Structure and Corrosion Behavior of Multiphase Intermetallic ZrCu-Based Alloys.

Zirconium-based alloys are highly regarded by the research community for their exceptional corrosion resistance, thermal stability, and mechanical properties. In our work, we investigated two newly developed alloys, Zr42.42Cu41.18Al9.35Ag7.05 and Zr46.81Cu35.44Al10.09Ag7.66, in the form of ingots and ribbons. In the course of our investigation, we conducted a comprehensive structural and thermal analysis. In addition, an examination of the corrosion activity encompassing electrochemical studies and an analysis of the corrosion mechanisms was carried out. To further evaluate the performance of the materials, tests of their mechanical properties were performed, including microhardness and resistance to abrasive wear. Structural analysis showed that both alloys studied had a multiphase, crystalline structure with intermetallic phases. The samples in the form of ribbons showed improved corrosion resistance compared to that of the ingots. The ingot containing a higher content of copper Zr42.42Cu41.18Al9.35Ag7.05 was characterized by better corrosion resistance, while showing lower average hardness and a higher degree of abrasive wear based on SEM observations after pin-on-disc tests.

Energetic Coordination Compounds: Investigation of Aliphatic Ligands and Development of Prototype Detonators.

In this work, energetic coordination compounds (ECCs) of transition metals (Fe, Ni, Cu, Zn) containing aliphatic amines as ligands were synthesized: ethylenediamine; 1,3-diaminopropane; tris(2-aminoethyl)amine; tris(3-aminopropyl)amine. The compounds were investigated in terms of ignition/explosion temperature, friction and impact sensitivity. For selected compounds, structural characterisation was presented (IR-ATR spectroscopy, Raman spectroscopy) and their morphology was determined (SEM, powder XRD). They were also investigated by differential scanning calorimetry (DSC). In order to assess the potential application of selected ECCs in detonators, underwater explosion tests were carried out, determining energetic performance. The results achieved for detonators containing ECCs were compared with those for reference detonators (containing pentaerythritol tetranitrate, PETN), indicating their potential use as a "green" alternative to nitric acid esters.

Ti/CuO Nanothermite-Study of the Combustion Process.

A study of the combustion processes of Ti/CuO and Ti/CuO/NC nanothermites prepared via electrospraying was conducted in this work. For this purpose, the compositions were thermally conditioned at 350, 550 and 750 °C, as selected based on our initial differential scanning calorimetry-thermogravimetry (DSC/TG) investigations. The tested compositions were analysed for chemical composition and morphology using SEM-EDS, Raman spectroscopy and XRD measurements. Additionally, the thermal behaviour and decomposition kinetics of compositions were explored by means of DSC/TG. The Kissinger and Ozawa methods were applied to the DSC curves to calculate the reaction activation energy. SEM-EDS analyses indicated that sintering accelerated with increasing equivalence ratio and there was a strong effect on the sintering process due to cellulose nitrate (NC) addition. The main combustion reaction was found to start at 420-450 °C, as confirmed by XRD and Raman study of samples annealed at 350 °C and 550 °C. Moreover, increasing the fuel content in the composition led to lower Ea, higher reaction heats and a more violent combustion process. Conversely, the addition of NC had an ambiguous effect on Ea. Finally, a multi-step combustion mechanism was proposed and is to some extent in line with the more general reactive sintering (RS) mechanism. However, unusual mass transfer was observed, i.e., to the fuel core, rather than the opposite, which is typically observed for Al-based nanothermites.

Influence of Nb and Mo Substitution on the Structure and Magnetic Properties of a Rapidly Quenched Fe79.4Co5Cu0.6B15 Alloy.

The importance of amorphous and nanocrystalline Fe-based soft magnetic materials is increasing annually. Thus, characterisation of the chemical compositions, alloying additives, and crystal structures is significant for obtaining the appropriate functional properties. The purpose of this work is to present comparative studies on the influence of Nb (1, 2, 3 at.%) and Mo (1, 2, 3 at.%) in Fe substitution on the thermal stability, crystal structure, and magnetic properties of a rapidly quenched Fe79.4Co5Cu0.6B15 alloy. Additional heat treatments in a vacuum (260-640 °C) were performed for all samples based on the crystallisation kinetics. Substantial improvement in thermal stability was achieved with increasing Nb substitution, while this effect was less noticeable for Mo-containing alloys. The heat treatment optimisation process showed that the least lossy states (with a minimum value of coercivity below 10 A/m and high saturation induction up to 1.7 T) were the intermediate state of the relaxed amorphous state and the nanocomposite state of nanocrystals immersed in the amorphous matrix obtained by annealing in the temperature range of 340-360 °C for 20 min. Only for the alloy with the highest thermal stability (Nb = 3%), the α-Fe(Co) nanograin grows, without the co-participation of the hard magnetic Fe3B, in a relatively wide range of annealing temperatures up to 460 °C, where the second local minimum in coercivity and core power losses exists. For the remaining annealed alloys, due to lower thermal stability than the Nb = 3% alloy, the Fe3B phase starts to crystallise at lower annealing temperatures, making an essential contribution to magneto-crystalline anisotropy, thus the substantial increase in coercivity and induction saturation. The air-annealing process tested on the studied alloys for optimal annealing conditions has potential use for this type of material. Additionally, optimally annealed Mo-containing alloys are less lossy materials than Nb-containing alloys in a frequency range up to 400 kHz and magnetic induction up to 0.8 T.

Study of the Combustion Mechanism of Zn/KMnO4 Pyrotechnic Composition.

This work aims to investigate the combustion mechanism for a pyrotechnic delay composition (PDC), consisting of zinc powder as a fuel and KMnO4 as an oxidising agent. For this purpose, the compositions were thermally conditioned at several set temperatures, chosen based on our previous work. Tests were also performed for post-combustion residues obtained via combustion of the PDCs in a manometric bomb. The samples were examined by scanning electron microscopy (SEM), Raman spectroscopy and X-ray diffractometry (XRD). Furthermore, the obtained results were correlated with previous studies by the authors and compared with data available in the literature. On the basis of tests carried out for thermally conditioned samples, a combustion mechanism was determined for Zn/KMnO4 as a function of temperature. The results show that the combustion process dynamics are independent of equilibrium ratio and limited mainly by diffusion of liquid fuel into the solid oxidising agent. Moreover, it has been revealed that Raman spectroscopy can be effectively used to determine combustion mechanisms for pyrotechnic compositions.

Production of Electrolytic Composite Powder by Nickel Plating of Shredded Polyurethane Foam.

Ni-poly(DPU) composite powder was produced under galvanostatic conditions from a nickel bath with the addition of pulverized polymer obtained during the shredding of polyurethane foam (poly(DPU)). The Ni-poly(DPU) composite powder was characterized by the presence of polymer particles covered with an electrolytical amorphous-nanocrystalline nickel coating. The phase structure, chemical composition, morphology, and the distribution of elements was investigated. The chemical analysis showed that the powder contains 41.7% Ni, 16.4% C, 15.7% O, 8.2% P and 0.10% S. The other components were not determined (nitrogen and hydrogen). The phase analysis showed the presence of NiC phase. Composite powder particles are created as a result of the adsorption of Me ions on the fragmented polymer. The current flowing through the galvanic bath forces the flow of the particles. The foam particles with adsorbed nickel ions are transported to the cathode surface, where the Ni2+ is discharged. The presence of compound phosphorus in galvanic solution generates the formation of amorphous-nanocrystalline nickel, which covers the polymer particles. The formed nickel-polymer composite powder falls to the bottom of the cell.

Structure and Magnetic Properties of Thermodynamically Predicted Rapidly Quenched Fe85-xCuxB15 Alloys.

In this work, based on the thermodynamic prediction, the comprehensive studies of the influence of Cu for Fe substitution on the crystal structure and magnetic properties of the rapidly quenched Fe85B15 alloy in the ribbon form are performed. Using thermodynamic calculations, the parabolic shape dependence of the ΔGamoprh with a minimum value at 0.6% of Cu was predicted. The ΔGamoprh from the Cu content dependence shape is also asymmetric, and, for Cu = 0% and Cu = 1.5%, the same ΔGamoprh value is observed. The heat treatment optimization process of all alloys showed that the least lossy (with a minimum value of core power losses) is the nanocomposite state of nanocrystals immersed in an amorphous matrix obtained by annealing in the temperature range of 300-330 °C for 20 min. The minimum value of core power losses P10/50 (core power losses at 1T@50Hz) of optimally annealed Fe85-xCuxB15 x = 0,0.6,1.2% alloys come from completely different crystallization states of nanocomposite materials, but it strongly correlates with Cu content and, thus, a number of nucleation sites. The TEM observations showed that, for the Cu-free alloy, the least lossy crystal structure is related to 2-3 nm short-ordered clusters; for the Cu = 0.6% alloy, only the limited value of several α-Fe nanograins are found, while for the Cu-rich alloy with Cu = 1.2%, the average diameter of nanograins is about 26 nm, and they are randomly distributed in the amorphous matrix. The only high number of nucleation sites in the Cu = 1.2% alloy allows for a sufficient level of grains' coarsening of the α-Fe phase that strongly enhances the ferromagnetic exchange between the α-Fe nanocrystals, which is clearly seen with the increasing value of saturation induction up to 1.7T. The air-annealing process tested on studied alloys for optimal annealing conditions proves the possibility of its use for this type of material.

Effect of Co Substitution and Thermo-Magnetic Treatment on the Structure and Induced Magnetic Anisotropy of Fe84.5-xCoxNb5B8.5P2 Nanocrystalline Alloys.

In the present work, we investigated in detail the thermal/crystallization behavior and magnetic properties of materials with Fe84.5-xCoxNb5B8.5P2 (x = 0, 5, 10, 15 and 20 at.%) composition. The amorphous ribbons were manufactured on a semi-industrial scale by the melt-spinning technique. The subsequent nanocrystallization processes were carried out under different conditions (with/without magnetic field). The comprehensive studies have been carried out using differential scanning calorimetry, X-ray diffractometry, transmission electron microscopy, hysteresis loop analyses, vibrating sample magnetometry and Mössbauer spectroscopy. Moreover, the frequency (up to 300 kHz) dependence of power losses and permeability at a magnetic induction up to 0.9 T was investigated. On the basis of some of the results obtained, we calculated the values of the activation energies and the induced magnetic anisotropies. The X-ray diffraction results confirm the surface crystallization effect previously observed for phosphorous-containing alloys. The in situ microscopic observations of crystallization describe this process in detail in accordance with the calorimetry results. Furthermore, the effect of Co content on the phase composition and the influence of annealing in an external magnetic field on magnetic properties, including the orientation of the magnetic spins, have been studied using various magnetic techniques. Finally, nanocrystalline Fe64.5Co20Nb5B8.5P2 cores were prepared after transverse thermo-magnetic heat treatment and installed in industrially available portable heating equipment.

Influence of Cu Content on Structure, Thermal Stability and Magnetic Properties in Fe72-xNi8Nb4CuxSi2B14 Alloys.

The effect of substitution of Fe by Cu on the crystal structure and magnetic properties of Fe72-xNi8Nb4CuxSi2B14 alloys (x = 0.6, 1.1, 1.6 at.%) in the form of ribbons was investigated. The chemical composition of the materials was established on the basis of the calculated minima of thermodynamic parameters: Gibbs free energy of amorphous phase formation ΔGamorph (minimum at 0.6 at.% of Cu) and Gibbs free energy of mixing ΔGmix (minimum at 1.6 at.% of Cu). The characteristic crystallization temperatures Tx1onset and Tx1 of the alpha-iron phase together with the activation energy Ea for the as-spun samples were determined by differential scanning calorimetry (DSC) with a heating rate of 10-100 °C/min. In order to determine the optimal soft magnetic properties, the wound cores were subjected to a controlled isothermal annealing process in the temperature range of 340-640 °C for 20 min. Coercivity Hc, saturation induction Bs and core power losses at B = 1 T and frequency f = 50 Hz P10/50 were determined for all samples. Moreover, for the samples with the lowest Hc and P10/50, the magnetic losses were determined in a wider frequency range 50 Hz-400 kHz. The real and imaginary parts of the magnetic permeability µ', µâ€³ along with the cut-off frequency were determined for the samples annealed at 360, 460, and 560 °C. The best soft magnetic properties (i.e., the lowest value of Hc and P10/50) were observed for samples annealed at 460 °C, with Hc = 4.88-5.69 A/m, Bs = 1.18-1.24 T, P10/50 = 0.072-0.084 W/kg, µ' = 8350-10,630 and cutoff frequency at 8-9.3 × 104 Hz. The structural study of as-spun and annealed ribbons was carried out using X-ray diffraction (XRD) and a transmission electron microscope (TEM).

The Structure and Magnetic Properties of Rapidly Quenched Fe72Ni8Nb4Si2B14 Alloy.

The complex structural and magnetic studies of the annealed rapidly quenched Cu-free Fe72Ni8Nb4Si2B14 alloy (metallic ribbons form) are reported here. Based on the calorimetric results, the conventional heat treatment process (with heating rate 10 °C/min and subsequent isothermal annealing for 20 min) for wound toroidal cores has been optimized to obtain the least lossy magnetic properties (for the minimum value of coercivity and magnetic core losses at 50 Hz). For optimal conditions, the complex permeability in the 104-108 Hz frequency range together with core power losses obtained from magnetic induction dependence up to the frequency of 400 kHz was successfully measured. The average and local crystal structure was investigated by the use of the X-ray diffraction method and the transmission electron microscopy observations and proved its fully glassy state. Additionally, for the three temperature values, i.e., 310, 340 and 370 °C, the glass relaxation process study in the function of annealing time was carried out to obtain a deeper insight into the soft magnetic properties: magnetic permeability and cut-off frequency. For this type of Cu-free soft magnetic materials, the control of glass relaxation process (time and temperature) is extremely important to obtain proper magnetic properties.

Fe-Co-B Soft Magnetic Ribbons: Crystallization Process, Microstructure and Coercivity.

In this work, a detailed microstructural investigation of as-melt-spun and heat-treated Fe67Co20B13 ribbons was performed. The as-melt-spun ribbon was predominantly amorphous at room temperature. Subsequent heating demonstrated an amorphous to crystalline α-(Fe,Co) phase transition at 403 °C. In situ transmission electron microscopy observations, carried out at the temperature range of 25-500 °C and with the heating rate of 200 °C/min, showed that the first crystallized nuclei appeared at a temperature close to 370 °C. With a further increase of temperature, the volume of α-(Fe,Co) crystallites considerably increased. Moreover, the results showed that a heating rate of 200 °C/min provides for a fine and homogenous microstructure with the α-(Fe,Co) crystallites size three times smaller than when the ribbon is heated at 20 °C/min. The next step of this research concerned the influence of both the annealing time and temperature on the microstructure and coercivity of the ribbons. It was shown that annealing at 485 °C for a shorter time (2 s) led to materials with homogenous distribution of α-(Fe,Co) crystallites with a mean size of 30 nm dispersed in the residual amorphous matrix. This was reflected in the coercivity (20.5 A/m), which significantly depended on the volume fraction of crystallites, their size, and distribution.

Influence of Cu Content on Structure and Magnetic Properties in Fe86-xCuxB14 Alloys.

Influence of Cu content on thermodynamic parameters (configurational entropy, Gibbs free energy of mixing, Gibbs free energy of amorphous phase formation), crystallization kinetics, structure and magnetic properties of Fe86-xCuxB14 (x = 0, 0.4, 0.55, 0.7, 1) alloys is investigated. The chemical composition has been optimized using a thermodynamic approach to obtain a minimum of Gibbs free energy of amorphous phase formation (minimum at 0.55 at.% of Cu). By using differential scanning calorimetry method the crystallization kinetics of amorphous melt-spun ribbons was analyzed. It was found that the average activation energy of α-Fe phase crystallization is in the range from 201.8 to 228.74 kJ/mol for studied samples. In order to obtain the lowest power core loss values, the isothermal annealing process was optimized in the temperature range from 260 °C to 400 °C. Materials annealed at optimal temperature had power core losses at 1 T/50 Hz-0.13-0.25 W/kg, magnetic saturation-1.47-1.6 T and coercivity-9.71-13.1 A/m. These samples were characterized by the amorphous structure with small amount of α-Fe nanocrystallites. The studies of complex permeability allowed to determine a minimum of both permeability values at 0.55 at.% of Cu. At the end of this work a correlation between thermodynamic parameters and kinetics, structure and magnetic properties were described.

Effect of Co Substitution on Crystallization and Magnetic Behavior of Fe85.45-xCoxCu0.55B14 Metallic Glass.

The effects of Co for Fe substitution on magnetic properties, thermal stability and crystal structure of Fe85.45-xCoxCu0.55B14 (x = 0, 2.5, 5, 7.5, 10) melt spun amorphous alloys were investigated. The Cu content was firstly optimized to minimize the energy of amorphous phase formation by the use of a thermodynamic approach. The formation of crystalline α-Fe type phase has been described using differential scanning calorimetry, X-ray diffractometry and transmission electron microscopy. The classical heat treatment process (with heating rate 10 °C/min) in vacuum for wound toroidal cores was optimized in the temperature range from 280 to 430 °C in order to obtain the best magnetic properties (magnetic saturation Bs and coercivity Hc obtained from the B(H) dependencies) at 50 Hz frequency. For optimal heat-treated samples, the complex magnetic permeability in the frequencies 104-108 Hz at room temperature was measured. Finally, magnetic core losses were obtained for 1 T/50 Hz and 1.5 T/50 Hz values for samples annealed at T = 310 °C. An analysis of transmission electron microscope images and electron diffraction patterns confirmed that high magnetic parameters are related to the coexistence of the amorphous and nanocrystalline phases.

Dielectric and electromagnetic interference shielding properties of high entropy (Zn,Fe,Ni,Mg,Cd)Fe2O4 ferrite.

The new (Zn,Mg,Ni,Fe,Cd)Fe2O4 high entropy ferrite with average crystallite size 11.8 nm was synthesized in two stages by annealing of co-precipitated amorphous precursor. The dielectric spectroscopy confirms, that the electrical conductivity and polarization processes are associated with the mobility of electrons in the structure of ferrite. It was concluded, that the both, high frequency complex dielectric permittivity as well as complex magnetic permeability are strongly temperature and frequency dependent. The AC electrical conductivity is associated with quantum mechanical tunneling of electrons and related to the transfer of charge carriers between Fe2+ and Fe3+ ions. Moreover, the microwave absorption properties were determined. The best microwave absorption properties have been confirmed in the frequency range 1.9 to 2.1 GHz for a layer which is 0.8-1 cm thick. For this range, reflection loss (RL) is lower than -25 dB and shielding effectiveness (SE) lower than -50 dB.

Magnetocaloric Properties of Mn1.1Fe0.9P0.5As0.5-xGex (0 ≤ x ≤ 0.1) Compounds.

Intermetallic compounds with the overall formula Mn1.1Fe0.9P0.5As0.5-xGex (x varies from 0 to 0.1) were investigated in order to study their magnetocaloric effect by monitoring the adiabatic temperature change, magnetic entropy change and their relation to structural parameters. It was found that the maximum of magnetocaloric effect was achieved for x = 0.02. Adiabatic temperature change for consolidated powder was equal to 2.75 K for the magnetic field change ΔB = 1.7 T for the sample with x = 0.02. For the pure non-doped sample, this parameter is much lower: ΔTad = 1.7 K @ ΔB = 1.7 T. This result was correlated with the change of structural parameters such as lattice constants and the unit cell volume.

Conversion of Natural Tannin to Hydrothermal and Graphene-Like Carbons Studied by Wide-Angle X-ray Scattering.

The atomic structure of carbon materials prepared from natural tannin by two different techniques, high-temperature pyrolysis and low-temperature hydrothermal carbonization, was studied by wide-angle X-ray scattering. The obtained diffraction data were converted to the real space representation in the form of pair distribution functions. The X-ray photoelectron spectroscopy measurements provided information about the chemical state of carbon in tannin-based materials that was used to construct final structural models of the investigated samples. The results of the experimental data in both reciprocal and real spaces were compared with computer simulations based on the PM7 semiempirical quantum chemical method. Using the collected detailed information, structural models of the tannin-based carbons were proposed. The characteristics of the investigated materials at the atomic level were discussed in relation to their preparation method. The rearrangement of the tannin molecular structure and its transformation to graphene-like structure was described. The structure of tannin-based carbons pyrolyzed at 900 °C exhibited coherently scattering domains about 20 Å in size, consisting of two defected atomic layers and resembling a graphene-like arrangement.

Effect of cryogrinding on chemical stability of the sparingly water-soluble drug furosemide.

PURPOSE: To investigate the effect of cryogrinding on chemical stability of the diuretic agent furosemide and its mixtures with selected excipients. METHODS: Furosemide was ground at liquid nitrogen temperature for 30, 60, 120 and 180 min. Mixtures of furosemide-PVP and furosemide-inulin (1:1) were milled under cryogenic conditions. Materials were analyzed by XRD, UPLC, MS and NMR. RESULTS: Upon increasing the milling time, a significant build-up of an unidentified impurity 1, probably the main degradation product, was noticed. Cogrinding of furosemide with PVP and inulin worsened chemical stabilization of the pharmaceutical. The main degradation product formed upon cryomilling was subsequently identified as 4-chloro-5-sulfamoylanthranilic acid (CSA). Based on some theoretical considerations involving specific milling conditions, the milling intensity and an expected specific milling dose have been calculated. Results indicate that cryogenic grinding is capable to initiate mechanically induced decomposition of furosemide. CONCLUSIONS: Cryogenic grinding can activate and accelerate not only structural changes (solid state amorphization) but also chemical decomposition of pharmaceuticals. A cryogenic milling device should be considered as a chemical reactor, where under favourable conditions chemical reactions could be mechanically initiated.