Powder-size driven facile microstructure control in powder-fusion metal additive manufacturing processes.

Microstructure control in metal additive manufacturing is highly desirable for superior and bespoke mechanical performance. Engineering the columnar-to-equiaxed transition during rapid solidification in the additive manufacturing process is crucial for its technological advancement. Here, we report a powder-size driven melt pool engineering approach, demonstrating facile and large-scale control in the grain morphology by triggering a counterintuitive response of powder size to the additively manufactured 316 L stainless steel microstructure.

A strong fracture-resistant high-entropy alloy with nano-bridged honeycomb microstructure intrinsically toughened by 3D-printing.

Strengthening materials via conventional "top-down" processes generally involves restricting dislocation movement by precipitation or grain refinement, which invariably restricts the movement of dislocations away from, or towards, a crack tip, thereby severely compromising their fracture resistance. In the present study, a high-entropy alloy AlCrCoFeNi is produced by the laser powder-bed fusion process, a "bottom-up" additive manufacturing process similar to how nature builds structures, with the microstructure resembling a nano-bridged honeycomb structure consisting of a face-centered cubic (fcc) matrix and an interwoven hexagonal net of an ordered body-centered cubic B2 phase. While the B2 phase, combined with high-dislocation density and solid-solution strengthening, provides strength to the material, the nano-bridges of dislocations connecting the fcc cells, i.

Development of hyaluronic acid-silica composites via in situ precipitation for improved penetration efficiency in fast-dissolving microneedle systems.

Fast-dissolving microneedles (DMNs) hold significant promise for transdermal drug delivery, offering improved patient compliance, biocompatibility, and functional adaptability for various therapeutic purposes. However, the mechanical strength of the biodegradable polymers used in DMNs often proves insufficient for effective penetration into human skin, especially under high humidity conditions. While many composite strategies have been developed to reinforce polymer-based DMNs, simple mixing of the reinforcements with polymers often results in ineffective penetration due to inhomogeneous dispersion of the reinforcements and the formation of undesired micropores.

Rational design and topochemical synthesis of polymorphs of a polymer.

Packing a polymer in different ways can give polymorphs of the polymer having different properties. β-Turn forming peptides such as 2-aminoisobutyric acid (Aib)-rich peptides adopt several conformations by varying the dihedral angles. Aiming at this, a β-turn-forming peptide monomer would give different polymorphs and these polymorphs upon topochemical polymerization would yield polymorphs of the polymer, we designed an Aib-rich monomer N-(Aib)-NHCH-C[triple bond, length as m-dash]CH.

Nanomechanical study of aqueous-processed h-BN reinforced PVA composites.

Hexagonal boron nitride (h-BN) as a filler has significantly improved the mechanical properties of various polymers composites. Among them, polyvinyl alcohol (PVA) is particularly important for its wide range of industrial applications and biocompatibility nature. However, preparing a homogenous composite of h-BN and PVA in water is troublesome as the aqueous processing of h-BN without any additives is challenging.

Molecular Architectonics of Cyclic Dipeptide Amphiphiles and Their Application in Drug Delivery.

Assembly and co-assemblies of peptide amphiphiles through specific noncovalent forces expand the space of molecular architectonics-driven construction of diverse nanoarchitectures with potential biological applications. In this work, cyclic dipeptide amphiphiles (CDPAs) of cyclo(Gly-Asp) with varying lengths of alkyl chains (-) were synthesized, and their molecular organization was studied. The noncovalent interactions of the components, CDP and alkyl chain, drive the molecular self-assembly of CDPAs into well-defined and diverse nanoarchitectures such as nanotubes, nanospheres, nano/microsheets, and flowers.

Extraction of mechanical properties of materials through deep learning from instrumented indentation.

Instrumented indentation has been developed and widely utilized as one of the most versatile and practical means of extracting mechanical properties of materials. This method is particularly desirable for those applications where it is difficult to experimentally determine the mechanical properties using stress-strain data obtained from coupon specimens. Such applications include material processing and manufacturing of small and large engineering components and structures involving the following: three-dimensional (3D) printing, thin-film and multilayered structures, and integrated manufacturing of materials for coupled mechanical and functional properties.

Guest Solvent-dependence of the Nanomechanical Response in Substituted Dihydropyrimidinone Crystals.

The nanomechanical responses of two crystalline phases of a dihydropyrimidine analogue (1) were similar irrespective of the presence (or absence) of the guest solvent. In contrast, the mechanical responses of two differently solvated forms of the second related (2) crystals were significantly different. These contrasting behaviors are rationalized in terms of intermolecular interactions and energy distributions.

Molecular Basis for the Mechanical Response of Sulfa Drug Crystals.

Comprehension of the nanomechanical response of crystalline materials requires the understanding of the elastic and plastic deformation mechanisms in terms of the underlying crystal structures. Nanoindentation data were combined with structural and computational inputs to derive a molecular-level understanding of the nanomechanical response in eight prototypical sulfa drug molecular crystals. The magnitude of the modulus, E, was strongly connected to the non-covalent bond features, that is, the bond strength, the relative orientation with the measured crystal facet and their disposition in the crystal lattice.

Elastic flexibility tuning via interaction factor modulation in molecular crystals.

We report the design of a series of nonhalogenated and halogenated molecular crystals with specific structural features, which are essential for pronounced elasticity. These features involve (a) isotropic weak and dispersive interactions, and (b) corrugated molecular packing with interlocked structures. The effects of intermolecular interactions on the elastic properties of the crystals are ascertained using nano-scale mechanical characterization methods.

Intermediate Temperature Brittleness in Metallic Glasses.

All metallic glasses (MGs), irrespective of their compositions, become brittle in the intermediate temperature range of 0.6-0.7 T However, most materials are expected to carry higher strains during deformation with increasing temperature.

Reversible Polymorphism, Liquid Crystallinity, and Stimuli-Responsive Luminescence in a Bola-amphiphilic π-System: Structure-Property Correlations Through Nanoindentation and DFT Calculations.

We report the design, synthesis, detailed characterization, and analysis of a new multifunctional π-conjugated bola-amphiphilic chromophore: oligo-(p-phenyleneethynylene)dicarboxylic acid with dialkoxyoctadecyl side chains (OPE-C-1). OPE-C-1 shows two polymorphs at 123 K (OPE-C-1') and 373 K (OPE-C-1″), whose crystal structures were characterized via single crystal X-ray diffraction. OPE-C-1 also exhibits thermotropic liquid crystalline property revealing a columnar phase.

Cavitation-Induced Fracture Causes Nanocorrugations in Brittle Metallic Glasses.

Brittle metallic glasses exhibit a unique and intriguing fracture morphology of periodic nanocorrugations whose spacing and amplitude are of the order of tens of nanometers. We show through continuum simulations that they fail by spontaneous and simultaneous cavitation within multiple weak zones arising due to intrinsic atomic density fluctuations ahead of a notch tip. Dynamic crack growth would then occur along curved but narrowly confined shear bands that link the growing cavities.

A first-principles study of pressure-induced phase transformation in a rare-earth formate framework.

Among the panoply of exciting properties that metal-organic frameworks (MOFs) exhibit, fully reversible pressure-induced phase transformations (PIPTs) are particularly interesting as they intrinsically relate to the flexibility of MOFs. Recently, a number of MOFs have been reported to exhibit this feature, which is attributed to bond rearrangement with applied pressure. However, the experimental assessment of whether a given MOF exhibits PIPT or not requires sophisticated instruments as well as detailed structural investigations.

Remarkable Improvement in the Mechanical Properties and CO2 Uptake of MOFs Brought About by Covalent Linking to Graphene.

Metal-organic frameworks (MOFs) are exceptional as gas adsorbents but their mechanical properties are poor. We present a successful strategy to improve the mechanical properties along with gas adsorption characteristics, wherein graphene (Gr) is covalently bonded with M/DOBDC (M=Mg(2+) , Ni(2+) , or Co(2+) , DOBDC=2,5-dioxido-1,4-benzene dicarboxylate) MOFs. The surface area of the graphene-MOF composites increases up to 200-300 m(2)  g(-1) whereas the CO2 uptake increases by ca.

Crystal chemistry and photomechanical behavior of 3,4-dimethoxycinnamic acid: correlation between maximum yield in the solid-state topochemical reaction and cooperative molecular motion.

A new monoclinic polymorph, form II (P21/c, Z = 4), has been isolated for 3,4-dimethoxycinnamic acid (DMCA). Its solid-state 2 + 2 photoreaction to the corresponding α-truxillic acid is different from that of the first polymorph, the triclinic form I ([Formula: see text], Z = 4) that was reported in 1984. The crystal structures of the two forms are rather different.

Structure-mechanical property correlations in mechanochromic luminescent crystals of boron difluoride dibenzoylmethane derivatives.

The structure and mechanical properties of crystalline materials of three boron difluoride dibenzoylmethane (BF2dbm) derivatives were investigated to examine the correlation, if any, among mechanochromic luminescence (ML) behaviour, solid-state structure, and the mechanical behaviour of single crystals. Qualitative mechanical deformation tests show that the crystals of BF2dbm( (t) Bu)2 can be bent permanently, whereas those of BF2dbm(OMe)2 exhibit an inhomogeneous shearing mode of deformation, and finally BF2dbmOMe crystals are brittle. Quantitative mechanical analysis by nano-indentation on the major facets of the crystals shows that BF2dbm( (t) Bu)2 is soft and compliant with low values of elastic modulus, E, and hardness, H, confirming its superior suceptibility for plastic deformation, which is attributed to the presence of a multitude of slip systems in the crystal structure.

Bioinspired Reductionistic Peptide Engineering for Exceptional Mechanical Properties.

A simple solution-processing and self-assembly approach that exploits the synergistic interactions between multiple hydrogen bonded networks and aromatic interactions was utilized to synthesize molecular crystals of cyclic dipeptides (CDPs), whose molecular weights (~0.2 kDa) are nearly three orders of magnitude smaller than that of natural structural proteins (50-300 kDa). Mechanical properties of these materials, measured using the nanoindentation technique, indicate that the stiffness and strength are comparable and sometimes better than those of natural fibres.

Hardness Alternation in α,ω-Alkanedicarboxylic Acids.

The variation of hardness as a function of the number of carbon atoms in α,ω-alkanedicarboxylic acids, C(N)H(2N-2)O4 (4≤N≤9), was examined by recourse to nanoindentation on the major faces of single crystals. Hardness exhibits odd-even alternation, with the odd acids being softer and the even ones harder; the differences decrease with increasing chain length. These variations are similar to those seen for other mechanical, physical, and thermal properties of these diacids.

Solid solution hardening of molecular crystals: tautomeric polymorphs of omeprazole.

In the context of processing of molecular solids, especially pharmaceuticals, hardness is an important property that often determines the manufacturing steps employed. Through nanoindentation studies on a series of omeprazole polymorphs, in which the proportions of the 5- and 6-methoxy tautomers vary systematically, we demonstrate that solid-solution strengthening can be effectively employed to engineer the hardness of organic solids. High hardness can be attained by increasing lattice resistance to shear sliding of molecular layers during plastic deformation.

Tuning mechanical properties of pharmaceutical crystals with multicomponent crystals: voriconazole as a case study.

Crystals of voriconazole, an antifungal drug, are soft in nature, and this is disadvantageous during compaction studies where pressure is applied on the solid. Crystal engineering is used to make cocrystals and salts with modified mechanical properties (e.g.

Designing elastic organic crystals: highly flexible polyhalogenated N-benzylideneanilines.

The intermolecular interactions and structural features in crystals of seven halogenated N-benzylideneanilines (Schiff bases), all of which exhibit remarkable flexibility, were examined to identify the common packing features that are the raison d'être for the observed elasticity. The following two features, in part related, were identified as essential to obtain elastic organic crystals: 1) A multitude of weak and dispersive interactions, including halogen bonds, which may act as structural buffers for deformation through easy rupture and reformation during bending; and 2) corrugated packing patterns that would get interlocked and, in the process, prevent long-range sliding of molecular planes.

Studying microstructure in molecular crystals with nanoindentation: intergrowth polymorphism in felodipine.

Intergrowth polymorphism refers to the existence of distinct structural domains within a single crystal of a compound. The phenomenon is exhibited by form II of the active pharmaceutical ingredient felodipine, and the associated microstructure is a significant feature of the compound's structural identity. Employing the technique of nanoindentation on form II reveals a bimodal mechanical response on specific single-crystal faces, demonstrating distinct properties for two polymorphic forms within the same crystal.

Pressure-induced bond rearrangement and reversible phase transformation in a metal-organic framework.

Pressure-induced phase transformations (PIPTs) occur in a wide range of materials. In general, the bonding characteristics, before and after the PIPT, remain invariant in most materials, and the bond rearrangement is usually irreversible due to the strain induced under pressure. A reversible PIPT associated with a substantial bond rearrangement has been found in a metal-organic framework material, namely [tmenH2][Er(HCOO)4]2 (tmenH2(2+)=N,N,N',N'-tetramethylethylenediammonium).

Kinematic and mechanical profile of the self-actuation of thermosalient crystal twins of 1,2,4,5-tetrabromobenzene: a molecular crystalline analogue of a bimetallic strip.

A paradigm shift from hard to flexible, organic-based optoelectronics requires fast and reversible mechanical response from actuating materials that are used for conversion of heat or light into mechanical motion. As the limits in the response times of polymer-based actuating materials are reached, which are inherent to the less-than-optimal coupling between the light/heat and mechanical energy in them, a conceptually new approach to mechanical actuation is required to leapfrog the performance of organic actuators. Herein, we explore single crystals of 1,2,4,5-tetrabromobenzene (TBB) as actuating elements and establish relations between their kinematic profile and mechanical properties.