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Microencapsulation helps to improve bioavailability of a functional whey protein, lactoferrin (Lf), in adults. Herein, we report the Lf loading capacity (LC) and retention efficiency (RE) in the microparticles of surface-reacted calcium carbonate (SRCC) of different types and compare them to those of widely used vaterite microparticles. The LCs and REs are analyzed in connection to the total surface area and the volume of intraparticle pores. The best performing SRCC3 demonstrates Lf LC of 11.00 wt% achieved in a single absorption step and 74% RE after two cycles of washing with deionized water. A much larger surface area of SRCC templates and a lower pH required to release Lf do not affect its antitumor activity in MCF-7 assay. Layer-by-Layer assembly of pepsin-tannic acid multilayer shell around Lf-loaded microparticles followed by acidic decomposition of the inorganic core produces microencapsulated Lf with a yield ~36 times higher than from vaterite templates reported earlier, while the scale of encapsulated Lf production is ~12,000 times larger. In vitro digestion tests demonstrate the protection of ~65% of encapsulated Lf from gastric digestion. The developed capsules are prospective candidates for functional foods fortified with Lf.

To explore the potential beneficial effect beyond shot peening (SP)’s conventional performance, ex-situ warm shot peening (WSP) of Ti-6Al-4V coupons have been carried out. The coupons were pre-heated to 200 and 400 °C, before they were immediately transferred into a SP booth for shot-peening. While high cycle fatigue (HCF) tests did not detect a favorable improvement in fatigue life at high (0.9F0.2) and medium loadings (0.7F0.2), a significant increase in cycle-to-failure (Nf) in low loading (0.5F0.2) was observed when the ex-situ WSP temperature was raised to 200 and further to 400 °C. Center hole drilling and electron backscatter diffraction (EBSD) were employed to unveil the mechanism for such fatigue improvement.

GeTe as one of the most promising medium temperature thermoelectrics has progressed leaps and bounds in recent years, largely thanks to a combination of its unique electronic, thermal and structural properties. Despite its various advantages, a major factor standing in the way of wide commercial adoptions lies in its unreliable mechanical properties. This work reports Re doping as a strategy to drastically enhance the mechanical properties of GeTe, resulting in Vickers microhardness as high as 342.6 Hv in Ge0.88Sb0.10Re0.02Te, which is more than double that of pristine GeTe (145 Hv). Ge0.88Sb0.10Re0.02Te also exhibited a Young's modulus of 64.1 GPa, substantially higher than many other binary chalcogenide thermoelectrics. The significant enhancement of GeTe in mechanical properties is mainly related to the mechanism of precipitation hardening. In addition, we found that while the electronic properties were slightly compromised with Re doping, the lattice thermal conductivity was reduced due to point defects scattering brought about by Re atoms. Therefore, a high zT value (>1.6) at 600–800 K is achieved in Ge0.88Sb0.10Re0.02Te. Furthermore, above 10% device efficiency can be expected for the operating temperature between 300–800 K. Such a solution to strengthen the mechanical properties of GeTe using Re doping is expected to play a major part in the push for full-scale GeTe-based thermoelectric devices.

The benefits of various functional foods are often negated by stomach digestion and poor targeting to the lower gastrointestinal tract. Layer-by-Layer assembled protein-tannic acid (TA) films are suggested as a prospective material for microencapsulation of food-derived bioactive compounds. Bovine serum albumin (BSA)-TA and pepsin-TA films demonstrate linear growth of 2.8 ± 0.1 and 4.2 ± 0.1 nm per bi-layer, correspondingly, as shown by ellipsometry. Both multilayer films are stable in simulated gastric fluid but degrade in simulated intestinal fluid. Their corresponding degradation constants are 0.026 ± 0.006 and 0.347 ± 0.005 nm−1 min−1. Milk proteins possessing enhanced adhesion to human intestinal surface, Immunoglobulin G (IgG) and β-Lactoglobulin (BLG), are explored to tailor targeting function to BSA-TA multilayer film. BLG does not adsorb onto the multilayer while IgG is successfully incorporated. Microcapsules prepared from the multilayer demonstrate 2.7 and 6.3 times higher adhesion to Caco-2 cells when IgG is introduced as an intermediate and the terminal layer, correspondingly. This developed material has a great potential for oral delivery of numerous active food-derived ingredients.

Phosphide-based thermoelectrics are a relatively less studied class of compounds, primarily due to the presence of light elements, which result in high thermal conductivity and inherent stability problems. In this work, we present a stable phosphide-tetrahedrite, Ag6Ge10P12, which possesses the highest zT (∼0.7) among all known phosphides at intermediate temperatures (750 K). We examine the intrinsic electronic and thermal transport properties of this compound by expressing the transport properties in terms of weighted mobility (μW), transport coefficient (σE0), and material quality factor (B), from which we are able to elucidate that the origin of its high zT can be attributed to the platelike Fermi surface and high level of band multiplicity related to its complex band structure. Finally, we discuss the origin of the low lattice thermal conductivity observed in this compound using experimental sound velocity, elastic properties, and Debye-Callaway model, thus laying the foundation for similar stable phosphides as potentially earth-abundant and nontoxic intermediate-temperature thermoelectric materials.

GeTe is highly sought-after due to its versatility as high-performance thermoelectrics, phase change materials, as well as ferroelectric Rashba semiconductor. Compared to most thermoelectric materials, it has an additional degree of freedom of rhombohedral-cubic phase transition at 673 K. At this temperature, the lattice thermal conductivity approaches theoretical minimum due to ferroelectric instability while the high-energy Σ and low-energy L bands converge to give outstanding electronic properties. Therefore, modulation of the phase transition temperature allows simultaneous and synergistic tuning of electronic and thermal transport properties to achieve high zT. In this work, Sn alloying together with Bi, Sb doping is used to suppress the phase transition to achieve a pure cubic structure with lattice thermal conductivity of around 0.4 W/mK and peak zT of 1.7 at 723 K with average zT of 1.23 between 400 and 800 K. Furthermore, Vickers hardness of 270, and Young’s modulus of 63.5 GPa in Ge0.4Sn0.4Bi0.02Sb0.12Te is by far the highest amongst binary chalcogenides. More importantly, the high quality factor achieved in this work enables ample room for further zT improvements. The fundamental insights drawn from this work provide a pathway towards engineering GeTe-based alloys to achieve high zT at any temperature of interest. Agency for Science, Technology and Research (A*STAR) Ministry of Education (MOE) Accepted version

Shot peening is a well-established surface treatment technique to improve metallic components’ fatigue lives by introducing compressive residual stress at their surface layers. Using α/β Ti–6Al–4V alloy as an example, the fatigue life of Ti64 was significantly enhanced after a compressive residual stress was introduced to a depth of 208 µm via shot peening treatment. The top ~24 µm layer from surface was found interestingly unable to be indexed under electron backscatter diffraction (EBSD), a depth coinciding with the presence of maximum compressive residual stress as revealed by center hole drilling method. Transmission electron microscope (TEM) with crystallographic orientation mapping was therefore employed to probe the top surface layer in order to unveil the origin of such thick non-indexed region observed in EBSD after shot peening and its effect on enhancement of component's fatigue life.

Silica nanomaterials have found prevailing use in biomedical applications due to their biocompatibility and non-toxicity. The use of a structure-directing agent in silica sol-gel synthesis enables us to direct the formation of silica nanostructures into forms that are otherwise difficult to obtain, allowing the exertion of a fine degree of control over the morphology, dimensions and architecture of the nanostructures. Single-tailed surfactants have been used extensively as soft templates to produce mesoporous silica materials. This study investigates the use of a double-tailed surfactant, a didodecyldimethylammonium phosphate surfactant (DDAH2PO4) as a structure-directing agent in the sol-gel synthesis of silica at ambient conditions in aqueous solution. The effects of varying reaction parameters such as surfactant concentration and solution temperature on resulting silica morphology are presented. Morphological transitions from nanobeads to hexagonal plates and toroidal concave particles are observed with increasing surfactant concentrations, as well as a gradual loss in templating ability at elevated solution temperatures (up to 25 °C). This allows us to access different morphologies and dimensions of nanostructures within the same synthesis scheme templated with DDAH2PO4.

Direct imprinting of metals is predominantly achieved by using polydimethylsiloxane (PDMS) molds to pattern metal nanoparticles and subsequently melting them to form continuous structures. Although such a combination can successfully imprint metals, the yield and reproducibility are usually low when sub-100 nm features over large areas are desired. In this work, we demonstrate a simple method involving the addition of a cross-linker ethylene glycol dimethacrylate (EDMA) to a palladium metal precursor, and its in situ free radical polymerization during imprinting, which not only dramatically increases the yield to ∼100% but also enables high reproducibility. Palladium mercaptide resist was formed by dissolving acetoxy(benzylthio)palladium, EDMA and azobis-(isobutyronitrile) in an organic solvent mixture. The resist underwent polymerization when imprinted using a silicon mold at 120 °C with pressures as low as 30 bar. Polymerization rigidly shapes the imprinted patterns, traps the metal atoms, reduces the surface energy and strengthens the structures, thereby giving ∼100% yield after demolding. Heat-treatment of the imprinted structures at 330 °C resulted in the loss of organics and their subsequent shrinkage without the loss of integrity or aspect ratio and converted them to palladium nanostructures as small as ∼35 nm wide, over areas >1 cm × 1 cm. With suitable precursors, our technique can potentially be extended to pattern noble metals such as platinum, gold and silver.

Lactoferrin (Lf) has considerable potential as a functional ingredient in food, cosmetic and pharmaceutical applications. However, the bioavailability of Lf is limited as it is susceptible to digestive enzymes in gastrointestinal tract. The shells comprising alternate layers of bovine serum albumin (BSA) and tannic acid (TA) were tested as Lf encapsulation system for oral administration. Lf absorption by freshly prepared porous 3 μm CaCO3 particles followed by Layer-by-Layer assembly of the BSA-TA shells and dissolution of the CaCO3 cores was suggested as the most efficient and harmless Lf loading method. The microcapsules showed high stability in gastric conditions and effectively protected encapsulated proteins from digestion. Protective efficiency was found to be 76 ± 6% and 85 ± 2%, for (BSA-TA)4 and (BSA-TA)8 shells, respectively. The transit of Lf along the gastrointestinal tract (GIT) of mice was followed in vivo and ex vivo using NIR luminescence. We have demonstrated that microcapsules released Lf in small intestine allowing 6.5 times higher concentration than in control group dosed with the same amount of free Lf. Significant amounts of Lf released from microcapsules were then absorbed into bloodstream and accumulated in liver. Suggested encapsulation system has a great potential for functional foods providing lactoferrin.

Although step-and-flash imprint lithography, or S-FIL, has brought about tremendous advancement in wafer-scale fabrication of sub-100 nm features of photopolymerizable organic and organo-silicon-based resists, it has not been successful in direct patterning of inorganic materials such as oxides because of the difficulties associated with resist formulation and its dispensing. In this paper, we demonstrate the proof-of-concept S-FIL of titanium dioxide (TiO2) carried by an acrylate-based formulation containing an allyl-functionalized titanium complex. The prepolymer formulation contains 48 wt % metal precursor, but it exhibits low enough viscosity (∼5 mPa·s) to be dispensed by an automatic dispensing system, adheres and spreads well on the substrate, is insensitive to pattern density variations, and rapidly polymerizes when exposed to broadband UV radiation to give a yield close to 95%. Five fields, each measuring 1 cm × 1 cm, consisting of 100 nm gratings were successively imprinted. Heat-treatment of the...

Development of composite polymer/graphene oxide (GO) materials attracts significant attention due to their unique properties. In this work, highly ordered arrays of hollow microchambers made of composite polyelectrolyte/GO multilayers (PEGOMs) are successfully fabricated via layer-by-layer assembly on sacrificial or sustainable templates having imprinted patterns of microwells on their surface. Mechanical and optical properties of PEGOMs are studied by nanoindentation and near-infrared (NIR) absorption spectroscopy. Incorporation of three GO layers in between the polyelectrolyte multilayer stacks increases Young's modulus and critical stress of the microchambers by a factor of 5.6 and 2.6, respectively. Optical density of this PEGOM film is found to decrease gradually from 0.14 at λ = 800 nm to 0.06 at λ = 1500 nm. Remote opening of PEGOM microchambers with NIR laser beam is also demonstrated. One of the possible applications of the developed structures includes micropackaging and delivery systems in biological tissues with remote triggering.

Flexible palladium-based H2 sensors have a great potential in advanced sensing applications, as they offer advantages such as light weight, space conservation, and mechanical durability. Despite these advantages, the paucity of such sensors is due to the fact that they are difficult to fabricate while maintaining excellent sensing performance. Here, we demonstrate, using direct nanoimprint lithography of palladium, the fabrication of a flexible, durable, and fast responsive H2 sensor that is capable of detecting H2 gas concentration as low as 50 ppm. High resolution and high throughput patterning of palladium gratings over a 2 cm × 1 cm area on a rigid substrate was achieved by heat-treating nanoimprinted palladium benzyl mercaptide at 250 °C for 1 h. The flexible and robust H2 sensing device was fabricated by subsequent transfer nanoimprinting of these gratings into a polycarbonate film at its glass transition temperature. This technique produces flexible H2 sensors with improved durability, sensitivity, and response time in comparison to palladium thin films. At ambient pressure and temperature, the device showed a fast response time of 18 s at a H2 concentration of 3500 ppm. At 50 ppm concentration, the response time was found to be 57 s. The flexibility of the sensor does not appear to compromise its performance.

Three-dimensional hierarchical patterning of metals is of paramount importance in diverse fields involving photonics, controlling surface wettability and wearable electronics. Conventionally, this type of structuring is tedious and usually involves layer-by-layer lithographic patterning. Here, we describe a simple process of direct nanoimprint lithography using palladium benzylthiolate, a versatile metal-organic ink, which not only leads to the formation of hierarchical patterns but also is amenable to layer-by-layer stacking of the metal over large areas. The key to achieving such multi-faceted patterning is hysteretic melting of ink, enabling its shaping. It undergoes transformation to metallic palladium under gentle thermal conditions without affecting the integrity of the hierarchical patterns on micro- as well as nanoscale. A metallic rice leaf structure showing anisotropic wetting behavior and woodpile-like structures were thus fabricated. Furthermore, this method is extendable for transferring imprinted structures to a flexible substrate to make them robust enough to sustain numerous bending cycles.

Although step-and-flash imprint lithography, or S-FIL, has brought about tremendous advancement in wafer-scale fabrication of sub-100 nm features of photopolymerizable organic and organo-silicon-based resists, it has not been successful in direct patterning of inorganic materials such as oxides because of the difficulties associated with resist formulation and its dispensing. In this paper, we demonstrate the proof-of-concept S-FIL of titanium dioxide (TiO(2)) carried by an acrylate-based formulation containing an allyl-functionalized titanium complex. The prepolymer formulation contains 48 wt % metal precursor, but it exhibits low enough viscosity (∼5 mPa·s) to be dispensed by an automatic dispensing system, adheres and spreads well on the substrate, is insensitive to pattern density variations, and rapidly polymerizes when exposed to broadband UV radiation to give a yield close to 95%. Five fields, each measuring 1 cm × 1 cm, consisting of 100 nm gratings were successively imprinted. Heat-treatment of the patterned structures at 450 °C resulted in the loss of organics and their subsequent shrinkage without the loss of integrity or aspect ratio and converted them to TiO(2) anatase nanostructures as small as 30 nm wide. With this approach, wafer-scale direct patterning of functional oxides on a sub-100 nm scale using S-FIL can become a distinct possibility.

We demonstrate a different approach to direct nanoimprint lithography of oxides, in particular TiO(2), using the metal methacrylate route which not only gives very high resolution ( approximately 20 nm) but also provides yields of approximately 100% over areas > 1 cm x 1 cm. TiO(2) was imprinted using a polymerizable liquid 'TiO(2) resin' consisting of a mixture of titanium methacrylate, ethylene glycol dimethacrylate, and azobis-(isobutyronitrile). The resin underwent free radical polymerization when imprinted using a silicon mold at 110 degrees C with pressures as low as 10 bar. Polymerization strengthens the imprinted structures, thereby giving approximately 100% yield after demolding. Heat-treatment of the imprinted structures at 400 degrees C resulted in the loss of organics and their subsequent shrinkage ( approximately 75%) without the loss of integrity or aspect ratio, and converted them to TiO(2) nanostructures as small as approximately 20 nm wide. Furthermore, our method demonstrates that large imprinted areas of sub-100-nm features can be achieved by sub-micron molds which translate into huge cost savings with the added flexibility of direct patterning of urinary as well as multi-component oxides.

Surface topographical patterning is a simple way to functionalize surfaces without changing material chemistry. Topographical patterning of nonplanar surfaces has remained a challenge, despite sought after applications in microfluidics, optics, and biomedical technologies. Here the authors develop transparent, reusable soft molds that allow facile micro- and nanopatterning of macroscopically curved surfaces. The authors use bilayer molds with a soft backing and a hard pattern carrying layer to overcome challenges that arise from the opposing need for mold compliance (to allow conformal contact with nonflat substrates) and rigidity (to maintain patterned feature resolution and fidelity). With our approach, high yield curved surface patterning (>98%) over large (2 × 1 cm) area can be effectively achieved. Structure replication down to 80 nm resolution is demonstrated.

After the cost of ownership of tool, the next significant cost involved in nanoimprint lithography is that of mold fabrication. The cost of mold fabrication is proportional to the area of pattern and follows an inverse relationship with the pattern resolution. In this work, the authors demonstrate proof-of-concept fabrication of Si and SiO2 grating molds of variable feature sizes, spacings, densities, and aspect ratios that can be generated from a single Si master mold of 2 μm line and space features. This process utilizes “SiO2 resin,” which can be imprinted via in situ thermal free radical polymerization. Heat-treatment of the patterned resin resulted in loss of organics, formation of SiOx and gave rise to known feature size reduction (∼65%). After the pattern transfer using SiOx as the etch mask, a Si daughter mold containing 0.7 μm wide gratings with 3.3 μm spacing was generated. The process of imprinting and heat-treatment was repeated using the daughter mold, which regenerated a mold that approximates the master mold feature profile. Our technique demonstrates that submicron-sized features can be achieved from Si molds containing micron-sized features and vice versa. Such flexibility may lead to substantial reduction in the cost of mold fabrication.

Nanostructuring of Al2O3 is predominantly achieved by the anodization of aluminum film and is limited to obtaining porous anodized aluminum oxide (AAO). One of the main restrictions in developing approaches for direct fabrication of various types of Al2O3 patterns, such as lines, pillars, holes, etc, is the lack of a processable aluminum-containing resist. In this paper, we demonstrate a stable precursor prepared by reacting aluminum tri-sec-butoxide with 2-(methacryloyloxy)ethyl acetoacetate, a chelating monomer, which can be used for large area direct nanoimprint lithography of Al2O3. Chelation in the precursor makes it stable against hydrolysis whilst the presence of a reactive methacrylate group renders it polymerizable. The precursor was mixed with a cross-linker and their in situ thermal free-radical co-polymerization during nanoimprinting rigidly shaped the patterns, trapped the metal atoms, reduced the surface energy and strengthened the structures, thereby giving a ∼100% yield after demolding. The imprinted structures were heat-treated, leading to the loss of organics and their subsequent shrinkage. Amorphous Al2O3 patterns with line-widths as small as 17 nm were obtained. Our process utilizes the advantages of sol–gel and methacrylate routes for imprinting and at the same time alleviates the disadvantages associated with both these methods. With these benefits, the chelating monomer route may be the harbinger of the universal scheme for direct nanoimprinting of metal oxides.

The use of polymerization to solidify, strengthen and imprint liquid organic materials is the basis of ultraviolet (UV) nanoimprint lithography. In spite of these advantages, the use of polymerization to pattern materials in thermal nanoimprint lithography is almost non-existent. In this study, we demonstrate a facile and general method to directly imprint a host of unary metal oxides (Fe2O3, ZrO2, TiO2, Nb2O5 and Ta2O5) at a very high resolution viain situ thermal free radical co-polymerization of various metal methacrylates in the presence of cross-linker ethylene glycol dimethacrylate using a silicon mold. Polymerization during nanoimprinting rigidly shapes the patterns, traps the metal atoms, reduces the surface energy and strengthens the structures, thereby giving ∼100% yield after demolding. It was found that the higher oxidation state of metal resulted in excessive cracking of imprinted structures. This could be due to a higher degree of cross-linking of the precursor leading to shrinkage-related stress. Optimization of the resin composition by partially replacing ethylene glycol dimethacrylate with methyl methacrylate alleviated this problem. Heat-treatment of the imprinted structures resulted in the loss of organics, their subsequent shrinkage and converted the patterns to their corresponding metal oxides with line-widths as small as 25 nm.