ti(IV) complexes toward a range of cell lines, including drug-resistant cells, are reported along with preliminary mechanistic insights. Five salan-Ti(IV) complexes were investigated toward eight different human and murine cancer-derived cell lines, including colon, ovarian, lung, cervical, pancreatic, leukemic, skin, and breast. The salan complexes are more active toward the cells analyzed than cisplatin and the known titanium compound (bzac)(2) Ti(OiPr)(2) , and no cell line resistant to the salan complexes was identified. Moreover, the salan-Ti(IV) complexes are highly active toward both cisplatin-sensitive (A2780) and cisplatin-resistant (A2780CisR) human ovarian cancer cell lines. Similarly, the salan complexes are cytotoxic toward multi-drug-resistant (ABCB1-expressing) mouse lymphoma cell lines HU-1 and HU-2. Importantly, minimal or no activity was observed toward primary murine cells (bone marrow, heart, liver, kidney, spleen, and lung), supporting selectivity for cancer cells. Additionally, the salan complexes maintain high cytotoxicity for up to 24 h following exposure to cell culture medium, whereas reference complexes (bzac)(2) Ti(OiPr)(2) and Cp(2) TiCl(2) rapidly lose much of their activity upon exposure to medium, within ~1 h. The upregulation of p53 followed by cell-cycle arrest in G(1) phase is likely one mechanism of action of the salan complexes. Taken together, the results indicate that these compounds are selectively toxic to cancer cells and are able to circumvent two independent mechanisms of drug resistance, thus expanding the scope of their potential medicinal utility.     

大堆积密度骨料配制的混凝土的性能(英文)

当今世界对可持续发展的关注促进了低水泥用量混凝土建筑工程的产生。增加混凝土中骨料体系的堆积密度是降低水泥用量的一个策略。增加骨料体系的堆积密度可以降低填充骨料颗粒间隙所需要的水泥浆体的量。研究了大堆积密度骨料配制的混凝土。这些混凝土比普通的结构混凝土低15%～25%的水泥用量,当骨料体系级配合理时混凝土工作性好。水泥浆体体积的降低在明显改进混凝土干缩与徐变性能的同时,也会对其工作性产生不利影响。骨料含量不会显著影响不同配比混凝土的抗压强度和劈裂强度。     

Spontaneous Imbibition Experiments of Enhanced Oil Recovery with Surfactants and Complex Nano-Fluids

Two types of porous media were analyzed with the intention of exploring alternative enhanced oil recovery methods. Core samples were taken from the Tensleep Formation of the Black Mountain Field in Hot Springs County, WY. The lithology is mainly sandstone and dolomite. The measured effective porosity values ranged from 13.0 to 18.0%, and permeabilities from 19 to 68 md. Production from the Tensleep and Phosphoria formations using conventional methods has resulted in a low secondary recovery factor, possibly due to high capillary forces and an oil-wet formation. Different surfactants were investigated to determine the viability of a possible enhanced oil recovery process using a spontaneous imbibition process in Amott cells. A very high enhanced recovery factor of more than 89% was achieved using a complex nano-fluid that consists of a mixture of surfactant, solvent, co-solvent and water. These recovery factors compared with 13% by brine imbibition and up to 21% using commercial surfactants. At the other end of the scale, very high porosity volcanic pumice was also subjected to the same tests. For this rock the porosity values ranged from 65 to 90% and permeabilities were 2.0–2.7 d. Secondary recovery showed values up to 81% on spontaneous imbibition and up to 91% when surfactants were employed. These experimental results indicate that pumice has favorable reservoir characteristics, but, due to its weak brittle nature, it would not be expected that it could withstand the overburden stress at any significant depth. However, it does represent a useful laboratory specimen.     

Application of a Technofunctional Caseinate Hydrolysate to Replace Surfactants in Ice Cream

There is a demand for a clean label of ice cream in the food industry. To meet this requirement, alternative surfactants and hydrocolloids without an additive number have to be found. Here, a caseinate hydrolysate with improved interfacial properties was investigated as such an additive. Replacing only the surfactant resulted in ice cream characteristics, comparable to using a commercial emulsifier (INS 472b). Thus, a clean labeling of the surfactant using this hydrolysate is possible. By contrast, replacing the hydrocolloid additionally led to an unfavorable ice cream texture and stability.     

CO2 capture efficiency in post‐combustion using MWNT‐PAA in a packed bed column

The adsorption capacity of polyaspartamide (PAA) and multi‐wall carbon nanotubes with polyaspartamide (MWNT‐PAA) was investigated through a packed bed column with the flowing of flue gas composed of 15 % CO₂, 5 % O₂ and the balance N₂. The adsorption performed at 25 °C, 110 kPa and inlet gas flow rate of 60 mL/min resulted in high CO₂ adsorption capacity of 5.70 and 10.20 mmol‐CO₂/g for PAA and MWNT‐PAA, respectively. The adsorption kinetics was very high, so 7 min were enough for the effluent gas to reach the breakthrough after saturation. The consistency of adsorbents in recurring regeneration was successful through a continuous TSA system of 10 cycle adsorption‐desorption with temperatures of 25–100 °C. The evaluation of heat through differential scanning calorimetry (DSC) resulted in exothermic adsorption with heat release of 45.14 kJ/mol and 124.38 kJ/mol for PAA and MWNT‐PAA, respectively. The heat release was found favourable to promote the desorption as the temperature could rise after adsorption. This is an advantage for energy efficiency, as it depicts the potential of energy recovery. Thus, both adsorbent PAA and MWNT‐PAA were demonstrated to be promising for CO₂ adsorption capture in post‐combustion.