Lamellar Nanostructures Research Articles

Rational Fabrication of Multiple Dimensional Assemblies from Tryptophan-Based Racemate.

Fabricating structural complex assemblies from simple amino acid-based derivatives is attracting great research interests due to their easy accessibility and preparation. However, the morphological regulation of racemates (an equimolar mixture of enantiomers) were largely overlooked. In this work, through rational modulation of kinetic and thermodynamic parameters, we achieved multiple dimensional architectures employing tryptophan-based racemate (RPWM). Upon assembling, 1D bundled nanofibers, 2D lamellar nanostructure and 3D urchin-like microflowers could be obtained depending on the solvents used. The corresponding morphology evolutions were successfully illustrated by changing the enantiomeric excess (ee) value. Moreover, for RPWM, uniform 0D nanospheres were formed in H2 O under 4 °C, which could spontaneously convert into lamella under ambient temperature. Taking advantages of its temperature-responsive phase change behavior, RPWM assemblies exhibited excellent removal efficiency for organic dye RhB, and could be reused for several consecutive cycles without significant changes in its removal performance. Taken together, it's rational to envision that the engineering of racemates assembly pathways can greatly increase the robustness in a wide variety of supramolecular materials and further lead to their blooming versatile applications.

Simple linear ionic polysiloxane showing unexpected nanostructure and mechanical properties

Polysiloxanes are ubiquitous materials in industry and daily life derived from silicates, an abundant resource. They exhibit various properties, which depend on the main-chain network structure. Linear (1D backbone) polysiloxanes provide amorphous materials. They are recognized as fluid materials in the form of grease or oil with a low glass transition temperature. Herein we report that a simple linear polysiloxane, poly(3-aminopropylmethylsiloxane) hydrochloride, shows an elastic modulus comparable to that of stiff resins such as poly(tetrafluoroethylene). By introducing an ammonium salt at all the units of this polysiloxane, inter- and intramolecular ionic aggregates form, immensely enhancing the elastic modulus. This polysiloxane is highly hygroscopic, and its modulus can be altered reversibly 100 million times between moist and dry atmospheres. In addition, it works as a good adhesive for glass substrates with a shear strength of more than 1 MPa in the dry state. Despite its simple structure with a flexible backbone, this polymer unexpectedly self-assembles to form an ordered lamellar nanostructure in dry conditions. Consequently, this work reveals new functions and possibilities for polysiloxanes materials by densely introducing ionic groups.

Effect of temporal pH variation of the reaction mixture on Mg(OH)2 morphology precipitated from an aqueous Mg(NO3)2-NaOH system

To understand the impact of temporal pH variation on the crystallisation process, Mg(OH)2 was synthesized via wet precipitation route from an aqueous Mg(NO3)2-NaOH system. A detailed analysis of morphological evolution and the nano-structural transformation was carried out to model the crystallisation process. Interestingly, low supersaturation at low pH level lying between 9.2 and 9.4 of the reaction mixture, was found to promote the growth of nanorod like 1-D structures. On the contrary, enhanced supersaturation created a chemical driving force favouring an edgewise growth of the nucleated primary nanocrystals along (101) and (110) crystallographic planes, which resulted in lamellar hexagonal nanostructures. The lamellar growth demonstrated an increment in the particle size and reduction in anisotropic strain and dislocation density due to proper nucleation in the samples. Such controlled growth and nucleation of the Mg(OH)2 morphology presents a great scope of potential applications of this material.

Shear-Rolling Process for Unidirectionally and Perpendicularly Oriented Sub-10-nm Block Copolymer Patterns on the 4 in Scale.

Shear alignment of the block copolymer (BCP) thin film is one of the promising directed self-assembly (DSA) methodologies for the unidirectional alignment of sub-10 nm microdomains of BCPs for next-generation nanolithography and nanowire-grid polarizers. However, because of the differences in the surface/interfacial energies at the top surface/bottom interface, the shear-induced ordering of BCP nanopatterns has been restricted to BCPs with spherical and cylindrical nanopatterns and cannot be realized for high-aspect-ratio perpendicular lamellar structures, which is essential for practical application to semiconductor pattern processes. It is still a difficult challenge to fabricate the unidirectional alignment in a short time over a large area. In this study, we propose an approach for combining the shear-rolling process with the filtered plasma treatment of BCP films for the fabrication of unidirectionally aligned and perpendicularly oriented lamellar nanostructures. This approach enables fabrication within 1 min on a 4 in scale. We treated filtered plasma on the BCP film for perpendicular orientation and executed the hot-rolling process with different roller and stage speeds. Large-scale shear was generated only at the location where the BCP film was in contact with both the roller and stage, effectively applying shear stress to a large area of the BCP film within a short time. The repeated application of this shear-rolling process can achieve a higher level of unidirectional alignment. Our aligned BCP vertical lamellae were used to fabricate a high-aspect-ratio sub-10-nm-wide metallic nanowire array via dry/wet processes. In addition, shear-rolling with chemoepitaxy patterns can achieve higher orientational order and lower defectivity.

Investigation on the structural quality dependent electromagnetic interference shielding performance of few-layer and lamellar Nb2CTx MXene nanostructures

Tunable Electromagnetic Interference (EMI) shielding behaviors of 2D MXene (Nb2CTx) were explored via different exfoliation conditions. Stacked, lamellar few-layer, oxygen-related surface functional groups, and structural defects along with oxidative products of Nb2CTx were identified by tuning chemical etching conditions during one-step exfoliation process. Exfoliation of Nb2CTx with a tightly packed stacked structure remarked at lower etching times. The unpacking of Nb2CTx into lamellar morphology followed by separated few-layer Nb2CTx remarked at moderate etching time, whereas structural misalignment, defects, and oxidation of Nb2CTx occurred during prolonged chemical etching times. Synergistic effect of one-step extracted few-layers and lamellar structured Nb2CTx favorably enrich the assembly of multiple electrical conductive pathways responsible for absorption dominated EMI shielding performance in X- and Ku-band region. The assembled wax nanocomposites with 80% of Nb2CTx loading exfoliated at 100 h etching time at a thickness of 1 mm exhibited EMI shielding effectiveness of about 44.09 ± 1.99 dB at 12 GHz, and its EMI attenuation mechanism explained by conduction and eddy current loss. The combined action of few-layer and lamellar Nb2CTx nanostructures could be interesting for making novel shielding materials; open a new avenue for niobium series in the MXene family for elaborated applications.

Oligodimethylsiloxane-Oligoproline Block Co-Oligomers: the Interplay between Aggregation and Phase Segregation in Bulk and Solution.

Discrete block co-oligomers (BCOs) assemble into highly ordered nanostructures, which adopt a variety of morphologies depending on their environment. Here, we present a series of discrete oligodimethylsiloxane-oligoproline (oDMS-oPro) BCOs with varying oligomer lengths and proline end-groups, and study the nanostructures formed in both bulk and solution. The conjugation of oligoprolines to apolar siloxanes permits a study of the aggregation behavior of oligoproline moieties in a variety of solvents, including a highly apolar solvent like methylcyclohexane. The apolar solvent is more reminiscent of the polarity of the siloxane bulk, which gives insights into the supramolecular interactions that govern both bulk and solution assembly processes of the oligoproline. This extensive structural characterization allows the bridging of the gap between solution and bulk assembly. The interplay between the aggregation of the oligoproline block and the phase segregation induced by the siloxane drives the assembly. This gives rise to disordered, micellar microstructures in apolar solution and crystallization-driven lamellar nanostructures in the bulk. While most di- and triblock co-oligomers adopt predictable morphological features, one of them, oDMS15-oPro6-NH2, exhibits pathway complexity leading to gel formation. The pathway selection in the complex interplay between aggregation and phase segregation gives rise to interesting material properties.

Hyperbolic Metamaterials via Hierarchical Block Copolymer Nanostructures

AbstractHyperbolic metamaterials (HMMs) offer unconventional properties in the field of optics, enabling opportunities for confinement and propagation of light at the nanoscale. In‐plane orientation of the optical axis, in the direction coinciding with the anisotropy of the HMMs, is desirable for a variety of novel applications in nanophotonics and imaging. Here, a method for creating localized HMMs with in‐plane optical axis, based on block copolymer (BCP) blend instability, is introduced. The dewetting of BCP thin film over topographically defined substrates generates droplets composed of highly ordered lamellar nanostructures in hierarchical configuration. The hierarchical nanostructures represent a valuable platform for the subsequent pattern transfer into a Au/air HMM, exhibiting hyperbolic behavior in a broad wavelength range in the visible spectrum. A computed Purcell factor as high as 32 at 580 nm supports the strong reduction in the fluorescence lifetime of defects in nanodiamonds placed on top of the HMM.

Correlations of nanoscale film morphologies and topological confinement of three-armed cage block copolymers

Three-armed cage block copolymers composed of immiscible blocks in near equivalent volume fractions formed topologically controlled sub-10 nm cylindrical and lamellar nanostructures in nanoscale films.

Understanding the hierarchical behavior of Bi2WO6 with enhanced photocatalytic nitrogen fixation activity.

Hierarchical Bi2WO6 nanostructures self-assembled with planar arranged nanosheets and dispersed Bi2WO6 nanosheets were synthesized with different dosages of EG via a simple hydrothermal route. The Bi2WO6 photocatalysts were analyzed by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS). A control experiment was conducted to test the effect of EG dosage on the growth mechanism and behavior of the highly (010) exposed hierarchical lamellar nanostructures and dispersed nanosheets. The photocatalytic nitrogen fixation rate of the hierarchical Bi2WO6 nanostructures was estimated to be 948 μmol g-1 h-1 across the full spectrum, which was 23% higher than that of the dispersed nanosheets (770 μmol g-1 h-1) due to chemisorption on the hierarchical structures and enhanced surface oxygen vacancies (OVs).

Elaboration of Lamellar and Nanostructured Materials Based on Manganese: Efficient Adsorbents for Removing Heavy Metals

The lamellar and nanostructured manganese oxide materials were chemically synthesized by soft and non-toxic methods. The materials showed a monophasic character, symptomatic morphologies, as well as the predominance of a mesoporous structure. The removal of heavy metals Cd(II) and Pb(II) by the synthesized materials Na-MnO2, Urchin-MnO2 and Cocoon-MnO2 according to the mineral structure and nature of the sites were also studied. Kinetically, the lamellar manganese oxide material Na-MnO2 was the most efficient of the three materials which had more vacancies in the MnO6 layers as well as in the space between the layers. The nanomaterials Urchin-MnO2 and Cocoon-MnO2 could exchange with the metal cations in their tunnels and cavities, respectively. The maximum adsorbed quantities followed the order (Pb(II): Na-MnO2 (297 mg/g)>Urchin-MnO2 (264 mg/g)>Cocoon-MnO2 (209 mg/g), Cd(II): Na-MnO2 (199 mg/g)>Urchin-MnO2 (191 mg/g)>Cocoon-MnO2 (172 mg/g)). Na-MnO2 material exhibited the best stability among the different structures, Na-MnO2 presented a very low amount of the manganese released. The results obtained showed the potential of lamellar manganese oxides (Na-MnO2) and nanostructures (Urchin-MnO2 and Cocoon-MnO2) as selective, economical, and stable materials for the removal of toxic metals in an aqueous medium.

Molten Electrolyte-Modulated Electrosynthesis of Multi-Anion Mo-Based Lamellar Nanohybrids Derived from Natural Minerals for Boosting Hydrogen Evolution.

The multi-anion molybdenum-based nanohybrids, N-doped β-Mo2C/MoP/MoOx (denoted as MoCPO), serving as a highly efficient catalyst for hydrogen evolution reaction (HER), are fabricated via a simple and scalable electrosynthesis in molten NaCl-KCl, which integrates pyrolysis/electroreduction/compounding into a one-pot strategy using polyphosphazenes (PPAs) and earth-abundant molybdenite (mainly MoS2) as precursors. The deliberately selected PPA and molten electrolyte ensure the unique lamellar nanostructures and the blending of multiple anions of C, N, P, and O in the obtained catalyst, specifically, triggering the in situ formation of the structural oxygen vacancies (VO) in MoCPO. The nature of the hybrids can be regulated by adjusting the synthesis condition. The optimized hybrid displays a low overpotential of 99.2 mV at 10 mA cm-2 for HER in 0.5 M H2SO4 and stays active over a broad pH range. The theoretical calculations reveal that VO in the hybrids serves as favorable active sites, thus contributing to the superior HER activity. Moreover, MoCPO is also effective for overall water splitting as a bifunctional catalyst.

“Soapy water” transformation of the “condenser” with self-cleaning ability and antibacterial activity

Superhydrophobic materials exhibit diverse application potential in various fields due to their excellent self-cleaning properties. However, it is still challenging to prepare bionic superhydrophobic materials employing the green methods. In this study, the “condenser” (simulated by a red copper spiral tube) with excellent self-cleaning properties and antibacterial activity has been prepared by a simple one-step “soapy water” immersion process without introducing any other reagents. The results demonstrate that the Cu[CH3(CH2)10COO]2 lamellar nanostructures are formed on the surface of “condenser” owing to the oxidation of copper upon immersion in the sodium laurate aqueous solution. The as-formed nanostructures exhibit excellent self-cleaning performance and can significantly inhibit the growth and proliferation of Escherichia coli and Staphylococcus aureus, which is significant for the upgradation of the safety and comfort features of the new generation air-conditioners. Moreover, the ruptured superhydrophobic coating on the copper tube can be effectively restored by a facile re-soaking process. Therefore, the present approach, with simple one-step solution-immersion process, low cost, short immersion period, environmental friendliness and optimal applicability to a variety of metal structures of different shapes, represents a promising strategy for fabricating the low-cost superhydrophobic surfaces applicable to the condenser and heat transfer systems, thereby, promoting the development of the self-cleaning and antibacterial smart devices.

DNA-π Amphiphiles: A Unique Building Block for the Crafting of DNA-Decorated Unilamellar Nanostructures.

The unparalleled ability of DNA to recognize its complementary strand through Watson and Crick base pairing is one of the most reliable molecular recognition events found in natural systems. This highly specific sequence information encoded in DNA enables it to be a versatile building block for bottom-up self-assembly. Hence, the decoration of functional nanostructures with information-rich DNA is extremely important as this allows the integration of other functional molecules onto the surface of the nanostructures through DNA hybridization in a highly predictable manner. DNA amphiphiles are a class of molecular hybrids where a short hydrophilic DNA is conjugated to a hydrophobic moiety. Since DNA amphiphiles comprise DNA as the hydrophilic segment, their self-assembly in aqueous medium always results in the formation of nanostructures with shell made of DNA. This clearly suggests that self-assembly of DNA amphiphiles is a straightforward strategy for the ultradense decoration of a nanostructure with DNA. However, initial attempts toward the design of DNA amphiphiles were primarily focused on long flexible hydrocarbon chains as the hydrophobic moiety, and it has been demonstrated in several examples that they typically self-assemble into DNA-decorated micelles (spherical or cylindrical). Hence, molecular level control over the self-assembly of DNA amphiphiles and achieving diverse morphologies was extremely challenging and unrealized until recently.In this Account, we summarize our recent efforts in the area of self-assembly of DNA amphiphiles and narrate the remarkable effect of the incorporation of a large π-surface as the hydrophobic domain in the self-assembly of DNA amphiphiles. Self-assembly of DNA amphiphiles with flexible hydrocarbon chains as the hydrophobic moiety is primarily driven by the hydrophobic effect. The morphology of such nanostructures is typically predicted based on the volume ratio of hydrophobic to hydrophilic segments. However, control over the self-assembly and prediction of the morphology become increasingly challenging when the hydrophobic moieties can interact with each other through other noncovalent interactions. In this Account, the unique self-assembly behaviors of DNA-π amphiphiles, where a large π-surface acts as the hydrophobe, are described. Due to the extremely strong π-π stacking in aqueous medium, the assembly of the amphiphile is found to preferably proceed in a lamellar fashion (bilayer) and hence the morphology of the nanostructures can easily be tuned by the structural modification of the π-surface. Design principles for crafting various DNA-decorated lamellar nanostructures including unilamellar vesicles, two-dimensional (2D) nanosheets, and helically twisted nanoribbons by selecting suitable π-surfaces are discussed. Unilamellar vesicular nanostructures were achieved by using linear oligo(phenylene ethynylene) (OPE) as the hydrophobic segment, where lamellar assembly undergoes folding to form unilamellar vesicles. The replacement of OPE with a strongly π-stacking hydrophobe such as hexabenzocoronene (HBC) or tetraphenylethylene (TPE) provides extremely strong π-stacking compared to OPE, which efficiently directed the 2D growth for the lamellar assembly and led to the formation of 2D nanosheets. A helical twist in the lamella was achieved by the replacement of HBC with hexaphenylbenzene (HPB), which is the twisted analogue of HBC, directing the assembly into helically twisted nanoribbons. The most beneficial structural feature of this kind of nanostructure is the extremely dense decoration of their surface with ssDNA, which can further be used for DNA-directed organization of other functional nanomaterials. By exploring this, their potential as a nanoscaffold for predefined assembly of plasmonic nanomaterials into various plasmonic 1D, 2D, and 3D nanostructures through DNA hybridization is discussed. Moreover, the design of pH-responsive DNA-based vesicles and their application as a nanocarrier for payload delivery is also demonstrated.

Synthesis and characterization of titania/graphene nanocomposite for application in photocatalysis

Titanium dioxide has been extensively investigated as a photocatalyst for water purification, presenting limitations such as recombination of electron-hole pairs generated by photons. The titania / graphene nanocomposites are promising materials to overcome these limitations due to the high specific area of graphene and unique electronic properties. In this work, an anatase-graphene nanocomposite was synthesized by a simple mixture assisted by ultrasound. Graphene was obtained by electrochemical exfoliation of graphite using the electrolysis technique. On the other hand, anatase was synthesized using the sol gel method. The obtained graphene, anatase and the nanocomposite material, were characterized with the X-ray diffraction technique (DRX), scanning electron microscopy (MEB) and transmission electron microscopy (MET). Using Raman spectroscopy, it was possible to verify that the graphite exfoliated correctly producing few layer-graphene. The lamellar nano-structure of the exfoliated graphite has crystallographic planes characteristic of graphite, graphene and graphene oxide. The presence of the anatase phase is shown in the diffraction spectrum of titania. The images obtained with SEM and TEM of the graphene sample show a layered lamellar structure and the TiO2 images show agglomerates of ellipsoidal nanoparticles. Obtained titania nanoparticles have a size of about 6 nm. Band gap value for such extremely low particle size nanocomposite is around 3.6 eV and presumably corresponds to the TiO2 (anatase) phase that completely surrounds the graphene. A nanocomposite model based on HRTEM observations is proposed. Considering the graphene electrical properties and the photocatalytic properties of TiO2, this nanocomposite promises to have applications in photocatalysis.

Lamellar Nanosheets of Water-Insoluble Amphiphiles via Aqueous Solution and Air/Liquid Interface Self-Assembly.

Two-dimensional (2D) lamellar nanostructures have attracted much interest due to their unique structure and properties. Various fabrication methods have been developed in recent years, including solution self-assembly, exfoliation, and Langmuir monolayer and Langmuir-Blodgett (LB) deposition. In this work, two kinds of facile methods were applied to fabricate lamellar structures of amphiphilic molecules, such as 10,12-pentacosadiynoic acid (PCDA). In method I, the amphiphilic molecules were introduced into aqueous solutions with dimethylformamide (DMF), a solvent miscible with water, through a mass transfer process across a planar liquid/liquid interface; in method II, the DMF solution of the amphiphilic molecules was added directly onto the aqueous solution surface. With the spread and diffusion of DMF, nanosheets with lamellar structures formed in the aqueous solution and at the air/liquid interface, respectively. It is very interesting that the nanosheets obtained through these two methods consist of an even number and odd number of PCDA monolayers, respectively, reflecting different fabrication mechanisms. Method I provides an approach to gently mix organic solutions with aqueous solutions, while method II can be regarded as an extension of the Langmuir monolayer technique, which combines the interfacial assembly with that in solution. These methods have been extended to a series of amphiphilic molecules, and ordered layered structures have been obtained successfully.

Enhanced gas sensing properties for formaldehyde based on ZnO/Zn2SnO4 composites from one-step hydrothermal synthesis

Formaldehyde gas sensor with high performance is indispensable for monitoring indoor air quality. Exploring novel nanostructured composites as gas sensing materials is considered to be a feasible way to enhance the sensing performance. In this work, one-step hydrothermal method was employed for facile synthesis of ZnO/Zn2SnO4 nanocomposites and the as-prepared sample took on a homogeneous hexagonal lamellar nanostructure with a diameter of 600 nm–900 nm and thickness of about 100 nm. Gas sensing properties of the sample were tested and the results demonstrated that the ZnO/Zn2SnO4 composites possessed excellent sensing performances to formaldehyde. At 160 °C, the ZnO/Zn2SnO4 composites based sensor exhibited a high response of 22.5 towards 100 ppm of formaldehyde and a detection limit as low as 500 ppb. Compared with pristine Zn2SnO4 and ZnO, ZnO/Zn2SnO4 composites showed higher sensitivity (increased by 80% and 120%), better selectivity and lower detection limit. The noteworthy improvement of formaldehyde sensing performances could be attributed to the synergetic effect as well as the formation of n-n type heterojunctions between Zn2SnO4 and ZnO. The mechanism involved in gas sensing performance of ZnO/Zn2SnO4 composites was also discussed.

Synthesis of bottlebrush block copolymers from bottlebrush polystyrene and bottlebrush random copolymer of ω‐end‐norbornyl polymethacrylates and their self‐assembly

AbstractSix different bottlebrush block copolymers (BBCPs) (A‐b‐(B‐co‐C)) from bottlebrush polystyrene (A) and bottlebrush random copolymers (B‐co‐C) of polymethacrylates were synthesized through living anionic polymerization and ring‐opening metathesis polymerization. To induce the phase separation of bottlebrush polystyrene (PNB‐g‐PS) (A) and bottlebrush poly(benzyl methacrylate) (PNB‐g‐PBzMA) (C)‐based BBCP with an extremely low Flory–Huggins interaction parameter (χ), three kinds of bottlebrush polymethacrylates (B): poly(norbornene‐g‐methyl methacrylate) (PNB‐g‐PMMA), poly(norbornene‐g‐tert‐butyl methacrylate) (PNB‐g‐PtBMA), and poly(norbornene‐g‐methacrylic acid) (PNB‐g‐PMAA), respectively, were randomly combined with C. An order–disorder phase transition of the BBCPs (A‐b‐(B‐co‐C)) was observed with a change in mole ratios of PMMA, PtBMA, or PMAA to PBzMA of 25, 50, and 75% in random copolymer blocks using field‐emission scanning microscopy. While the BBCP with 25% of PMAA in the random copolymer block showed an ordered lamellar nanostructure, a disordered morphology was revealed at 75% PMAA. SEM showed that the incorporation of PtBMA and PBzMA showed better‐ordered lamellar morphologies than was the case with PMMA and PBzMA at the same mole ratios.

Nucleation, Pattern Development, and Fidelity in the Photoelectrodeposition of Se-Te Nanostructures

The electrochemical growth of Se-Te under polarized illumination results in anisotropic, highly-ordered lamellar nanostructures, tunable by input wavelength. This spontaneous growth occurs at room temperature, in an isotropic solution, with no templating or chemically-directing agents, and with mW-cm-2 illumination intensity with no requirement for coherency. The deposition process is compatible with a wide variety of conductive substrates and can be performed over large areas of unpatterned substrates. However, pattern fidelities in these films are generally low. Improving the potentially broad applicability of this patterning method requires an understanding of pattern development and of factors contributing to the long-range order of films deposited through this phenomenon.Methods of quantifying pattern fidelity have been developed using Fourier-transform (FT) analysis of large-area images of photoelectrodeposited Se-Te films. Nominally identical illumination conditions during the deposition of Se-Te on crystalline (111)-oriented Si substrates doped degenerately with either p- or n-type dopants produced a variation in the morphology of Se-Te films. Films deposited on p+-Si generally displayed much less defective patterns, with a higher degree of anisotropy and a more well-defined pattern period versus films deposited on n+-Si. These results are attributed to the energetics at the dynamic junction formed by growing Se-Te and the Si substrate.Analysis of film morphologies at early levels of mass addition to growth substrates elucidate the mechanism by which junction energetics affect resulting film morphologies. Higher nucleation densities are generally observed under conditions that produced Se-Te films with relatively higher pattern fidelities. Control of pattern fidelity by control of nucleation density, through substrate choice and tuning of applied deposition potential, is demonstrated.

Investigations of strength and ductility in Ni-xCo-10Al alloys via discontinuous precipitation

The occurrence of discontinuous precipitation (DP) in alloys is usually considered to be deleterious to the mechanical properties. However recent studies have shown that the Ni-Co-Al alloys can produce lamellar nanostructure via DP, which can be used to strengthen the alloys similar to pearlites in steel. In this study, the microstructure and mechanical properties of Ni-Co-Al alloys with different compositions and aging conditions were studied. The results indicate that near complete DP transformation can effectively improve both the strength and ductility. The competing transformation behavior between continuous and discontinuous precipitation as well as the strengthening mechanism are analyzed and discussed using electron diffraction.

Heterogeneous precipitation mediated heterogeneous nanostructure enhances strength-ductility synergy in severely cryo-rolled and annealed CoCrFeNi2.1Nb0.2 high entropy alloy

Possibilities of enhancing mechanical properties of brittle intermetallic containing high entropy alloys (HEAs) using novel processing and microstructural design strategies were investigated in the present work. For this purpose, homogenized CoCrFeNi2.1Nb0.2 HEA consisting of FCC matrix and complex Laves phase particles was successfully processed by severe cold- or cryo-rolling to 90% reduction in thickness followed by annealing (800 °C/1 hour(h)). As compared to cold-rolling, cryo-rolling resulted in a finer lamellar nanostructure and decidedly greater fragmentation of the Laves phase. Upon annealing, the cold-rolled HEA showed a recrystallized FCC matrix dispersed with D019 structured ε nano-precipitates. In contrast, the finer nanostructure and greater driving force for accelerated precipitation of profuse nano-precipitates at the early stages of annealing inhibited recrystallization in the cryo-rolled HEA and resulted in the formation of heterogeneous microstructure consisting of retained deformed and recrystallized regions. The novel heterogeneous microstructure of the cryo-rolled and annealed HEA resulted in a remarkable enhancement in strength-ductility synergy. The present results indicated that cryo-rolling could be used as an innovative processing strategy for tailoring heterogeneous microstructure and achieving novel mechanical properties.