Improving corrosion resistance of additively manufactured WE43 magnesium alloy by high temperature oxidation for biodegradable applications

Laser powder bed fusion(L-PBF)has been employed to additively manufacture WE43 magnesium(Mg)alloy biodegradable implants,but WE43 L-PBF samples exhibit excessively rapid corrosion.In this work,dense WE43 L-PBF samples were built with the relativity density reaching 99.9%.High temperature oxidation was performed on the L-PBF samples in circulating air via various heating temperatures and holding durations.The oxidation and diffusion at the elevated temperature generated a gradient structure composed of an oxide layer at the surface,a transition layer in the middle and the matrix.The oxide layer consisted of rare earth(RE)oxides,and became dense and thick with increasing the holding duration.The matrix was composed ofα-Mg,RE oxides and Mg_(24)RE_(5) precipitates.The precipitates almost disappeared in the transition layer.Enhanced passivation effect was observed in the samples treated by a suitable high temperature oxidation.The original L-PBF samples lost 40%weight after 3-day immersion in Hank’s solution,and broke into fragments after 7-day immersion.The casted and solution treated samples lost roughly half of the weight after 28-day immersion.The high temperature oxidation samples,which were heated at 525℃ for 8 h,kept the structural integrity,and lost only 6.88%weight after 28-day immersion.The substantially improved corrosion resistance was contributed to the gradient structure at the surface.On one hand,the outmost dense layer of RE oxides isolated the corrosive medium;on the other hand,the transition layer considerably inhibited the corrosion owing to the lack of precipitates.Overall,high temperature oxidation provides an efficient,economic and safe approach to inhibit the corrosion of WE43 L-PBF samples,and has promising prospects for future clinical applications.

A Nitride-Reinforced NbMoTaWHfN Refractory High-Entropy Alloy with Potential Ultra-High-Temperature Engineering Applications

Refractory high-entropy alloys(RHEAs)have promising applications as the new generation of hightemperature alloys in hypersonic vehicles,aero-engines,gas turbines,and nuclear power plants.This study focuses on the microstructures and mechanical properties of the NbMoTaW(HfN)_(x)(x=0,0.3,0.7,and 1.0)RHEAs.The alloys consist of multiple phases of body-centered cubic(BCC),hafnium nitride(HfN),or multicomponent nitride(MN)phases.As the x contents increase,the grain size becomes smaller,and the strength gradually increases.The compressive yield strengths of the NbMoTaWHfN RHEA at ambient temperature,1000,1400,and 1800℃ were found to be 1682,1192,792,and 288 MPa,respectively.The high-temperature strength of this alloy is an inspiring result that exceeds the high temperature and strength of most known alloys,including high-entropy alloys,refractory metals,and superalloys.The HfN phase has a significant effect on strengthening due to its high structural stability and sluggish grain coarsening,even at ultra-high temperatures.Its superior properties endow the NbMoTaWHfN RHEA with potential for a wide range of engineering applications at ultra-high temperatures.This work offers a strategy for the design of high-temperature alloys and proposes an ultra-high-temperature alloy with potential for future engineering applications.

Effect of heat treatment on microstructure and mechanical properties of Ti-containing low alloy martensitic wear-resistant steel

Effects of quenching temperature and cooling conditions(water cooling and 10%NaCl cooling)on microstructure and mechanical properties of a 0.2%Ti low alloy martensitic wear-resistant steel used for die casting ejector plate were investigated.The results show that lath martensite can be obtained after austenitizing in the range of 860-980℃and then water cooling.With an increase in austenitizing temperature,the precipitate content gradually decreases.The precipitates are mainly composed of TiC and Ti4C2S2,and their total content is between 1.15wt.%and 1.64wt.%.The precipitate phase concentration by water-cooling is higher than that by10%NaCl cooling due to the lower cooling rate of water cooling.As the austeniting temperature increases,the hardness and tensile strength of both water cooled and 10%NaCl cooled steels firstly increase and then decrease.The experimental steel exhibits the best comprehensive mechanical properties after being austenitized at 900℃,cooled by 10%NaCl,and then tempered at 200℃.Its hardness,ultimate tensile strength,and wear rate reach551.4 HBW,1,438.2 MPa,and 0.48×10^(-2)mg·m^(-1),respectively.

Fretting Wear Characteristics of Nuclear Fuel Cladding in High-Temperature Pressurized Water

In pressurized water reactor(PWR),fretting wear is one of the main causes of fuel assembly failure.Moreover,the operation condition of cladding is complex and harsh.A unique fretting damage test equipment was developed and tested to simulate the fretting damage evolution process of cladding in the PWR environment.It can simulate the fretting wear experiment of PWR under different temperatures(maximum temperature is 350℃),displacement amplitude,vibration frequency,and normal force.The fretting wear behavior of Zr-4 alloy under different temperature environments was tested.In addition,the evolution of wear scar morphology,profile,and wear volume was studied using an optical microscope(OM),scanning electron microscopy(SEM),and a 3D white light interferometer.Results show that higher water temperature evidently decreased the cladding wear volume,the wear mechanism of Zr-4 cladding changed from abrasive wear to adhesive wear and the formation of an oxide layer on the wear scar reduced the wear volume and maximum wear depth.

Phase-Transitions at High, Very High, and Very Low Temperatures upon Nano-Indentations: Onset Forces and Transition Energies

This paper describes the phase-transition energies from published loading curves on the basis of the physically deduced FN = k-h3/2 law that does not violate the energy law by assuming h2 instead, as still do ISO-ASTM 14,577 standards. This law is valid for all materials and all “one-point indentation” temperatures. It detects initial surface effects and phase-transition kink-unsteadiness. Why is that important? The mechanically induced phase-transitions form polymorph interfaces with increased risk of crash nucleation for example at the pickle forks of airliners. After our published crashing risk, as nucleated within microscopic polymorph-interfaces via pre-cracks, had finally appeared (we presented microscopic images (5000×) from a model system), 550 airliners were all at once grounded for 18 months due to such microscopic pre-cracks at their pickle forks (connection device for wing to body). These pre-cracks at phase-transition interfaces were previously not complained at the (semi)yearlycheckups of all airliners. But materials with higher compliance against phase- transitions must be developed for everybody’s safety, most easily by checking with nanoindentations, using their physically correct analyses. Unfortunately, non-physical analyses, as based on the after all incredible exponent 2 on h for the FN versus h loading curve are still enforced by ISO-ASTM standards that cannot detect phase-transitions. These standards propagate that all of the force, as applied to the penetrating cone or pyramid shall be used for the depth formation, but not also in part for the pressure to the indenter environment. However, the remaining part of pressure (that was not consumed for migrations, etc.) is always used for the elastic modulus detection routine. That severely violates the energy-law! Furthermore, the now physically analyzed published loading curves contain the phase-transition onsets and energies information, because these old-fashioned authors innocently (?) published (of course correct) experimental loading curves. These follow as ever the physically deduced FN = k-h3/2 relation that does not violate the energy law. Nevertheless, the old-fashioned authors stubbornly assume h2instead of h3/2 as still do ISO-ASTM 14,577 standards according to an Oliver-Pharr publication of 1992 and textbooks. The present work contributes to understanding the temperature dependence of phase-transitions under mechanical load, not only for aviation and space flights, which is important. The physical calculations use exclusively regressions and pure algebra (no iterations, no fittings, and no simulations) in a series of straightforward steps by correcting for unavoidable initial effects from the axis cuts of the linear branches from the above equation exhibiting sharp kink unsteadiness at the onset of phase transitions. The test loading curves are from Molybdenum and Al 7075 alloy. The valid published loading curves strictly follow the FN = k-h3/2 relation. Full applied work, conversion work, and conversion work per depth unit show reliable overall comparable order of magnitude values at temperature increase by 150°C (Al 7075) and 980°C (Mo) when also considering different physical hardnesses and penetration depths. It turns out how much the normalized endothermic phase-transition energy decreases upon temperature increase. For the only known 1000°C indentation we provide reason that the presented loading curves changes are only to a minor degree caused by the thermal expansion. The results with Al 7075 up to 170°C are successfully compared. Al 7075 alloy is also checked by indentation with liquid nitrogen cooling (77 K). It gives two endothermic and one very prominent exothermic phase transition with particularly high normalized phase-transition energy. This indentation loading curve at liquid nitrogen temperature reveals epochal novelties. The energy requiring endothermic phase transitions (already seen at 20°C and above) at 77 K is shortly after the start of the second polymorph (sharply at 19.53 N loading force) followed by a strongly exothermic phase-transition by producing (that is losing) energy-content. Both processes at 77 K are totally unexpected. The produced energy per depth unit is much higher energy than the one required for the previous endothermic conversions. This exothermic phase-transition profits from the inability to provide further energy for the formation of the third polymorph as endothermic obtained at 70°C and above. That is only possible because the very cold crystal can no longer support endothermic events but supports exothermic ones. Both endothermic and exothermic phase-transitions at 77 K under load are unprecedented and were not expected before. While the energetic support at 77 K for endothermic processes under mechanical load is unusual but still understandable (there are also further means to produce lower temperatures). But strongly exothermicphase-transition under mechanical load for the production of new modification with negative energy content (less than the energy content of the ambient polymorph) at very low temperature is an epochal event here on earth. It leads to new global thinking and promises important new applications. The energy content of strongly exothermic transformed material is less than the thermodynamic standard zero energy-content on earth. And it can only be reached when there is no possibility left to produce an endothermic phase-transition. Such less than zero-energy-content materials should be isolated, using appropriate equipment. Their properties must be investigated by chemists, crystallographers, and physicists for cosmological reasons. It could be that such materials will require cooling despite their low energy content (higher stability!) and not survive at ambient temperatures and pressures on earth, but only because we do not know of such negative-energy-content materials with our arbitrary thermodynamic standard zeros on earth. At first one will have to study how far we can go up with temperature for keeping them stable. Thus, the apparently never before considered unprecedented result opens up new thinking for the search of new polymorphs that can, of course, not be reached by heating. Various further applications including cosmology and space flight explorations are profiting from it.

High-temperature tribological properties of Ni-P alloy coatings deposited by electro-brush plating

High-temperature tribological properties of Ni-P alloy coatings processed by electro-brush plating on 20CrMo steel have been investigated. A baU-on-disc configuration was employed and 4 mm diameter Si3N4 balls were used as static counterpart. All the wear tests were carried out at 450℃ for 180 rain without lubricants. The electro-brush plating Ni-P coating is amorphous in as-deposited condition, and it becomes polycrystalline with the formation of Ni and Ni3P after heat treatment at 450℃for 1 h. The friction coefficient of the Ni-P coating is just 50% of that of the 20CrMo steel at the friction temperature of 450℃. A mild adhesive wear mechanism was found for the electro-brush plating Ni-P coating tested at 450℃, whereas for the 20CrMo steel at the same temperature a mixed adhesive and abrasive wear mechanism was observed.

Friction of Alloys at High Temperature

A brief review is given about the friction and wear properties of high temperature alloys. Above a critical temperature, if the oxide becomes ductile, it will flow over the surface and prevent metal-to-metat contact. In order to study the tribology of oxide lubrication. a series of tests were carried out using Cu(ReO4)2 as a lubricant. The effects of time. Surface finish. substrates. load and temperature were investigated. A mechanism of lubrication is proposed in which the surface slip predominates along with mechanical attachment of oxide to the surface.

CONTROLLING HIGHTEMPERATURE DEFORMATION BY VARYING MICROSTRUCTURE IN A Ti47Al2Cr2Nb ALLOY

A Ti 47Al 2Cr 2Nb alloy was made by powder extrusion methods. By varying extrusion temperature, different microstructures were produced. At an extrusion temperature of 1 400 ℃ (above α transus), a uniform, fully lamellar structure was observed. In contrast, when powders were extruded at 1 150 ℃, an inhomogeneous microstructure consisting of γ,α 2 and metastable β phases was obtained. It was demonstrated that, while alloy extruded at 1 400 ℃ exhibited an excellent creep resistance, alloy with the same composition extruded at 1 150 ℃ exhibited superplasticity. The good creep resistance was resulted from the presence of fine lamellae which restrict dislocation slip within γ grains. These fine lamellae also promote the nucleation of deformation twins which impede dislocation glide along the interfaces ( γ/γ and γ/α 2) and, thus, reduces creep rate. In the case of low temperature extrusion, an elongation value of over 300% was obtained at a strain rate of 2×10 -5 s -1 and at a temperature as low as 800 ℃, which is close to the ductile to brittle transition temperature. This is in contrast to the prior major observations of superplastic behaviors in TiAl in which typical temperatures of 1 000 ℃ have usually been required for superplasticity. It was proposed that the occurrence of superplasticity at 800 ℃ is caused by the presence of a B2 phase which, during superplastic deformation (grain boundary sliding), accommodates sliding strains to reduce the propensity for cavitation at grain triple junctions and, thus, delays the fracture process.

ISOCHRONOUS STRESS-STRAIN CURVES OF LOW ALLOY STEEL CROSS-WELD-SPECIMEN AT HIGH TEMPERATURE

In this work, a parametric approach is presented and utilized to determine the creep properties of weldments; then the model of creep strain for cross weld specimen is given. On the basis of the experimental results, attempt has been made to establish equations of the isochronous stress-strain for weld joint that can predict the function of loading and service time in use of the creep data of base metal and weld metal.

DEVELOPMENT OF MoS_2-CONTAINING Ni-Cr BASED ALLOYS AND THEIR HIGH-TEMPERATURE TRIBOLOGICAL PROPERTIES

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Dynamic compressive property and failure behavior of extruded Mg-Gd-Y alloy under high temperatures and high strain rates

For the purpose of investigating the dynamic deformational behavior and failure mechanisms of magnesium under high strain rates,the Split Hopkinson Pressure Bar(SHPB)was used for investigating dynamic mechanical properties of extruded Mg-Gd-Y Magnesium alloy at ambient temperature(300 K),200℃(473 K)and 300℃(573 K)temperature.The samples after compression were analyzed by scanning electron microscope(SEM)and metallographic microscope.Dynamic mechanical properties,crack performance and plastic deformation mechanism of extruded Mg-Gd-Y Magnesium alloy along the extrusion direction(ED)were discussed.The results show that,extruded Mg-Gd-Y Magnesium alloy has the largest dynamic compressive strength which is 535 MPa at ambient temperature(300 K)and strain rate of 2826 s^(−1).When temperature increases,dynamic compressive strength decreases,while ductility increases.The dynamic compression fracture mechanism of extruded Mg-Gd-Y Magnesium alloy is multi-crack propagation and intergranular quasi-cleavage fracture at both ambient temperature and high temperature.The dynamic compressive deformation mechanism of extruded Mg-Gd-Y Magnesium alloy is a combination of twinning,slipping and dynamic recrystallization at both ambient temperature and high temperature.

A new die-cast magnesium alloy for applications at higher elevated temperatures of 200-300℃

The development of lightweight magnesium(Mg)alloys capable of operating at elevated temperatures of 200-300℃and the ability of using high pressure die casting for high-volume manufacturing are the most advanced developments in manufacturing critical parts for internal combustion engines used in power tools.Here we report the microstructure and mechanical properties of a newly developed die-cast Mg-RE(La,Ce,Nd,Gd)-Al alloy capable of working at higher elevated temperatures of 200-300℃.The new alloy delivers the yield strength of 94 MPa at 300℃,which demonstrates a 42%increase over the benchmark AE44 high temperature die-cast Mg alloy.The new alloy also has good stiffness at elevated temperatures with its modulus only decreasing linearly by 13%from room temperature up to 300℃.Thermal analysis shows a minor peak at 364.7℃in the specific heat curve of the new alloy,indicating a good phase stability of the alloy up to 300℃.Nd and Gd have more affinity to Al for the formation of the minority of divorced Al-RE(Nd,Gd)based compounds,and the stable Al-poor Mg_(12)RE(La_(0.22)Ce_(0.13)Nd_(0.31)Gd_(0.31))Zn_(0.39)Al_(0.13)compound acts as the continuous inter-dendritic network,which contribute to the high mechanical performance and stability of the new die-cast Mg alloy at 200-300℃.

High temperature mechanical behaviour of Mg-6Zn-1Y alloy with 1 wt.% calcium addition:Reinforcing effect due to I-(Mg3Zn6Yi)and Mg6Zn3Ca2 phases

The infiuence of small calcium additions on the high-temperature mechanical behaviour in an extruded Mg-6Zn-l Y(wt.%)alloy reinforced by the I-phase has been investigated.Calcium promotes the formation of the intermetallic Mg6Zn3Ca2 phase instead of 1-phase,which results in a noticeable improvement of the yield strength and ultimate tensile strength of the alloy above 100℃.The strength of the alloys was analysed taking into account the contribution due to the grain size,the crystallographic texture and the volume fraction and nature of second phase particles.In situ synchrotron radiation diffraction experiments have been used to evaluate the load partitioning between the magnesium matrix and the second phase particles(1-and MgeZgCa?phases)in both alloys.The load transfer from the magnesium matrix towards the MgeZihCa?phase is markedly more effective than that for the I-phase over the entire temperature range,especially at 200°C,temperature at which the reinforcement effect of the I-phase is null.

Phase Transformation and Thermal Stability of Aged Ti-Ni-Hf High Temperature Shape Memory Alloys

The use of Ni-rich TiNiHf alloys as high temperature shape memory alloys （SMAs） through aging has been presented. For Ni-rich Ti80-xNixHf20 alloys, their phase transformation temperatures are averagely increased more than 100 K by aging at 823 K for 2 h. Especially for the alloys with Ni-content of 50.4 at. pct and 50.6 at. pct, their martensitic transformation start temperatures （Ms） are more than 473 K after aging. TEM observation confirmed that some fine particles precipitate from the matrix during aging. The aged Ni-rich TiNiHf SMAs show the better thermal stability of phase transformation temperatures than the solutiontreated TiNiHf alloys. The fine particles precipitated during aging should be responsible for the increase of phase transformation temperatures and its high stability.

High-temperature Compressive Performance of Mg Alloy Foams Coated with Ni-P Layer

Mg/Ni hybrid foams were fabricated by the electroless method.The Ni-P(Nickel-Phosphorous)coatings were deposited on the surface of closed-cell Mg alloy foams.The composition,microstructure and phases of the Ni-P coatings were characterized by scanning electron microscopy(SEM),energy-dispersive X-ray spectroscopy(EDS)and X-ray diffraction(XRD),respectively.The compressive tests were performed on the Mg/Ni hybrid foams at 400℃using the Mg alloy foams as a reference.The experimental results show that the yield strength,plateau stress and energy absorption capacity of the closed-cell Mg alloy foams at high temperature were improved by the Ni-P coating.And there are four main modes for the Mg/Ni hybrid foam failure at 400℃,i e,shearing in cell wall,bending in cell edge,shedding and cracking in Ni-P coating.

LAVES PHASE ALLOYS FOR HIGH TEMPERATURE APPLICATIONS

Ternary Laves phases with transition metals and aluminium were overviewed with respect to their use for structural high temperature applications. The relation between constitution, phase stability, crystal structure and basic mechanical properties was discussed. The crystal structure-hexagonal C14 structure or cubic C15 structure-is a function of atomic radii and valence electron concentration. A strong positive correlation of basic mechanical properties-hardness, yield stress-with the sublimation energy of the phases was found. The brittle to ductile transition temperature was observed at about 60% of the melting temperature. The regarded ternary Laves phases allow alloying to form stable equilibria with the less hard and brittle B2 aluminides. Advantageous examples are alloys of type NbNiAl NiAl, TaNiAl NiAl, and TaFeAl FeAl. Multiphase NiAl Ta Cr alloys are regarded as promising for structural high temperature applications and have been selected for a materials development which aims at applications in gas turbines at temperatures above those of Ni base superalloys, such alloy can be prepared by ingot metallurgy and powder metallurgy and hot forming is possible. Characteristic data were presented with respect to mechanical behaviour. The alloys showed a high thermoshock resistance in spite of the comparatively high brittle to ductile transition temperature. The prospects of alloy development were discussed.

Fatigue small crack growth threshold determination of a high-Nb TiAl alloy at different temperatures by in-situ observation

The purpose of this paper is to estimate the fatigue crack growth threshold of a high-Nb TiAl alloy at the different temperatures based on scanning electron microscopy （SEM） in-situ observation. The results indicated that the fatigue crack growth threshold △Kth of a nearly lamellar high-Nb TiAl alloy with 8% Nb content at room temperature and 750℃ was determined as 12.89 MPa.m^1/2 and 8.69 MPa.m^1/2, respectively. The effect of the elevated temperature on the fatigue crack growth threshold cannot be ignored. At the same time, the early stage of fatigue crack propagation exhibited multicrack initiation and bridge-link behavior.

Effect of Ca on microstructure and high temperature creep properties of AM60-1Ce alloy

A series of AM60-1Ce-xCa(x=0, 0.5, 1.5, 2.5) magnesium alloys were prepared by gravity casting method and analyzed by means of XRD, DSC and SEM. The effects of Ca on normal temperature mechanical properties and high temperature creep behavior of alloys were characterized by tensile and constant creep test.Microstructure analysis indicated that Ca was preferentially combined with Al in the alloy to form the high melting point Al_2Ca phase at the grain boundary. The addition of Ca can refine the crystal grains and reduces the content of β-Mg_(17)Al_(12) phase. With the increase of Ca content in the alloy, Al_2Ca phases at the grain boundary gradually changed to the network of lamellar structure, and replaced the β-Mg_(17)Al_(12) phase as the main strengthening phase gradually. The creep resistance of the alloy continuously increases because the high-temperature stable phase Al_2Ca firmly nailed at grain boundaries impedes the sliding of grain boundaries. However, when the addition of Ca was more than 1.5%, mechanical properties of the alloy started to decrease, which was probably due to the large amount of irregularly shaped Al_2Ca phases at the grain boundary. Experimental results show that the optimal addition amount of Ca is 1.5 wt.%.

Effect of the precipitation state on high temperature tensile and creep behaviors of Mg-15Gd alloy

Due to the effective precipitation strengthening effect of the β phase, Mg-Gd alloys exhibit excellent room temperature mechanical behaviors. However, when served at high temperatures, the metastable β phase will transform to other phases, resulting in severe performance degradation. In this study, we investigated the effect of precipitation state achieved by different heat treatments on high temperature tensile and creep behaviors of the Mg-15Gd alloy by comparing the properties of the as-cast, solid-solutioned(T4) and peak-aged(T6) alloys. The results showed that the tensile mechanical properties of the T6 alloy were always highest from room temperature to 300 ℃, in spite of an abnormal strength increase with temperature existed in the T4 alloy. For tensile creep properties, the T6 alloy exhibited the lowest steady creep rate below 235 ℃ while the T4 alloy possessed the best properties above 260 ℃. Microstructure characterization revealed that the transition was caused by the stress-promoted precipitation of β phase in the T4 alloy and rapid phase transformation in the T6 alloy at high temperatures. At 260 ℃, the calculated stress exponent n was 3.1 and 2.8 for the T4 and T6 alloys, respectively, suggesting the creep deformation mechanism was dislocation slip, which was further confirmed by the microstructure after creeping. Our findings can provide new insights into the heat treatment process of Mg-Gd alloys served at high temperatures.

Effect of Lanthanum on Mechanical Properties of ZL702 Alloy at Room and High Temperature Condition

Effects of lanthanum on microstructure and mechanical properties of ZL702 alloy at room and high temperature conditions are studied. The experiment shows that high temperature intermetallics reticularly distributing at grain boundary are formed with La and Al, Si, Fe etc. elements of alloy, which enhances the thermal stability of the alloy. With appropriate content of La (0.10%～ 0.15%), the mechanical properties of the alloy, such as strength, at room temperature and high temperature can be improved.