Phase Competitions behind the Giant Magnetic Entropy Variation: Gd5Si2Ge2 and Tb5Si2Ge2 Case Studies

Magnetic materials with strong spin-lattice coupling are a powerful set of candidates for multifunctional applications because of their multiferroic, magnetocaloric (MCE), magnetostrictive and magnetoresistive effects. In these materials there is a strong competition between two states (where a state comprises an atomic and an associated magnetic structure) that leads to the occurrence of phase transitions under subtle variations of external parameters, such as temperature, magnetic field and hydrostatic pressure. In this review a general method combining detailed magnetic measurements/analysis and first principles calculations with the purpose of estimating the phase transition temperature is presented with the help of two examples (Gd5Si2Ge2 and Tb5Si2Ge2). It is demonstrated that such method is an important tool for a deeper understanding of the (de)coupled nature of each phase transition in the materials belonging to the R5(Si,Ge)4 family and most possibly can be applied to other systems. The exotic Griffiths-like phase in the framework of the R5(SixGe1-x)4 compounds is reviewed and its generalization as a requisite for strong phase competitions systems that present large magneto-responsive properties is proposed

Tailoring Negative Thermal Expansion via Tunable Induced Strain in La–Fe–Si-Based Multifunctional Material

Zero thermal expansion (ZTE) composites are typically designed by combining positive thermal expansion (PTE) with negative thermal expansion (NTE) materials acting as compensators and have many diverse applications, including in high-precision instrumentation and biomedical devices. La(Fe1–x,Six)13-based compounds display several remarkable properties, such as giant magnetocaloric effect and very large NTE at room temperature. Both are linked via strong magnetovolume coupling, which leads to sharp magnetic and volume changes occurring simultaneously across first-order phase transitions; the abrupt nature of these changes makes them unsuitable as thermal expansion compensators. To make these materials more useful practically, the mechanisms controlling the temperature over which this transition occurs and the magnitude of contraction need to be controlled. In this work, ball-milling was used to decrease particles and crystallite sizes and increase the strain in LaFe11.9Mn0.27Si1.29Hx alloys. Such size and strain tuning effectively broadened the temperature over which this transition occurs. The material’s NTE operational temperature window was expanded, and its peak was suppressed by up to 85%. This work demonstrates that induced strain is the key mechanism controlling these materials’ phase transitions. This allows the optimization of their thermal expansion toward room-temperature ZTE applications

Functionalized magnetic composite nano/ microfibres with highly oriented van der Waals CrI3 inclusions by electrospinning

This study reports on the synthesis of highly oriented chromium triiodide (CrI3) magnetic inclusions inside nano/microfibres with a polyethylene oxide matrix, prepared by the electrospinning technique. The structural, microstructural and spectroscopic analysis shows uniformly dispersed CrI3 nanosized inclusions inside the fibres, presenting a C2/m monoclinic structure at room temperature, where their c-axis is perpendicular to the fibre mat plane and the ab layers are in-plane. Analysis of the magnetic properties show that the samples have a ferromagnetic-paramagnetic phase transition at ∼55-56 K, lower than that of bulk CrI3. Noticeably, a field-driven metamagnetic transition is observed below ∼45 K, from M versus H curves, when the applied magnetic field is perpendicular to the fibre mat plane, while it is strongly reduced when the field is in-plane. This anisotropic behaviour is attributed to the field-induced changes from antiferromagnetic to ferromagnetic interlayer magnetic moment alignment along the CrI3 c-axis stacked layers. These CrI3 electrospun fibres then show an efficient cost-effective route to synthesize magnetic composite fibres with highly oriented van der Walls inclusions, for spintronic applications, taking advantage of their anisotropic 2D layered materials properties.We are grateful to the Fundacao Para a Ciencia e a Tecnologia (FCT) for the financial support through the Physics Centers of the Universities of Minho and Porto (Ref. UIDB/04650/2020) and projects UTAPEXPL/NTec/0046/2017, NORTE-01-0145-FEDER-028538 and PTDC/FIS-MAC/29454/2017. J H Belo thanks FCT for the Grant SFRH/BD/88440/2012, the project PTDC/FIS-MAC/31302/2017 and his contract DL57/2016 reference SFRH-BPD-87430/2012. J P Araujo and J H Belo thank the funding from the project, with reference POCI-01-0145-FEDER-032527. V B Isfahani acknowledges a Post-Doc grant from the project NORTE-01-0145-FEDER-028538. L Boddapati acknowledges the Nano TRAIN for Growth II program by the European Commission through the Horizon 2020 Marie Sklodowska-Curie COFUND Programme and support provided by the International Iberian Nanotechnology Laboratory. We are gratefull to Professor Michael Belsley, of the Physics Department at Minho University, for the fruitfull discussions on the manuscript

Indium segregation in Gd5(Si, Ge)4 magnetocaloric materials

Chemical substitution is one of the most efficient tools to tune and optimize magnetic and magnetocaloric properties of the giant magnetocaloric materials. In particular, Indium substitutions could be useful both for tuning properties of these interesting intermetallic materials and to unveil their local-scale behavior across the magnetostructural transition via hyperfine techniques. Hence, in order to investigate the effect of Indium additions on the crystal structure, micro-structure, magnetic and magnetocaloric properties, a series of In-containing samples derived from the base Gd5Si1.2Ge2.8 stoichiometry were prepared. The major findings are that while In is insoluble in the 5: 4 phase, it will instead promote the emergence of the impurity 5: 3 phase and segregates into this phase. Hence, In leads to major crystallographic changes, which enhance atomic disorder and disrupt the Si to Ge ratio in the 5: 4 phase. Subsequently, a higher 5: 4 unit cell volume and a lower magnetic ordering temperature are found in the In-substituted samples. Finally, the magnetocaloric properties of the In-substituted samples reveal a detrimental effect on the maximum magnetic entropy change.Work is partially supported by the projects POCI/CTM/61284/2004, PTDC/CTM-NAN/115125/2009, FEDER/POCTI n0155/94 from Fundacão para a Ciência ex Tecnologia (FCT), Portugal. A.M.P. thanks FCT for the Grant No. SFRH/BPD/63150/2009. J H Belo thanks FCT for the Grant SFRH/BD/88440/2012, the project PTDC/FISMAC/ 31302/2017 and his contract DL57/2016 reference SFRH-BPD-87430/2012. Work at IFIMUP is supported by the following funding projects: POCI-01-0145-FEDER-032527, POCI-01–0145-FEDER-029454 and CERN-FIS-PAR-0005-2017. Work at the INMA is supported by the Spanish Ministerio de Ciencia, Innovacion y Universidades through project MAT2017-82970-C2, PID2020-112914RB-I00 and Spanish DGA (grant no. E28−20R). The research at Ames Laboratory is supported by the Materials Sciences and Engineering Division, Office of Basic Energy Sciences of the U.S. Department of Energy (DOE). Ames Laboratory is operated for the U.S DOE by Iowa State University under Contract No. DE-AC02-07CH11358.Peer reviewe

Comparison of Physical/Chemical Properties of Prussian Blue Thin Films Prepared by Different Pulse and DC Electrodeposition Methods

Prussian Blue (PB) thin films were prepared by DC chronoamperometry (CHA), symmetric pulse, and non-symmetric pulse electrodeposition techniques. The formation of PB was confirmed by infrared spectroscopy (FTIR), energy-dispersive X-ray spectroscopy (EDX) and UV-Vis transmission measurements. X-ray diffraction (XRD) shows the stabilization of the insoluble form of PB. From scanning electron microscopy (SEM) studies, an increase in porosity is obtained for the shorter pulse widths, which tends to improve the total charge exchange and electrochemical stability of the films. While the film prepared by CHA suffered a degradation of 82% after 260 cycles, the degradation reduced to 24% and 34% for the samples prepared by the symmetric and non-symmetric pulse methods, respectively. Additionally, in the non-symmetric pulse film, the improvement in the charge exchange reached ~522% after 260 cycles. According to this study, the deposition time distribution affects the physical/chemical properties of PB films. These results then render pulse electrodeposition methods especially suitable to produce high-quality thin films for electrochemical devices, based on PB

Comparison of physical/chemical properties of Prussian Blue thin films prepared by different pulse and DC electrodeposition methods

Prussian Blue (PB) thin films were prepared by DC chronoamperometry (CHA), symmetric pulse, and non-symmetric pulse electrodeposition techniques. The formation of PB was confirmed by infrared spectroscopy (FTIR), energy-dispersive X-ray spectroscopy (EDX) and UV-Vis transmission measurements. X-ray diffraction (XRD) shows the stabilization of the insoluble form of PB. From scanning electron microscopy (SEM) studies, an increase in porosity is obtained for the shorter pulse widths, which tends to improve the total charge exchange and electrochemical stability of the films. While the film prepared by CHA suffered a degradation of 82% after 260 cycles, the degradation reduced to 24% and 34% for the samples prepared by the symmetric and non-symmetric pulse methods, respectively. Additionally, in the non-symmetric pulse film, the improvement in the charge exchange reached ~522% after 260 cycles. According to this study, the deposition time distribution affects the physical/chemical properties of PB films. These results then render pulse electrodeposition methods especially suitable to produce high-quality thin films for electrochemical devices, based on PB.This work was supported by the Portuguese Foundation for Science and Technology (FCT), through the projects POCI-01-0145-FEDER-029454, NORTE-01-0145-FEDER-028538, PTDC/NANMAT/0098/2020 and UID/QUI/0686/2020. It was also funded by the R&D project “SOLPOWINS”, with reference PTDC/CTM-REF/4304/2020, and E-Field- “Electric-Field Engineered Lattice Distortions (E-FiELD) for optoelectronic devices”, ref. PTDC/NAN-MAT/0098/2020, financed by the FCT

Structural dynamics of first-order phase transition in giant magnetocaloric La(Fe,Si)13: the free energy landscape

Maximizing the performance of magnetic refrigerators and thermomagnetic energy harvesters is imperative for their successful implementation and can be done by maximizing their operation frequency. One of the features delimiting the frequency and efficiency of such devices is the phase transition kinetics of their magnetocaloric/thermomagnetic active material. While previous studies have described the magnetic component governing the kinetics of the magnetovolume phase transition in La(Fe,Si)13 giant magnetocaloric materials, a comprehensive description of its structural component has yet to be explored. In this study, in situ synchrotron X-ray diffraction is employed to describe the structural changes upon magnetic field application/removal. Long magnetic field dependent relaxation times up to a few hundred seconds are observed after the driving field is paused. The phase transition is found to be highly asymmetric upon magnetic field cycling due to the different Gibbs energy landscapes and the absence of an energy barrier upon field removal. An exponential relationship is found between the energy barriers and the relaxation times, suggesting the process is governed by a non-thermal activation over an energy barrier process. Such fundamental knowledge on first-order phase transition kinetics suggests pathways for materials optimization and smarter design of magnetic field cycling in real-life devices

New Frontiers in Colorectal Cancer Treatment Combining Nanotechnology with Photo- and Radiotherapy

Colorectal cancer is the third most common cancer worldwide. Despite recent advances in the treatment of this pathology, which include a personalized approach using radio- and chemotherapies in combination with advanced surgical techniques, it is imperative to enhance the performance of these treatments and decrease their detrimental side effects on patients’ health. Nanomedicine is likely the pathway towards solving this challenge by enhancing both the therapeutic and diagnostic capabilities. In particular, plasmonic nanoparticles show remarkable potential due to their dual therapeutic functionalities as photothermal therapy agents and as radiosensitizers in radiotherapy. Their dual functionality, high biocompatibility, easy functionalization, and targeting capabilities make them potential agents for inducing efficient cancer cell death with minimal side effects. This review aims to identify the main challenges in the diagnosis and treatment of colorectal cancer. The heterogeneous nature of this cancer is also discussed from a single-cell point of view. The most relevant works in photo- and radiotherapy using nanotechnology-based therapies for colorectal cancer are addressed, ranging from in vitro studies (2D and 3D cell cultures) to in vivo studies and clinical trials. Although the results using nanoparticles as a photo- and radiosensitizers in photo- and radiotherapy are promising, preliminary studies showed that the possibility of combining both therapies must be explored to improve the treatment efficiency

Characterisation of microbial attack on archaeological bone

As part of an EU funded project to investigate the factors influencing bone preservation in the archaeological record, more than 250 bones from 41 archaeological sites in five countries spanning four climatic regions were studied for diagenetic alteration. Sites were selected to cover a range of environmental conditions and archaeological contexts. Microscopic and physical (mercury intrusion porosimetry) analyses of these bones revealed that the majority (68%) had suffered microbial attack. Furthermore, significant differences were found between animal and human bone in both the state of preservation and the type of microbial attack present. These differences in preservation might result from differences in early taphonomy of the bones. © 2003 Elsevier Science Ltd. All rights reserved