Nanocrystalline Cellulose to Reduce Superplasticizer Demand in 3D Printing of Cementitious Materials.

One challenge for 3D printing is that the mortar must flow easily through the printer nozzle, and after printing, it must develop compressive strength fast and high enough to support the layers on it. This requires an exact and difficult control of the superplasticizer (SP) dosing. Nanocrystalline cellulose (CNC) has gained significant interest as a rheological modifier of mortar by interacting with the various cement components. This research studied the potential of nanocrystalline cellulose (CNC) as a mortar aid for 3D printing and its interactions with SPs. Interactions of a CNC and SP with cement suspensions were investigated by means of monitoring the effect on cement dispersion (by monitoring the particle chord length distributions in real time) and their impact on mortar mechanical properties. Although cement dispersion was increased by both CNC and SP, only CNC prevented cement agglomeration when shearing was reduced. Furthermore, combining SP and CNC led to faster development of compressive strength and increased compressive strength up to 30% compared to mortar that had undergone a one-day curing process.

High Milling Time Influence on the Phase Stability and Electrical Properties of Fe50Mn35Sn15 Heusler Alloy Obtained by Mechanical Alloying.

Fe50Mn35Sn15 Heusler alloy, obtained by mechanical alloying, was subjected to larger milling times in the range of 30-50 h to study the phase stability and morphology. X-ray diffraction studies have shown that the milled samples crystallise in a disordered A2 structure. The A2 structure was found to be stable in the milling range studied, contrary to the computation studies performed on this composition. Using Rietveld refinements, the lattice parameter, mean crystallite size, and lattice strain were computed. The nature of the obtained phases by milling was found to be nanocrystalline with values below 50 nm. A linear increase rate of 0.00713 (h-1) was computed for lattice strain as the milling time increased. As the milling time increases, the lattice parameter of the cubic Heusler was found to have a decreasing behaviour, reaching 2.9517 Å at 50 h of milling. The morphological and elemental distribution-characterised by scanning electron microscopy and energy-dispersive X-ray spectroscopy-evidenced Mn and Sn phase clustering. As the milling time increased, the morphology of the sample was found to change. The Mn and Sn cluster size was quantified by elemental line profile. Electrical resistivity evolution with milling time was analysed, showing a peak for 40 h of milling time.

Molecular and Dissociative Adsorbed Water Concentration and Surface Protonic Conduction in Nanocrystalline TiO2.

Surface protonic conduction in porous nanocrystalline oxides is commonly involved in catalytic processes. The configuration of surface adsorbed water on oxides plays a crucial role in surface protonic conduction. However, studies on the impact of complex surface adsorbed water configuration on the surface water concentration and diffusivity remain limited, and hinder an in-depth understanding of surface proton transport mechanisms, and the design of better surface proton conductors. Here, in situ Raman spectroscopy is utilized to quantitatively identify the contribution of dissociative and molecular adsorbed water components on porous nanocrystalline TiO2 surfaces between 25 and 200 °C. The variations in molecular and dissociative adsorbed water concentration agree with the predominant surface proton conduction mechanisms at three different temperature stages. From 40 to 125 °C, the reduced coverage of molecular adsorbed water layer results in the decreasing proton diffusivity. Water dissociation on the nanocrystalline TiO2 surface is easier in wet N2 than in wet O2, resulting in higher proton conductivity in wet N2; while the surface proton diffusivities in these two atmospheres are similar. The in situ spectroscopy technique enables the improvement of surface proton conducting oxides through quantitative evaluation and modulation of the surface proton concentration and diffusivity.

Real-Space Tilting Method for Atomic Resolution STEM Imaging of Nanocrystalline Materials.

Atomic-resolution scanning transmission electron microscopy (STEM) characterization requires precise tilting of the specimen to a high symmetric zone axis, which is usually processed in reciprocal space by following the diffraction patterns. However, for small-sized nanocrystalline materials, their diffraction patterns are often too faint to guide the tilting process. Here, a simple and effective tilting method is developed based on the diffraction contrast change of the shadow image in the Ronchigram. The misorientation angle of the specimen can be calculated and tilted to the zone axis based on the position of the shadow image with lowest intensity. This method requires no prior knowledge of the sample and the maximum misorientation angle that can be corrected is >±6.9° with sub-mrad accuracy. It operates in real space, without recording the diffraction patterns of the specimens, making it particularly effective for nanocrystalline materials. Combined with the scripting to control the microscope, the sample can be automatically tilted to the zone axis under low dose conditions (<0.17 e- Å- 2 s-1), facilitating the imaging of beam sensitive materials such as zeolites or metal-organic frameworks. This automated tilting method can significantly contribute to the atomic-scale characterization of the nanocrystalline materials by STEM imaging.

3D-Printed Hydrogels with Engineered Nanocrystalline Domains as Functional Vascular Constructs.

Three-dimensionally printed (3DP) hydrogel-based vascular constructs have been investigated in response to the impaired function of blood vessels or organs by replicating exactly the 3D structural geometry to approach their function. However, they are still challenged by their intrinsic brittleness, which could not sustain the suture piercing and enable the long-term structural and functional stability during the direct contact with blood. Here, we reported the high-fidelity digital light processing (DLP) 3D printing of hydrogel-based vascular constructs from poly(vinyl alcohol)-based inks, followed by mechanical strengthening through engineering the nanocrystalline domains and subsequent surface modification. The as-prepared high-precision hydrogel vascular constructs were imparted with highly desirable mechanical robustness, suture tolerance, swelling resistance, antithrombosis, and long-term patency. Notably, the hydrogel-based bionic vein grafts, with precise valve structures, exhibited excellent control over the unidirectional flow and successfully fulfilled the biological functionalities and patency during a 4-week implantation within the deep veins of beagles, thus corroborating the promising potential for treating chronic venous insufficiency.

Magnetic shielding properties of an iron-based nanocrystalline alloy for induction heating systems.

A nanocrystalline alloy, with an iron-based composition (Fe58.5Si16.7B6.5Nb5.1Cu13.2) and a Curie temperature of 570 °C, was investigated for its effectiveness as magnetic shielding films in an induction heating system. The primary focus of the research was to evaluate the shielding performance of the 3-turned (9-layered) shielding films with dimensions of 135 mm × 17 mm × 0.15 mm. Upon winding, these films formed a cylindrical structure that enveloped the coil, with a diameter of 13.9 mm and a height of 17 mm. The results showed that increasing the degree of fragmentation within the nanocrystalline shielding films significantly reduced the magnetic permeability by decreasing the real component from 11,500 to 400 and the imaginary part from 2800 to 20. However, a lower degree of fragmentation led to a 10 % increase in the resistance (Rs) of the heating module, although this effect was less pronounced as the relative permeability continued to increase. Furthermore, observations on preheating time to a set temperature of 400 °C and total energy consumption over a duration of 250s revealed an initial downward trend, followed by a rapid increase that even exceeded the initial values as the magnetic permeability of the nanocrystalline shielding films augmented. Notably, the study emphasized that nanocrystalline shielding films with a relative permeability value of 1000 demonstrated exceptional magnetic shielding performance, resulting in a 12.5 % reduction in preheat time and 7 % less energy consumption during preheating. In addition to empirical findings, the study developed a theoretical model elucidating the shielding mechanism inherent in induction heating systems. This model serves as a robust framework for the application of nanocrystalline shielding materials in such systems, laying the groundwork for enhanced magnetic shielding capabilities in future applications.

Molecular dynamics analysis of subsurface brittleness mechanism of nanocrystalline 3C-SiC rough friction surface.

To study the effect of polycrystalline 3C-SiC rough friction surface on the mechanism of subsurface brittleness during nanocrystalline grinding. Initial grinding models of polycrystalline 3C-SiC and diamond abrasive grains on rough friction surfaces are developed using molecular dynamics methods and the Voronoi method for constructing polycrystalline abrasive grains. The processing mechanism of 3C-SiC is analyzed by post-processing methods such as dislocation defect analysis, atomic arrangement analysis and stress analysis. At 2.6 nm, "stress concentration" occurs between the abrasive particles and the workpiece, forming irregular force shapes. The larger the grain size, the smaller the crystal hardness, the greater the possibility of crystal fracture, and it is obvious in the crystal of larger grains. At 8 nm, the crystal breaks and creates vacancies. The roughness of the polycrystalline 3C-SiC friction surface and the cross-cutting mechanism between grains with grain boundaries are found to be effective in ameliorating the damage in the subsurface layer.

Predictive modelling of laser powder bed fusion of Fe-based nanocrystalline alloys based on experimental data using multiple linear regression analysis.

This study harnessed bivariate correlational analysis, multiple linear regression analysis and tree-based regression analysis to examine the relationship between laser process parameters and the final material properties (bulk density, saturation magnetization (M s ), and coercivity (H c )) of Fe-based nano-crystalline alloys fabricated via laser powder bed fusion (LPBF). A dataset comprising of 162 experimental data points served as the foundation for the investigation. Each data point encompassed five independent variables: laser power (P), laser scan speed (v), hatch spacing (h), layer thickness (t), and energy density (E), along with three dependent variables: bulk density, M s , and H c . The bivariate correlational analysis unveiled that bulk density exhibited a significant correlation with P, v, h, and E, whereas M s and H c displayed significant correlations exclusively with v and P, respectively. This divergence may stem from the strong influence of microstructure on magnetic properties, which can be impacted not only by the laser process parameters explored in this study but also by other factors such as oxygen levels within the build chamber. Furthermore, our statistical analysis revealed that bulk density increased with rising P, h, and E, while decreased with higher v. Regarding the magnetic properties, a high M s was achievable through low v, while low H c resulted from high P. It was concluded that P and v were considered as the primary laser process parameters, influencing h and t due to their control over the melt-pool size. The application of multiple linear regression analysis allowed the prediction of the bulk density by using both laser process parameters and energy density. This approach offered a valuable alternative to time-consuming and costly trial-and-error experiments, yielding a low error of less than 1 % between the mean predicted and experimental values. Although a slightly higher error of approximately 6 % was observed for M s , a clear association was established between M s and v, with lower v values corresponding to higher M s values. Additionally, a further comparison was conducted between multiple linear regression and three tree-based regression models to explore the effectiveness of these approaches.

Operando pair distribution function analysis of nanocrystalline functional materials: the case of TiO2-bronze nanocrystals in Li-ion battery electrodes.

Structural modelling of operando pair distribution function (PDF) data of complex functional materials can be highly challenging. To aid the understanding of complex operando PDF data, this article demonstrates a toolbox for PDF analysis. The tools include denoising using principal component analysis together with the structureMining, similarityMapping and nmfMapping apps available through the online service 'PDF in the cloud' (PDFitc, https://pdfitc.org/). The toolbox is used for both ex situ and operando PDF data for 3 nm TiO2-bronze nanocrystals, which function as the active electrode material in a Li-ion battery. The tools enable structural modelling of the ex situ and operando PDF data, revealing two pristine TiO2 phases (bronze and anatase) and two lithiated Li x TiO2 phases (lithiated versions of bronze and anatase), and the phase evolution during galvanostatic cycling is characterized.

Improving the Mechanical Properties of Glass Ionomer Cement With Nanocrystalline Cellulose From Rice Husk.

This study aimed to evaluate the effect of incorporating nanocrystalline cellulose (NCC) sourced from rice husk on the mechanical properties of a commercial glass ionomer cement (GIC). NCC was isolated through acid hydrolysis, and its crystallinity, chemical structure, and morphology were characterized through x-ray diffractometry, Fourier-transform infrared spectroscopy, and transmission electron microscopy, respectively. Various concentrations of NCC (0%, 0.5%, 1%, and 1.5%) were added to reinforce the GIC matrix. Mechanical tests including compressive strength, flexural strength, hardness, and shear bond strength were conducted on the modified GIC samples. The addition of NCC resulted in increased hardness and shear bond strength values, with 1% NCC showing the highest values compared to other concentrations. However, there was no significant improvement observed in the compressive and flexural strength of the modified GIC. Failure mode test revealed a reduction in adhesive failure with the addition of NCC. Incorporating small amounts of NCC (0.5%-1%) suggests a promising and affordable modification of GIC restorative material using biomass residue, resulting in improved mechanical properties.

Morphology Variation of Ternary PdCuSn Nanocrystalline Assemblies and Their Electrocatalytic Oxidation of Alcohols.

Metal alloys not only increase the composition and spatial distribution of elements but also provide the opportunity to adjust their physicochemical properties. Recently, multimetallic alloy nanocatalysts have attracted great attention in energy applications and the chemical industry. This work presents the production of three ternary PdCuSn nanocrystalline assemblies with similar compositions via a one-step hydrothermal method. The shape variation of assembly units from nanosheets and nanowires to nanoparticles were realized by adjusting the percentage of Sn in metal precursors. Experimental data show that PdCuSn nanowire networks showed the best catalytic activity by virtue of their optimized morphological characteristics and microscopic electronic structure. With electrooxidation of methanol, ethanol, ethylene glycol, and glycerol at 30 °C, PdCuSn nanowire networks demonstrated catalytic activity of 1129, 2111, 2540, and 1445 mA mg-1, respectively. The catalytic activity for alcohol oxidation is attributed to the production of the electronic structure and morphology features that are most suitable. This is achieved by introducing the proper quantities of Cu and Sn components in the first stage of synthesis. This study would help with the construction of high-efficiency nanostructured alloy catalysts by regulating the electronic structure and morphology.

Heavy Boron-Doped Silicon Tunneling Inter-layer Enables Efficient Silicon Heterojunction Solar Cells.

P-type hydrogenated nanocrystalline silicon (nc-Si:H) has been used as a hole-selective layer for efficient n-type crystalline silicon heterojunction (SHJ) solar cells. However, the presence of an additional valence band offset at the interface between intrinsic amorphous hydrogenated silicon and p-type nc-Si:H films will limit the hole carrier transportation. In this work, it has been found that when a heavily boron-doped silicon oxide layer deposited with high hydrogen dilution to silane (pB) was inserted into their interface, the fill factor of SHJ solar cells increases 3% absolutely because of the reduced valence band offset and the increased opportunity to provide a hopping tunnel assisted by the doping energy level and valence band tail states. Furthermore, the additional boron incorporation in intrinsic amorphous silicon adjacent to pB helps to enhance the built-in electric field, thus increasing the hole selectivity. By these means, the power conversion efficiency was improved from 23.9% to approximately 25%.

Chemical Modification of Nanocrystalline Cellulose for Manufacturing of Osteoconductive Composite Materials.

Cellulose is one of the main renewable polymers whose properties are very attractive in many fields, including biomedical applications. The modification of nanocrystalline cellulose (NCC) opens up the possibility of creating nanomaterials with properties of interest as well as combining them with other biomedical polymers. In this work, we proposed the covalent modification of NCC with amphiphilic polyanions such as modified heparin (Hep) and poly(αL-glutamic acid) (PGlu). The modification of NCC should overcome two drawbacks in the production of composite materials based on poly(ε-caprolactone) (PCL), namely, (1) to improve the distribution of modified NCC in the PCL matrix, and (2) to provide the composite material with osteoconductive properties. The obtained specimens of modified NCC were characterized by Fourier-transform infrared spectroscopy and solid-state 13C nuclear magnetic resonance spectroscopy, dynamic and electrophoretic light scattering, as well as thermogravimetric analysis. The morphology of PCL-based composites containing neat or modified NCC as filler was studied by optical and scanning electron microscopy. The mechanical properties of the obtained composites were examined in tensile tests. The homogeneity of filler distribution as well as the mechanical properties of the composites depended on the method of NCC modification and the amount of attached polyanion. In vitro biological evaluation showed improved adhesion of human fetal mesenchymal stem cells (FetMSCs) and human osteoblast-like cells (MG-63 osteosarcoma cell line) to PCL-based composites filled with NCC bearing Hep or PGlu derivatives compared to pure PCL. Furthermore, these composites demonstrated the osteoconductive properties in the experiment on the osteogenic differentiation of FetMSCs.

Triple Junction Segregation Dominates the Stability of Nanocrystalline Alloys.

We present large-scale atomistic simulations that reveal triple junction (TJ) segregation in Pt-Au nanocrystalline alloys in agreement with experimental observations. While existing studies suggest grain boundary solute segregation as a route to thermally stabilize nanocrystalline materials with respect to grain coarsening, here we quantitatively show that it is specifically the segregation to TJs that dominates the observed stability of these alloys. Our results reveal that doping the TJs renders them immobile, thereby locking the grain boundary network and hindering its evolution. In dilute alloys, it is shown that grain boundary and TJ segregation are not as effective in mitigating grain coarsening, as the solute content is not sufficient to dope and pin all grain boundaries and TJs. Our work highlights the need to account for TJ segregation effects in order to understand and predict the evolution of nanocrystalline alloys under extreme environments.

0,1,2,3D nanostructures, types of bulk nanostructured materials, and drug nanocrystals: An overview.

Functional materials are required to meet the needs of society, such as environmental protection, energy storage and conversion, integrated product production, biological and medical processing. bulk nanostructured materials are a research concept that combines nanotechnology with other research fields such as supramolecular chemistry, materials science, and life science to develop logically functional materials from nanodevices. In this review article, nanostructures are synthetized by different methods based on the types and nature of the nanomaterials. In a broad sense "top-down" and "bottom-up" are the two foremost methods to synthesize nanomaterials. In top-down method bulk materials have been reduced to nanomaterials, and in case of bottom-up method, the nanomaterials are synthesized from elementary level. The different methods which are being used to synthesize nanomaterials are chemical vapor deposition method, thermal decomposition, hydrothermal synthesis, solvothermal method, pulsed laser ablation, templating method, combustion method, microwave synthesis, gas phase method, and conventional Sol-Gel method. We also briefly discuss the various physical and chemical methods for producing nanomaterials. We then discuss the applications of functional materials in many areas such as energy storage, supercapacitors, sensors, wastewater treatment, and other biological applications such as drug delivery and drug nanocrystals. Finally, future challenges in materials nanoarchitecture and concepts for further development of functional nanomaterials are briefly discussed.

A Review: Application of Doped Hydrogenated Nanocrystalline Silicon Oxide in High Efficiency Solar Cell Devices.

Due to the unique microstructure of hydrogenated nanocrystalline silicon oxide (nc-SiOx:H), the optoelectronic properties of this material can be tuned over a wide range, which makes it adaptable to different solar cell applications. In this work, the authors review the material properties of nc-SiOx:H and the versatility of its applications in different types of solar cells. The review starts by introducing the growth principle of doped nc-SiOx:H layers, the effect of oxygen content on the material properties, and the relationship between optoelectronic properties and its microstructure. A theoretical analysis of charge carrier transport mechanisms in silicon heterojunction (SHJ) solar cells with wide band gap layers is then presented. Afterwards, the authors focus on the recent developments in the implementation of nc-SiOx:H and hydrogenated amorphous silicon oxide (a-SiOx:H) films for SHJ, passivating contacts, and perovskite/silicon tandem devices.

Influence of Long Milling Time on the Electrical Resistivity of Nanocrystalline Ni2MnSn Heusler Alloy Obtained by Mechanosynthesis.

A Ni2MnSn Heusler alloy was obtained as a single B2 phase after 12 h of mechanical milling. The influence of prolonged milling on the phase stability was analysed for milling times up to 50 h, related to mean crystallite size, lattice strain, and electrical resistivity. The nature of the powders in the milled range was found to be nanocrystalline, with a mean crystallite size of about 33 ± 2 nm. An evaluation of the internal stresses induced by milling was performed, a linear behaviour was found, and a coefficient of the internal stress increase with milling time was proposed. Particle size distributions of milled samples were analysed, and the morphology of the powders was visualised by scanning electron microscopy. The elemental distribution of milled samples was quantified by energy-dispersive X-ray spectroscopy. Electrical resistivity measurements were performed on compacted samples, and their behaviour with milling time was analysed.

Fast, Efficient Tailoring Growth of Nanocrystalline Diamond Films by Fine-Tuning of Gas-Phase Composition Using Microwave Plasma Chemical Vapor Deposition.

Nanocrystalline diamond (NCD) films are attractive for many applications due to their smooth surfaces while holding the properties of diamond. However, their growth rate is generally low using common Ar/CH4 with or without H2 chemistry and strongly dependent on the overall growth conditions using microwave plasma chemical vapor deposition (MPCVD). In this work, incorporating a small amount of N2 and O2 additives into CH4/H2 chemistry offered a much higher growth rate of NCD films, which is promising for some applications. Several novel series of experiments were designed and conducted to tailor the growth features of NCD films by fine-tuning of the gas-phase compositions with different amounts of nitrogen and oxygen addition into CH4/H2 gas mixtures. The influence of growth parameters, such as the absolute amount and their relative ratios of O2 and N2 additives; substrate temperature, which was adjusted by two ways and inferred by simulation; and microwave power on NCD formation, was investigated. Short and long deposition runs were carried out to study surface structural evolution with time under identical growth conditions. The morphology, crystalline and optical quality, orientation, and texture of the NCD samples were characterized and analyzed. A variety of NCD films of high average growth rates ranging from 2.1 µm/h up to 6.7 µm/h were successfully achieved by slightly adjusting the O2/CH4 amounts from 6.25% to 18.75%, while that of N2 was kept constant. The results clearly show that the beneficial use of fine-tuning of gas-phase compositions offers a simple and effective way to tailor the growth characteristics and physical properties of NCD films for optimizing the growth conditions to envisage some specific applications.

Tomographic assessment of bone changes in atrophic maxilla treated by split-crest technique and dental implants with platelet-rich fibrin and NanoBone® versus platelet-rich fibrin alone: Randomized controlled trial.

BACKGROUND: This study evaluated the clinical benefits of adding NanoBone® with split-crest technique and simultaneous implant placement covered with platelet-rich fibrin membrane in horizontally deficient maxillary ridges in terms of crestal and horizontal bone changes and patient morbidity. METHODS: Forty patients indicated for maxillary ridge splitting and simultaneous implant placement were assigned randomly to the study groups: control group (Platelet Rich Fibrin membrane) and test group (Platelet Rich Fibrin membrane + Nanobone®). The Cone Beam Computed Tomography Fusion technique was utilized to assess crestal and horizontal bone changes after five months of the surgical procedure. Patient morbidity was recorded for one week post-surgical. RESULTS: Five months post-surgical, buccal crestal bone resorption was 1.26 ± 0.58 mm for the control group and 1.14 ± 0.63 mm for the test group. Lingual crestal bone resorption was 1.40 ± 0.66 mm for the control group and 1.47 ± 0.68 mm for the test group. Horizontal bone width gain was 1.46 ± 0.44 mm for the control group and 1.29 ± 0.73 mm for the test group. There was no significant statistical difference between study groups regarding crestal and horizontal bone changes and patient morbidity. CONCLUSIONS: The tomographic assessment of NanoBone® addition in this study resulted in no statistically significant difference between study groups regarding crestal and horizontal bone changes and patient morbidity. More randomized controlled clinical trials on gap fill comparing different bone grafting materials versus no grafting should be conducted. GOV REGISTRATION NUMBER: NCT02836678, 13th January 2017.

Experimental Parametric Investigation of Nanosecond Laser-Induced Surface Graphitization of Nano-Crystalline Diamond.

While nano-crystalline diamond (NCD) is a promising engineering composite material for its unique mechanical properties, achieving the ultrahigh surface quality of NCD-based components through conventional grinding and polishing is challenging due to its exceptional hardness and brittleness. In the present work, we experimentally investigate the nanosecond laser ablation-induced graphitization characteristics of NCD, which provides a critical pretreatment method of NCD for realizing its superlative surface finish. Specifically, systematic experimental investigations of the nanosecond pulsed laser ablation of NCD are carried out, in which the characteristics of graphitization are qualitatively characterized by the Raman spectroscopy detection of the ablated area of the microhole and microgroove. Subsequently, the influence of laser processing parameters on the degree and morphological characteristics of graphitization is evaluated based on experimental data and related interpretation, from which optimized parameters for maximizing the graphitization of NCD are then identified. The findings reported in the current work provide guidance for promoting the machinability of NCD via laser irradiation-induced surface modification.