Magnesium alloys, with good biocompatibility and mechanical-compatibility, can be developed as next generation promising biomaterials. This paper summerizes the principle and the cutting-edge advances of alloying of magnesium alloys as degradable biomaterials. The effects of alloy elements on the material and biological properties of magnesium alloys are analyzed. The focus is laid on the influence of microstructure (grain size, secondary phase or intermetallic compound, long-period stacking ordered (LPSO) phase and quasi-crystal phase), heat treatment and surface oxide film on degradation and their critical progress on corrosion morphology and mechanism. Several outlooks on bio-magnesium alloys are proposed.
High strength Fe-Ni base austenitic alloys, such as A286 and JBK-75, are widely used in gas turbine jet engines and hydrogen service and so on because of their excellent corrosion resistance and low hydrogen embrittlement sensitivity. The ordered coherent γ' [Ni3(Al,Ti)], precipitated during ageing, is thought to have the main contribution on the strength. Thus, it is very important to understand the characterization of the precipitation. However, few previous studies are focused on atomic scale evolution of the precipitated phase. Atom probe tomography (APT) is a unique microscopy technique that provides 3D analytical mapping of materials at near atomic resolution and a high detection sensitivity for all elements. The present research is focused on the microstructure evolution at ageing temperature at different time scales using APT. A Fe-Ni base austenite alloy were aged at 620 ℃ for different time after solution treated at 980 ℃ for 2 h. Hardness testing indicates that a sharp increase is observed when the ageing time is less than 6 h. The hardness is up to 205 HV from the initial 145 HV at the ageing time 6 h. After that the hardness increases slowly. The hardness is 251 HV at 120 h. APT results reveal that Ti-rich nanoclusters precipitate obviously at the initial stage of ageing, which contain Fe, Cr, Ni, Mo and Al elements. As the ageing time increases, more Ni and Al atoms are segregated in the Ti-rich nanoclusters while the Fe, Cr and Mo are ejected from the nanoclusters. When the ageing time is up to 120 h, the Ni/(Ti+Al) ration is approximately close to 3. The precipitates can be identified as γ' phase. The results reveal that the formation of γ' involves nucleation and growth. Effect of the number density and the size of the γ' precipitates on the hardening of the alloy has been estimated.
42CrMo steel was widely used in many industry fields for its excellent hardenability and high temperature strength. Many transmission mechanisms and fasteners, such as roller and heat-resistant gear, are made of this steel. However, the ductility of 42CrMo steel is relatively low after quenching and tempering. During high tempering Mo riched carbides at grain boundary and undecomposable martensite at low tempering are the main reasons for poor ductility of 42CrMo steel. Grain refinement can enhance both strength and ductility significantly, but traditional refinement technology will cause intergranular oxidation so that strengthening effect was weak. Although thermomechanical treatment can achieve dynamic recrystallization, its refinement effect is unstable. Elecropulsing treatment, which makes significant change in microstructure and properties of metals, has been applied in many fields such as, modification of solidified microstructure of liquid metal, healing of fatigue crack, nanocrystallization of amorphous materials and so on. Moreover, this process can produce superior mechanical properties in metals. In order to improve the mechanical properties of 42CrMo steel better, high-energy and instantaneous electropulsing treatment was applied. In this contribution, 42CrMo steel was subjected to traditional and electropulsing treatment individually. It was found that EPQ treatment (480 ms electropulsing treatment, water cooled) results in finer grain, promoting the formation of retained austenite and twin martensite; EPT treatment (180 ms electropulsing treatment, air cooled) can stabilize retained austenite in EPQ specimen and induce multiphase structure. Mechanical properties results indicate that strength-ductility balance of EPQ and EPQ+EPT specimen are 32% and 13.9% higher than that of TQ (traditional quenched) and EPQ+TT (traditional tempered) specimen respectively.
Fatigue fracture is the main failure forms of drill steel, and the hard oxide with large size is one of the main reasons for the fatigue fracture of drill steel. Therefore, the miniaturization and softening of inclusion can effectively improve the anti-fatigue performance of drill steel and prolong its service life. Rare earth elements have very good affinity with oxygen and sulfur in molten steel, and the hardness of resulting rare earth compounds is very low. In this work, the rare earth element cerium was added into drill steel to investigate the effect of Ce on the MgAl2O4 and sulfides. The composition, morphology, number, and size of inclusions in drill steel were analyzed by using SEM and EDS. The evolution process and modification mechanism of Ce on MgAl2O4 and sulfides were clarified by experimental results and calculated by thermodynamic software. The type of inclusions in drill steel without Ce addition is MgAl2O4 and (Ca, Mn)S. As the Ce content in drill steel reaches to 0.0078% (mass fraction), the type of inclusions changes to Ce-O and Ce-S. In addition, a few complex inclusions, mixture of Ce-O and MgO, were also found. The size of inclusions in drill steel decreases significantly as the oxides and sulfides were modified into Ce-O and Ce-S. The calculated results show that MgAl2O4 and (Ca, Mn)S in drill steel can be effectively modified into Ce-O and Ce-S as the Ce added into molten steel, and the modification sequence of Ce on the MgAl2O4 is as follows: MgAl2O4→CeAlO3+MgO→Ce2O3+MgO→Ce2O3. The content of Ce in drill steel has great influence on the type of inclusions. The modification mechanism of Ce on MgAl2O4 calculated by Factsage 6.3 agrees well with the experimental observations.
β-type alloys have a wide application prospect in aerospace, biomedical and marine engineering and other fields, owing to their high specific strength, good corrosion resistance and low elastic modulus. Their yield strength and uniform elongation are affected by the second phase precipitation, plastic deformation mode and interstitial element, especially the oxygen element. In this work, the effect of tensile pre-deformation induced {332}<113> twins combined with isothermal ω-phase after subsequent ageing on the mechanical properties of β-type Ti-15Mo alloy with different oxygen contents from 0.1% to 0.5% (mass fraction) was examined by OM, XRD, TEM and DSC, Vickers hardness tester and tensile testing machine. The results indicated that with increasing the oxygen content, the formation of mechanical twins and isothermal ω-phase in the alloy was suppressed, and the effect of pre-deformation induced twins on the precipitation of isothermal ω-phase was negligible. After pre-deformation combined with subsequent ageing, the alloy with low oxygen content had the relatively high yield strength and large uniform elongation, but it with high oxygen content exhibited the brittle fracture. A good combination of strength with ductility in the alloy with low oxygen content was contributed to the twinning and dislocation slip coupled deformation. The high yield strength was mainly dominated by the dislocation slip, and the large uniform elongation was due to the static and dynamic grain refinement effects, which were caused by the pre-deformation induced twins and subsequent twinning deformation, respectively. Through utilizing the alloying element of oxygen effectively, and changing the plastic deformation mode and phase precipitation behavior based on the reasonable process of pre-deformation and heat treatment, the combination of strength and ductility can be controlled in a large range for the β-type titanium alloys.
The 6xxx series aluminum alloys (Al-Mg-Si(-Cu) alloys) are widely used for the industrial applications in the lightweight construction, automotive and architecture because of their light weight, medium to high strength, excellent formability and good corrosion resistance. It has been reported that trace Sn addition can accelerate ageing kinetics and increase peak hardness of Al-Mg-Si alloys when ageing at high temperatures (>210 ℃). However, the mechanism about it has not been investigated comprehensively yet. For Mg-excess Al-Mg-Si alloys, when aged at 250 ℃, the alloys are hardened by the β'-precipitates. While after applying natural ageing prior to artificial ageing, the β"-precipitates will be formed, with the percentage of which increasing with natural ageing time, and eventually become the main hardening precipitates. In this work, the effect of Sn on natural ageing and subsequent artificial ageing at 250 ℃ in a Mg-rich Al-Mg-Si alloy was investigated by Vickers microhardness measurements and TEM. The results show that adding a small amount (0.2%, mass fraction) of Sn in the Mg-rich Al-Mg-Si alloy can modify the precipitation pathways upon 250 ℃-ageing: when the alloy is directly artificially aged, the β"-precipitates are dominant, whereas when the alloy is subjected to "natural ageing+artificial ageing" treatment, upon prolonged natural ageing time, the percentage of β"-precipitates would not increase but decrease and that of β'-precipitates would not decrease but increase, but ultimately the β"-precipitates are still dominant over the β'-precipitates. The Sn-induced modification of the precipitation pathways can significantly enhance the age-hardening potential of the alloy upon high-temperature artificial ageing. The addition of Sn increases the effective Si-concentration in the matrix, and consequently changes the precipitation pathways in the Sn-free alloy, which is different from the explanation proposed in literatures.
Magnetic anisotropy is one of the most important fundamental properties of magnetic thin film. The strength of magnetic anisotropy determines the ferromagnetic resonance frequency of magnetic films in the high-frequency applications. Because of the directionality of conventional static magnetic anisotropy in magnetic film, the high-frequency device usually shows an obvious directionality. When the microwave magnetic ?eld deviates from the perpendicular direction of magnetic anisotropy, the devices cannot reveal their best performance. The magnetic ?lm with a stripe magnetic domain structure displays an in-plane rotatable magnetic anisotropy, which can be an important strategy to solve the problem of magnetic ?eld orientation dependent performance in high-frequency device. Therefore, the magnetic domain, the magnetic anisotropy, and the high-frequency behaviors for magnetic ?lms with a stripe magnetic domain structure have received extensive attention. Previously, most of the studies focused on the stripe magnetic domain structure of polycrystalline thin films. However, less attention was paid on amorphous magnetic thin films. Since the amorphous magnetic films have no long-range ordered crystal structure, no magnetocrystalline anisotropy, no grain boundary defects resistance hindering the domain wall displacement, they usually show excellent soft magnetic properties and have been widely applied in high-frequency devices. CoFeB alloy is one of the most important amorphous magnetic materials and has been extensively applied in various spintronic devices. In this work, amorphous CoFeB magnetic thin films were prepared by using a method of oblique sputtering technique at room temperature. The influences of oblique sputtering on the stripe magnetic domain structure, the in-plane static magnetic anisotropy, the in-plane rotational magnetic anisotropy, and the perpendicular magnetic anisotropy of the amorphous CoFeB films were studied by scanning probe microscope, vibrating sample magnetometer, ferromagnetic resonance. It is found that the method of oblique sputtering could effectively reduce the critical thickness for the appearance of stripe magnetic domain in amorphous CoFeB films. For a non-oblique sputtered CoFeB film, the critical thickness for the appearance of the stripe magnetic domain is above 240 nm. In contrast, after been subjected to the oblique sputtering, the critical thickness becomes below 240 nm. The different magnetic characterizations indicate that for the growth of CoFeB films with stripe magnetic domain structure, the oblique sputtering could not only enhance the strength of in-plane static magnetic anisotropy, but also improve the in-plane rotational magnetic anisotropy and the perpendicular magnetic anisotropy. All of the magnetic anisotropies are increased with the angle of oblique sputtering. The observation results of XRD and TEM prove that the prepared CoFeB thin films tend to amorphous structure. The characterization of SEM observation indicates that although the amorphous CoFeB films do not possess long-range ordered crystalline structure, they still could form a kind of columnar structure. The slanted columnar structure of CoFeB films could significantly increase the perpendicular magnetic anisotropy, thus lead to the appearance of stripe magnetic domain structure.
Hydrous hydrazine (N2H4·H2O) is a water-like liquid with a high hydrogen density (8%, mass fraction), relatively low cost, and satisfactory stability under ambient conditions. Owing to these favorable attributes, N2H4·H2O has attracted considerable attention as a promising hydrogen carrier for onboard or portable applications. The synthesis of highly active and selective catalysts is a central issue in developing practical hydrous hydrazine-based hydrogen generation systems. The development of high-performance catalysts requires fundamental knowledge of the correlation between the surface composition of the catalyst and its catalytic performance. In the present work, a supported Ni-Pt/CeO2 bimetallic nanocatalyst was prepared by a one-pot co-reduction method, and its use for catalyzing hydrous hydrazine decomposition to generate hydrogen was reported. The surface composition of the Ni-Pt/CeO2 catalyst was regulated by heat treatments under different atmospheres, such as air, NH3, H2, and CO and at different temperatures. It was found that changing the annealing conditions may result in altered Ni/Pt ratio at the catalyst surface, and as a consequence the catalytic performance can be tailored. When the molar Ni/Pt ratio at the catalyst surface was 0.8~1.14, the catalyst has been found to possess remarkable catalytic activity towards hydrous hydrazine decomposition. Additionally, it was found that incorporation of non-metallic N element on the catalyst surface may result in remarkably improved catalytic activity of Ni-Pt/CeO2 towards hydrous hydrazine decomposition. This finding may open new avenues for the development of high-performance catalyst for promoting hydrogen generation from hydrous hydrazine.
With the development of space technology, the ability of manufacturing in space is a necessary guarantee for a long-term space mission. To achieve the repair and maintenance of spacecraft structure in space, a metal additive manufacturing method named resistance heating metal wire additive manufacturing process has been proposed in this work. During the experiments, the wire and the base plate are short-circuited, the current output from the programmable power source flows through the wire and the base plate to generate resistance heat, and then the wire begins to melt and transfer to the base plate. A real-time synchronization system has been used to record the current, voltage and image of metal wire synchronously, to study the melting process of metal wire by resistance heating. The direct current and pulse current with different amplitudes which were supplied by programmable power source have been used to study the effect of the current style and value on the melting process and transition behavior of metal wire. The change characteristic of the resistance in the wire and base plate has been analyzed during wire melting, to study the relationship between the current resistance and the wire state. The effect of gravity on the wire melting process has been studied by the wire transfer experiments at different space locations. The results show that when the metal wire was heated by the constant current, the total heat of metal melt could be controlled by controlling the current value, but it was difficult to precisely control the heating speed and the heat input. When using pulse current heating, both the heating speed and the heat input could be precisely controlled by pulse frequency and pick value. In the melt transfer stage, the constant current provides a fixed force on the molten wire, but the pulse current makes the molten wire swing by the intermittent force. The real-time resistance of metal wire during heating could be used to reflect the melting state of wire in both current styles. On the ground environment, the surface tension and electromagnetic contraction force make the melting wire against the gravity and transfer to the base plate, which illustrated the feasibility of using this process in space environment.
With the development of ocean engineering, various metallic materials have been applied to the marine environment. It is an urgent requirement to study the galvanic series and alloy composition optimization of metallic materials in the tropical marine environment. In this work, open circuit potentials (OCP) and galvanic series of 36 kinds of metallic materials in Sanya seawater were studied. By considering the response of OCP to tidal changes, the anti-corrosion effects of alloying elements were also analyzed. The results show that the OCP of metallic materials in Sanya seawater has a large range. The galvanic series order of metallic materials from high to low in Sanya seawater is: nickel alloy, duplex stainless steel, austenitic stainless steel and pure copper, ferritic stainless steel, martensitic stainless steel, copper alloy, low alloy steel, carbon steel, cast iron, aluminum alloy and aluminum anode. Low-carbon high-alloy content carbon steel and high Cr, Ni contents stainless steel have higher OCP. The potential fluctuations of carbon steel with tidal changes involves two phases: (1) under the dynamics control, the OCP of carbon steel is more negative at high tide; (2) under the diffusion control, the OCP is more positive at high tide. The potential fluctuations of metallic materials reflect the effect of the corrosion product film on the change of ionization balance, and metals with less potential fluctuations have better inhibition on ion diffusion. In Sanya seawater, the carbon steel, which has more alloying content and less carbon content, has less potential fluctuations with the tidal changes and has good oxygen diffusion resistance. The potential fluctuations of austenitic stainless steel with tidal changes are less than that of ferritic stainless steel and martensitic stainless steel. After 2700 h immersion, austenitic stainless steel and martensitic stainless steel, which have a higher content of Mo, have more stable OCP. In other words, the corrosion film gets a better corrosion resistance. The OCP of aluminum anode in Sanya seawater environment increases when the oxygen content is brought up. The OCP of Zn-containing or Ga-containing aluminum anode remains relatively stable. Al bronze and T2 copper have less potential fluctuations with tidal changes, and perform good corrosion resistance in Sanya seawater.
Microelectromechanical systems (MEMS) have become increasingly prevalent in engineering applications. In these MEMS, a lot of micro-components, such as thin films, nanowires, micro-beams and micropillars, are utilized. The characteristic geometrical size of those components is at the same scale as that of grain, the mechanical behavior of crystal materials exhibits significant size effect and discontinuous deformation. In addition, those MEMS are often subjected to high strain rate at work, such as collision and impact loading. The coupling deformation characteristics of small scale crystals and high strain rate makes their mechanical behavior more complicated. Accordingly, investigation of the effect of the strain rate on crystal materials at micron scale is significant for both the academia and industry. In this work, a plastic deformation model of fcc crystal under axial compression was developed based on three-dimensional discrete dislocation dynamics (3D-DDD), which considered the influence of externally applied stress, interaction force between dislocation segments, dislocation line tension and image force from free surface on dislocation movement during the process of plastic deformation. It was applied to simulate the plastic deformation process of a Ni single crystal micropillar during compression under different loading strain rates. 3D-DDD and theoretical analysis are carried out to extensively investigate the effect of strain rate on flow stress and deformation mechanisms during plastic deformation process of crystal materials. The results show that the flow stress and the dislocation density increased with the loading strain rate. In the case of low strain rate, the flow stress was dominated by the activation stress of Freak-Read (FR) source in plastic deformation. With the increase of strain rate, the contribution of activation stress of FR source to the flow stress decreases and the effective stress gradually dominated the flow stress. Under high strain rate loading, with the increase of the initial FR source, the dislocation density also increased at the same strain correspondingly, which makes it easier to meet the requirement of the loading strain rate, so the flow stress is smaller. In addition, under the low strain rate loading, a few activated FR sources can meet the requirement of the plastic deformation, a single slip deformation come up as a result. While, as the loading strain rate increases, more and more activated FR sources would be needed to coordinate the plastic deformation, the deformation mechanisms of the single crystal micropillar transformed from single slip to multiple slip.
Multilayered metallic composites have attracted great interest because of their excellent characteristics. In recent years, the mechanical behavior of Cu/Ti composites is described in terms of macroscopic or mesoscopic scales, but the micromechanism regarding dislocation slip, twinning and shear banding at heterogeneous interfaces remains unclear. In this work, the molecular dynamics method is used to study the uniaxial tensile and plane strain compression deformation of the Cu/Ti multilayered composites with characteristic initial crystal orientations. The simulation results show that under the tensile load, dislocations are preferentially nucleated at the heterogeneous interface between Cu and Ti, and then slip along {111} plane within the Cu layers. The corresponding mechanism is confined layer slip. With the multiplication of dislocations, dislocations interact with each other, and intrinsic stacking faults and deformation twins are formed in Cu layers. However, no dislocation slip or twinning is activated within the Ti layers at this stage of deformation. As the load increases, the stress concentration at the Cu/Ti interface leads to the fracture of the composites. For the composites under plane strain compression, the stress concentration at the Cu/Ti interface triggers the formation of shear bands in the Ti layer, and there are only very limited dislocations within the shear bands and their adjacent area. With the increase of applied strain, the common action of various deformation mechanisms causes the grains to rotate, and the disorder degree of complex atoms increases. In addition, the micro-plastic deformation mechanism and mechanical properties of Cu/Ti complex with different initial orientations and strain rates are significantly different. The results reveal the microscopic deformation mechanism of the laminated composites containing hcp metals.
