Unconventional elastic properties, deformation behavior and fracture characteristics of newly developed rare earth bulk metallic glasses

Significant differences in the thermal, elastic and mechanical behavior of bulk metallic glasses (BMGs) based on rare earth (RE) elements (i.e., Pr-based, Ce-based and Nd-based) have been found when comparing them with archetypical Zr-based and Ti-based amorphous metallic alloys. Our results show that RE-BMG exhibits a large supercooled liquid region, low elastic constants and concomitant elastic softening, low hardness, complete lack of macroscopic plasticity and compressive fracture angles, ψ_C,F, larger than 45° (as opposed to polycrystalline materials, where ψ_C,F = 45°, and conventional BMGs, where ψ_C,F ≤ 45°). Most of these features stem from the rather low glass transition temperature displayed by these alloys, which is relatively close to room temperature. However, contrary to some previous studies, our observations reveal that the lack of plasticity of these materials cannot be simply rationalized in terms of their Poisson’s ratio but is also due to some tensile features (i.e., dilatational effects) accompanying compressive fracture behavior.     

Effect of minor Cu content on microstructure and mechanical property of NiTiCu bulk alloys fabricated by crystallization of metallic glass powder

Ultrafine-grained Ni_50.2−xTi_49.8Cu_x (x = 0, 2.5, 5, and 7.5) bulk shape memory alloys were fabricated by sintering of metallic glass (MG) powder and crystallization of amorphous phase. Non-isothermal crystallization kinetic analysis reveals that the crystallization mechanism of the synthesized x = 5 MG powder is typical interface-controlled two dimensional growth of nuclei followed by volume diffusion-controlled three dimensional growth of nuclei. In contrast, the crystallization mechanism of the synthesized x = 7.5 MG powder is typical volume diffusion-controlled three dimensional growth of nuclei in whole crystallization process. Correspondingly to different crystallization mechanisms, the two sintered and crystallized (SCed) bulk alloys have the same crystallized phases of bcc B2, fcc NiTi₂ phases, and monoclinic B19′, but these phases display different morphologies and distributions. The SCed x = 5 bulk alloy has a microstructure of bcc B2 matrix surrounding fcc NiTi₂ phase region, while the SCed x = 7.5 bulk alloy possesses discontinuous bcc B2 phase region. Consequently, the different crystallization mechanisms and microstructures causes extreme high yield strength and large plasticity for the SCed x = 5 bulk alloy and low strength and no plasticity for the SCed x = 7.5 bulk alloy. Especially, the yield strength of the SCed x = 5 bulk alloy is at least two times of that of the counterpart alloy prepared by melt solidification. The results provide a method fabricating high performance bulk alloys by tailoring crystallization mechanism using powder metallurgy.     

Towards improved integrated properties in FeCrPCB bulk metallic glasses by Cr addition

Fe-based soft-magnetic metallic glasses (MGs) of Fe_80−xCr_xP₉C₉B₂ (x = 0, 2, 5, 8 and 16 at.%) with high glass-forming ability (GFA), good soft-magnetic properties and high corrosion resistance are fabricated. With the addition of Cr to FePC-based alloys, the GFA and saturation magnetization (M_s) slightly decrease while the corrosion resistance effectively increases. The Fe–Cr–P–C–B BMGs exhibit good GFA and fully glassy rods can be produced up to 1.8 and 1.5 mm in diameter for the 2 and 5 at.% Cr added alloys, respectively. The alloys with 2 and 5 at.% Cr addition also show good soft-magnetic properties featured by high M_s of 1.16 and 1.04 T, low coercivity of 2.7 and 2.2 A/m, respectively. Besides, the corrosion behavior of the alloys was studied by immersion tests and potentiodynamic polarization measurements. It was found that the addition of Cr efficiently enhances the corrosion resistance of Fe–Cr–P–C–B alloys and the glassy alloy with 5 at.% Cr addition exhibits better corrosion resistance in comparison with the stainless steel SUS304 in 3 mass% NaCl solution. The combination of large GFA, good soft-magnetic properties, high corrosion resistance as well as low cost makes the Fe–Cr–P–C–B alloys as promising soft-magnetic and anti-corrosive materials for industrial applications.     

Optical reflection spectroscopy of thick corrosion layers on 304 stainless steel

Corrosion resistant structural materials of both iron and nickel based alloys are used in the electric power industry for the construction of the coolant loops of both conventional and nuclear power generating stations. These materials, in the presence of high temperature (e.g. 287 °C), high pH (e.g. 10.0 at 20 °C) water with dissolved hydrogen will oxidize and form corrosion films that are double metal oxides (or spinels) of the form AB₂O₄. This work describes optical reflectivity techniques that have been developed to study the growth of these films in situ. The optical technique uses a dual-beam specular reflection spectrometer to measure the spectrum of reflected light in small angle (i.e. <15°) scatter. The reflection spectra are then calibrated using a set of corrosion coupons with corrosion films that are well known. Results are compared with models based on multilayer reflection and Mie scattering from a particle size distribution. Surface roughness is found to be the dominant cause of reduced reflection as the films grow.     

Precision die-casting of optical MU/SC conversion sleeve

The performance of MU/SC conversion sleeve produced by bulk metallic glass (Zr₅₅Al₁₀Ni₅Cu₃₀) was examined. A precision die-casting method was applied to improve size accuracy. The size accuracy of the conversion sleeve produced by the precision die-casting method was ±1 μm, and optical insertion loss (Li) was less than 0.3 dB for a standard value. The wear resistance of metallic glass is improved by surface oxidation treatment in air at 673 K. The MU/SC conversion sleeve produced from bulk metallic glass has superior characteristics for optical parts.     

Microstructure and properties of intermetallic composite coatings fabricated by selective laser melting of Ti–SiC powder mixtures

Transition metal silicides and carbides are attractive advanced materials possessing unique combinations of physical and mechanical properties. However, conventional synthesis of bulk intermetallics is a challenging task because of their high melting point. In the present research, titanium carbides and silicides composites were fabricated on the titanium substrate by a selective laser melting (SLM) of Ti–(20,30,40 wt.%)SiC powder mixtures by an Ytterbium fiber laser with 1.075 μm wavelength, operating at 50 W power, with the laser scanning speed of 120 mm/s. Phase analysis of the fabricated coatings showed that the initial powders remelted and new multiphase structures containing TiC_x, Ti₅Si₃C_x, TiSi₂ and SiC phases in situ formed. Investigation of the microstructure revealed two main types of inhomogeneities in the composites, (i) SiC particles at the interlayer interfaces and, (ii) chemical segregation of the elements in the central areas of the tracks. It was suggested and experimentally proven that an increase in laser power to 80 W was an efficient way to improve the laser penetration depth and the mass transport in the liquid phase, and therefore, to fabricate more homogeneous composite. The SLM Ti–(20,30,40 wt.%)SiC composites demonstrated high hardness (11–17 GPa) and high abrasive wear resistance (3.99 × 10⁻⁷–9.51 × 10⁻⁷ g/Nm) properties, promising for the applications involving abrasive wear.     

Ternary La–Al–C bulk metallic glasses

Glass formation, thermal stability, elastic moduli and mechanical properties of La–Al–C bulk metallic glasses (BMGs) were investigated. The BMGs of La_57.5Al_32.5C₁₀, La₆₀Al₃₀C₁₀, and La_62.5Al_27.5C₁₀ with the maximal diameters up to 3 mm can be synthesized. Compared with other La-based glassy systems, like La–Al–(Co, Ni, Cu), the La–Al–C BMGs with the similar La concentration exhibit higher glass transition temperatures (507–577 K) and elastic constants. The La–Al–C BMGs with the unusual T_g and elastic moduli fill a gap in thermal and elastic properties between light rare-earth-based BMGs and heavy rare-earth-based ones. The compressive yield strength of La_57.5Al_32.5C₁₀ BMG reaches to ∼1.1 GPa, higher than that of other reported La-based BMGs. The ternary BMGs with simple element constituent, high glass-forming ability and superior mechanical properties are significant for fundamental research as model materials.     

Enhancement on GFA and mechanical properties of Ni-based bulk metallic glasses through Fe addition

Bulk Ni_76-xFe_xP₁₄B₆Ta₄ (x = 10, 20, 30, all in at.%) glassy alloy rods with diameters of 1.5–3.0 mm are synthesized by combining fluxing treatment and J-quenching technique, and the effects of Fe substitution for Ni on the glass forming ability (GFA), thermal stability, mechanical properties, and corrosion resistance of the present Ni-based bulk metallic glasses (BMGs) have been studied systematically in this work. It is found that the appropriate substitution of Fe for Ni can greatly enhance the GFA of the present Ni-based alloys, and the critical diameter for fully glass formation gets to the maximum value of 3.0 mm when the substitution content of Fe for Ni is 20 at.%. The corrosion tests show that the substitution of Fe for Ni causes a certain reduction of the corrosion resistance of the present Ni-based BMGs, but the corrosion current densities in both 1 M NaCl and 1 M HCl solutions are below the order of magnitude of 10⁻⁵ A/cm² and the corrosion rate in1 M HCl solution is in the order of magnitude of 0.1 mm/year, still exhibiting a good corrosion resistance. The present Ni-based BMGs exhibit a compressive strength of more than 2.6 GPa and, more significantly, the substitution of Fe for Ni greatly enhances the compressive plasticity of the present Ni-based BMGs and the compressive plastic strain gets up to 6.6% when 20 at.% of Ni is substituted by Fe. This work indicates that the GFA and mechanical properties of Ni-based BMGs can be enhanced significantly through the Fe addition.     

Effect of Nb addition on microstructure evolution and nanomechanical properties of a glass-forming Ti–Zr–Si alloy

The glass-forming Ti₇₅Zr₁₀Si₁₅ alloy is regarded as a potential material for implant applications due to its composition of non-toxic, biocompatible elements and some interesting mechanical properties. The effects of partial substitution of 15 at.% Ti by Nb on the microstructure and the mechanical behaviour have been investigated by X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray analysis, transmission electron microscopy and nanoindentation techniques. Copper mold casting and melt-spinning methods have been applied to study the influence of the cooling rate on the properties of both alloys, Ti₇₅Zr₁₀Si₁₅ and Ti₆₀Zr₁₀Nb₁₅Si₁₅. As a result of different cooling rates, significant microstructural variations from multiphase crystalline states in cast rods to nanocomposite structures in ribbons were observed. The limited glass-forming ability (GFA) of the Ti₇₅Zr₁₀Si₁₅ alloy results for melt-spun ribbons mainly in nanocomposite structures with β-type nanocrystals being embedded in a glassy matrix. Addition of Nb increases the glass-forming ability. Raising the overheating temperature of the melt prior to melt-spinning from 1923 K to 2053 K yields for both alloys a higher amorphous phase fraction. The mechanical properties were investigated using compression tests (bulk samples) and the nano-indentation technique. A decrease of hardness (H), ultimate stress and reduced Young's modulus (E_r) is observed for Ti₆₀Zr₁₀Nb₁₅Si₁₅ rods as compared to Ti₇₅Zr₁₀Si₁₅ ones. This is attributed to an increase of the fraction of the β-type phase. The melt-spun ribbons show an interesting combination of very high hardness values (H) and moderate reduced elastic modulus values (E_r). This results in comparatively very high H/E_r ratios of >0.075 which suggests these new materials for applications demanding high wear resistance.     

Thermal stability,magnetic and mechanical properties of Fe–Dy–B–Nb bulk metallic glasses with high glass-forming ability

The effects of Dy addition on the thermal stability, glass-forming ability (GFA), magnetic and mechanical properties of quaternary (Fe_0.76−xDy_xB_0.24)₉₆Nb₄ (x = 0–0.07) bulk metallic glasses (BMGs) were investigated. Increasing Dy content from x = 0 to 0.05 extended the supercooled liquid region up to 112 K, allowing the fabrication by copper mold casting of BMGs rods with 5.5 mm in diameter. The high GFA was found to be related to the structure of primary crystalline phase. For the x = 0.05 alloy, the competitive formation process of the complex Fe₂₃B₆ and Dy₂Fe₁₄B phases enabled to obtain the largest GFA value. Moreover, the Fe–Dy–B–Nb BMGs exhibited good soft-magnetic properties, i.e., high saturation magnetization of 1.18–0.56 T and low coercive force of 1.9–21.6 A/m. In addition, the glassy alloy rods also showed high compressive fracture strengths of 4400–4150 MPa and high Vickers hardness of 1110–1090 kg/mm².     

Assessment of the surface state behaviour of Al71Cu10Fe9Cr10 and Al3Mg2 complex metallic alloys in sliding contacts

Electrochemical measurements and friction measurements during continuous and intermittent unidirectional sliding tests are used to monitor and to evaluate the surface characteristics of two types of metallic materials characterized by a huge unit cell, namely Al₇₁Cu₁₀Fe₉Cr₁₀ and Al₃Mg₂. The modification of the surface characteristics results from the periodic mechanical removal of a surface film during sliding, and the subsequent (electro)chemical re-growth of a surface film in-between successive sliding contacts. Al₇₁Cu₁₀Fe₉Cr₁₀ and Al₃Mg₂ materials were tested in a phosphate buffer solution pH 7 at 25 °C to compare their depassivation and subsequent repassivation behaviour. The Al₃Mg₂ material was also tested in a 0.1 M KOH solution pH 13 and 25 °C to reveal the role of constituting metallic elements on the surface film formation. The effect of film formation and removal on the coefficient of friction recorded during unidirectional sliding is discussed.     

Synthesis and properties of CaCd2Sb2 and EuCd2Sb2

High density polycrystalline CaCd₂Sb₂ and EuCd₂Sb₂ intermetallics are synthesized by Spark Plasma Sintering and their thermoelectric properties are investigated. X-ray diffraction measurements reveal both materials have a structure in space group, containing a small amount of CdSb as a second phase. Thermoelectric measurements indicate both are p-type conductive materials. The figure of merit value of CaCd₂Sb₂ is 0.04 at 600 K and that of EuCd₂Sb₂ is 0.60 at 617 K. Theoretical calculations show that CaCd₂Sb₂ is a degenerate semiconductor with a band gap of 0.63 eV, while EuCd₂Sb₂ is metallic with DOS of 13.02 electrons/eV. For deeper understanding of the better thermoelectric properties of EuCd₂Sb₂, its low temperature magnetic, transport and heat capacity properties are investigated. Its Nèel temperature is 7.22 K, convinced by heat capacity anomaly at 7.13 K. Hall effect convinced that it is a p-type conductive material. It has high Hall coefficient, high carrier concentration and high carrier mobility of +1.426 cm³/C, 4.38 × 10¹⁸/cm³ and 182.40 cm²/Vs, respectively. They are all in the magnitude of good thermoelectric materials. The Eu 4f level around Fermi energy and antiferromagnetic order may count for the better thermoelectric properties of EuCd₂Sb₂ than that of CaCd₂Sb₂.     

Chromium–palladium films on 316L stainless steel by pulse electrodeposition and their corrosion resistance in hot sulfuric acid solutions

Chromium–palladium alloy films with good adhesive strength and higher micro-hardness have been deposited on 316L stainless steel by pulse electroplating. The films are composed mainly of chromium and palladium crystallites in the metallic state, with grain sizes less than 100 nm. On the film surface Cr(OH)₃ and Cr₂O₃ are present. The co-deposited Cr and Pd in the films show a synergetic effect on passivation. In boiling 20 wt.% H₂SO₄ solution, boiling acetic–formic acid mixture, and simulated PEM fuel cells environment, the Cr–Pd-plated 316L steel shows excellent corrosion resistance.     

Structure of Al–Ni intermetallic composite layers produced on the Inconel 600 by the glow discharge enhanced-PACVD method

The Plasma Assisted Chemical Vapor Deposition (PACVD) treatment conducted under glow discharge conditions in an atmosphere of trimethylaluminum vapors applied to an Inconel 600 substrate yielded composite surface layers built of intermetallic phases of the Al–Ni system with the outer zone composed of aluminum oxides. Such layers have very advantageous performance properties, such as high hardness, good corrosion and frictional wear resistance and, good adherence to the substrate.The present study is dedicated to microstructure characterization of the layers. The layers were examined using a variety of methods. Based on the results of these examinations, the microstructure of the composite layers was described as a multizone one with an outer Al₂O₃ zone, an intermediate AlNi₃ + Al₂O₃ zone and a diffusion zone of type Ni(Al,Cr,Fe) + AlNi₃ + Cr₇C₃. The mechanism of layer formation as well as the correlation between the microstructure and the observed improvement of the surface properties of the Inconel 600 alloy are discussed.     

A quinary Ti–Zr–Hf–Be–Cu high entropy bulk metallic glass with a critical size of 12 mm

A quinary Ti₂₀Zr₂₀Hf₂₀Be₂₀Cu₂₀ high entropy bulk metallic glass (HE-BMG), with a critical diameter (D_c) of 12 mm—the largest size in the reported quinary high entropy alloys (HEAs), has been successfully prepared by copper mold casing. This novel HE-BMG possesses a supercooled liquid region ΔT (=T_x − T_g) of 78 K, indicating a better thermal stability than those of other HE-BMGs. In addition, the HE-BMG exhibits a relatively good compressive plasticity (2.2 ± 0.1%) among the HE-BMGs. The newly developed HE-BMG may offer insights for the indepth understanding of the fundamental issues associated with the glass formation and the unique structure-property relationship when combining the features of HEAs and BMGs together.     

Effects of ion irradiation on Zr52.5Cu17.9Ni14.6Al10Ti5 (BAM-11) bulk metallic glass

Bulk metallic glasses are intriguing candidates for nuclear applications due to their inherent amorphous structure, but their radiation response is largely unknown due to the relatively recent nature of innovations in bulk metallic glass fabrication. Here, microstructural and mechanical property evaluations have been performed on a Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ bulk metallic glass (BAM-11) irradiated with 3 MeV Ni⁺ ions to 0.1 and 1.0 dpa at room temperature and 200 °C. Nanoindentation hardness and Young's modulus both decreased by 6–20% in samples irradiated at room temperature, with the sample irradiated to 1.0 dpa experiencing the greatest change in mechanical properties. However, no significant changes in properties were observed in the samples irradiated at 200 °C, and transmission electron microscopy showed no visible evidence of radiation damage or crystallization following ion irradiation at any of the tested conditions. These results suggest that BAM-11 bulk metallic glass may be useful for certain applications in nuclear environments.     

Effects of lutetium addition on formation,oxidation and tribological properties of a Zr-based bulk metallic glass

Enhancement of glass-forming ability (GFA) and surface properties are important for the application of Zr-based bulk metallic glasses (BMGs), and surface oxidation is an effective strategy for surface strengthening. In this paper, the effects of rare earth element Lu addition on GFA and oxidation properties of a Zr₅₀Ti₂Cu₃₈Al₁₀ bulk metallic glass were studied. The tribological properties of Lu-free and Lu-doping BMGs before and after oxidation were also investigated. It is found that 2 at.% Lu addition in this alloy significantly enhance the critical diameter (d_c) from 5 mm to 20 mm. The oxidation rate of 2 at.% Lu-doping alloy is higher than Lu-free alloy, indicating that the addition of Lu facilitates the formation of oxidized scale on the surface of Zr₅₀Ti₂Cu₃₈Al₁₀ alloy. Moreover, surface oxidation treatment remarkably improves the wear resistance of Zr₅₀Ti₂Cu₃₈Al₁₀ and (Zr_0.5Ti_0.02Cu_0.38Al_0.1)₉₈Lu₂. This study is beneficial for the improvement of surface properties and further application of Zr-based BMGs.     

Critical obstacle size to deflect shear banding in Zr-based bulk metallic glass composites

The Zr₅₃Cu₂₂Ni₉Al₈Ta₈ bulk metallic glass composite (BMGC) rods have been reported to present superior plastic strain up to 30% at room temperature. The remarkable plasticity is demonstrated to be contributed by the in-situ Ta-rich precipitates in micro-sized (10–20 micro-meter) plus nano-sized (5–15 nm) scales, homogeneously distributed in the amorphous matrix. These Ta-rich particles act as discrete obstacles, separating and restricting the highly localized shear-banding, avoiding catastrophic shear-through of the whole sample and dramatically enhancing plasticity, as compared with the ZrCuNiAl monolithic BMG. To explore the critical particle size that can effectively deflect the shear banding, the Zr-based BMGC rods were plastically deformed to different strain levels (3%–25%) before fracture for investigating the interaction between the Ta-rich particles (micro- and nano-sized) and shear banding. The results suggest that the critical size of single particle or particle cluster for deflecting the shear band is greater than 20 nm and less than 100 nm. The best estimation suggests about 80 ± 20 nm.     

Enhancement of plasticity in Zr-based bulk metallic glasses electroplated with copper coatings

Electrodeposition was used to coat copper films on the surface of the BMG pillars (bulk metallic glasses) of Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ (Vit. 105) with the film thicknesses of 71.5 and 161.1 μm. The experimental results of the compression tests of the bare Vit. 105 pillars and the coated Vit. 105 pillars revealed that the copper costing increased the density of shear bands in the Vit. 105 pillars formed during the tests, resulting in the improvement of plasticity. The plastic strain was 6.1% for the coated pillars with a coating thickness of 161.1 μm, which is 3.59 times of 1.7% of the bare Vit. 105 pillars. The deformation of the copper films dissipated the strain energy and limited the propagation of shear bands, which led to the initiation and formation of multiple shear bands. The technique developed in this work provides an effective way to enhance the plasticity of BMGs at room temperature.     

Fe-based soft magnetic amorphous alloys with high saturation magnetization above 1.5 T and high corrosion resistance

Fe-rich amorphous alloys with minor-addition of Cr and/or Nb were examined with the aim of developing Fe-based amorphous alloys exhibiting simultaneously high saturation magnetization above 1.5 T and good corrosion properties. Fe₈₂Cr₂B₈P₄Si₃C and Fe₈₂NbB₉P₄Si₃C amorphous alloys were found to exhibit high saturation magnetizations of 1.49 T and 1.57 T, respectively, and rather good corrosion resistance in 3.5 mass% NaCl solution at 298 K. The minor-addition of Cr or Nb enables the formation of amorphous alloy particles without harmful oxide layer by water atomization process which makes these alloys suitable for applications as soft magnetic core materials. The addition of 1 at% Nb improved the corrosion resistance through the increase in E_corr value, which makes easy to reach passive state, and the suppression of pitting corrosion. Besides, it has been proved that the simultaneous addition of Nb and Cr has an effect on forming protective passive film.