Lignin-based fibers were produced by electrospinning aqueous dispersions of lignin, poly(vinyl alcohol) (PVA), and cellulose nanocrystals (CNCs). Defect-free nanofibers with up to 90 wt % lignin and 15% CNCs were achieved. The properties of the aqueous dispersions, including viscosity, electrical conductivity, and surface tension, were examined and correlated to the electrospinnability and resulting morphology of the composite fibers. A ternary lignin-PVA-water phase diagram was constructed as a tool to rationalize the effect of mixing ratios on the dispersion electrospinability and morphology of the resulting fibers. The influence of reinforcing CNCs on the thermal properties of the multicomponent fibers was investigated by using thermal gravimetric analysis and differential scanning calorimetry. The thermal stability of the system was observed to increase owing to a strong interaction of the lignin-PVA matrix with the dispersed CNCs, mainly via hydrogen bonding, as observed in Fourier transform infrared spectroscopy experiments.

The standard Oliver-Pharr nanoindentation analysis tacitly assumes that the specimen is structurally rigid and that it is both semi-infinite and homogeneous. Many specimens violate these assumptions. We show that when the specimen flexes or possesses heterogeneities, such as free edges or interfaces between regions of different properties, artifacts arise in the standard analysis that affect the measurement of hardness and modulus. The origin of these artifacts is a structural compliance (C s ), which adds to the machine compliance (C m ), but unlike the latter, C s can vary as a function of position within the specimen. We have developed an experimental approach to isolate and remove C s . The utility of the method is demonstrated using specimens including (i) a silicon beam, which flexes because it is supported only at the ends, (ii) sites near the free edge of a fused silica calibration standard, (iii) the tracheid walls in unembedded loblolly pine (Pinus taeda), and (iv) the polypropylene matrix in a polypropylene-wood composite.

The challenges of reducing gate leakage current and dielectric breakdown beyond the 45 nm technology node have shifted engineers' attention from the traditional and proven dielectric SiO 2 to materials of higher dielectric constant also known as high-k materials such as hafnium oxide ͑HfO 2 ͒ and aluminum oxide ͑Al 2 O 3 ͒. These high-k materials are projected to replace silicon oxide ͑SiO 2 ͒. In order to address the complex process integration and reliability issues, it is important to investigate the mechanical properties of these dielectric materials in addition to their electrical properties. In this study, HfO 2 and Al 2 O 3 have been fabricated using atomic layer deposition ͑ALD͒ on ͑100͒ p-type Si wafers. Using nanoindentation and the continuous stiffness method, we report the elastomechanical properties of HfO 2 and Al 2 O 3 on Si. ALD HfO 2 thin films were measured to have a hardness of 9.5 Ϯ 2 GPa and a modulus of 220 Ϯ 40 GPa, whereas the ALD Al 2 O 3 thin films have a hardness of 10.5 Ϯ 2 GPa and a modulus of 220 Ϯ 40 GPa. The two materials are also distinguished by very different interface properties. HfO 2 forms a hafnium silicate interlayer, which influences its nanoindentation properties close to the interface with the Si substrate, while Al 2 O 3 does not exhibit any interlayer.For the past 40 years the microelectronics industry has relied on the scaling down of device size in order to improve the performance, functionality, and bit density of chips, as described by Moore's law. As microelectronics is transitioning into deep nanotechnology, the drawback of the increasing miniaturization of devices is the increase of gate leakage current and oxide breakdown. 1 To reduce the gate leakage current and breakdown field across the gate insulator, researchers are looking into high-k dielectric materials. High-k materials such as HfO 2 and Al 2 O 3 will increase the transistor drive current and the transistor switching speed. 2 HfO 2 is predicted to replace SiO 2 , SiO x N y , and Si 3 N 4 as the gate dielectric of complementary metal oxide semiconductor ͑CMOS͒ devices at the 45 nm technology node and beyond. HfO 2 and Al 2 O 3 have dielectric constants of approximately k = 25 and 8, respectively, 3 which compare favorably with k = 3.9 for SiO 2 . Various deposition techniques have been used to deposit high-k materials. Among these growth techniques are metallorganic chemical vapor deposition ͑MOCVD͒, 4-6 pulsed laser deposition ͑PLD͒, 7 and atomic layer deposition ͑ALD͒. 4-6,8 MOCVD and PLD require a high temperature during processing and film fabrication. 9 For example, a minimum temperature of 600°C is required to deposit HfO 2 with MOCVD, whereas HfO 2 crystallizes once the temperature reaches 600°C. 10 ALD is a chemical reactionbased deposition technique that requires only relatively low temperatures. ALD provides absolute film deposition uniformity ͑atomic layer by atomic layer͒, precise composition control, high conformality, and completely self-limiting surface reactions, which makes ALD the most...

Sub-100 nm resolution local thermal analysis, X-ray photoelectron spectroscopy (XPS), and water contact angle (WCA) measurements were used to relate surface polymer distribution with the composition of electrospun fiber mats and spin coated films obtained from aqueous dispersions of lignin, polyvinyl alcohol (PVA), and cellulose nanocrystal (CNC). Defect-free lignin/PVA fibers were produced with radii which were observed to increase with lignin concentration and with the addition of CNCs. XPS and WCA results indicate a nonlinear relationship between the surface and the bulk compositions. A threshold around 50 wt % bulk composition was identified in which extensive partitioning of PVA and lignin components occurred on the surface below and above this value. In 75:25 wt % lignin/PVA solvent cast films, phase separated domains were observed. Using nanoscale thermal analyses, the continuous phase was determined to be lignin-rich and the discontinuous phase had a lignin/PVA dispersion. Importantly, the size of the phase separated domains was reduced by the addition of CNCs. When electrospun fiber surfaces were lignin-rich, the addition of CNCs affected their surfaces. In contrast, no surface effects were observed with the addition of CNCs in PVA-rich fibers. Overall, we highlight the importance of molecular interactions and phase separation on the surface properties of fibers from lignin as an abundant raw material for the fabrication of new functional materials.

Whenever a nanoindent is placed near an edge, such as the free edge of the specimen or heterophase interface intersecting the surface, the elastic discontinuity associated with the edge produces artifacts in the load–depth data. Unless properly handled in the data analysis, the artifacts can produce spurious results that obscure any real trends in properties as functions of position. Previously, we showed that the artifacts can be understood in terms of a structural compliance, Cs, which is independent of the size of the indent. In the present work, the utility of the SYS (Stone, Yoder, Sproul) correlation is demonstrated in its ability to remove the artifacts caused by Cs. We investigate properties: (i) near the surface of an extruded polymethyl methacrylate rod tested in cross section, (ii) of compound corner middle lamellae of loblolly pine (Pinus taeda) surrounded by relatively stiff wood cell walls, (iii) of wood cell walls embedded in a polypropylene matrix with some poorly bonded wood–matrix interfaces, (iv) of AlB2 particles embedded in an aluminum matrix, and (v) of silicon-on-insulator thin film on substrate near the free edge of the specimen.

Despite the importance of cell wall diffusion to nearly all aspects of wood utilization, diffusion mechanisms and the detailed effects of moisture remain poorly understood. In this perspective, we introduce and employ approaches established in polymer science to develop a phenomenological framework for understanding the effects of moisture on diffusion in unmodified wood cell walls. The premise for applying this polymer-science-based approach to wood is that wood polymers (cellulose, hemicelluloses, and lignin) behave like typical solid polymers. Therefore, the movement of chemicals through wood cell walls is a diffusion process through a solid polymer, which is in contrast to previous assertions that transport of some chemicals occurs via aqueous pathways in the cell wall layers. Diffusion in polymers depends on the interrelations between free volume in the polymer matrix, molecular motions of the polymer, diffusant dimensions, and solubility of the diffusant in the polymer matrix. Because diffusion strongly depends on whether a polymer is in a rigid glassy state or soft rubbery state, it is important to understand glass transitions in the amorphous wood polymers. Through a review and analysis of available literature, we conclude that in wood both lignin and the amorphous polysaccharides very likely have glass transitions. After developing and presenting this polymer-science-based perspective of diffusion through unmodified wood cell walls, suggested directions for future research are discussed. A key consideration is that a large difference between diffusion through wood polymers and typical polymers is the high swelling pressures that can develop in unmodified wood cell walls. This pressure likely arises from the hierarchical structure of wood and should be taken into consideration in the development of predictive models for diffusion in unmodified wood cell walls.

Understanding and controlling molecular-scale interactions between adhesives and wood polymers are critical to accelerate the development of improved adhesives for advanced wood-based materials. The submicrometer resolution of synchrotron-based X-ray fluorescence microscopy (XFM) was found capable of mapping and quantifying infiltration of Br-labeled phenol-formaldehyde (BrPF) into wood cell walls. Cell wall infiltration of five BrPF adhesives with different average molecular weights (MWs) was mapped. Nanoindentation on the same cell walls was performed to assess the effects of BrPF infiltration on cell wall hygromechanical properties. For the same amount of weight uptake, lower MW BrPF adhesives were found to be more effective at decreasing moisture-induced mechanical softening. This greater effectiveness of lower MW phenolic adhesives likely resulted from their ability to more intimately associate with water sorption sites in the wood polymers. Evidence also suggests that a BrPF interpenetrating polymer network (IPN) formed within the wood polymers, which might also decrease moisture sorption by mechanically restraining wood polymers during swelling.

We produced defect-free electrospun fibers from aqueous dispersions of lignin, poly(vinyl alcohol) (PVA), and cellulose nanocrystals (CNCs), which were used as reinforcing nanoparticles. The thermomechanical performance of the lignin-based electrospun fibers and the spin-coated thin films was improved when they were embedded with CNCs. Isochronal dynamic mechanical analysis (DMA) was used to assess the viscoelastic properties of the lignin:PVA electrospun fiber mats loaded with CNCs. DMA revealed that α relaxation processes became less prominent with an increased lignin content, an effect that correlated with the loss tangent (tan δ = E″/E') and α peak (Tg) that shifted to higher temperatures. This can be ascribed to the restraint of the segmental motion of PVA in the amorphous regions caused by strong intermolecular interactions. The reinforcing effect and high humidity stability attained by addition of CNCs (5, 10, or 15 wt %) in the multicomponent fiber mats were revealed. Nanoindentation was performed to assess the elastic modulus and hardness of as-prepared and cross-section surfaces of spin-coated lignin:PVA (75:25) films loaded with CNC. The properties of the two surfaces differed, and only the trend in cross-section elastic modulus correlated with DMA results. After addition of 5 wt % CNCs, both the DMA and nanoindentation elastic modulus remained constant, while after addition of 15 wt % CNCs, both increased substantially. An indentation size effect was observed in the nanoindentation hardness, and the results provided insight into the effect of addition of CNCs on the microphysical processes controlling the yield behavior in the composites.