Nanomechanics of cellulose crystals and cellulose-based polymer composites

Cellulose-polymer composites have potential applications in aerospace and transportation areas where lightweight materials with high mechanical properties are needed. In addition, these economical and biodegradable composites have been shown to be useful as polymer electrolytes, packaging structures, optoelectronic devices, and medical implants such as wound dressing and bone scaffolds. In spite of the above mentioned advantages and potential applications, due to the difficulties associated with synthesis and processing techniques, application of cellulose crystals (micro and nano sized) for preparation of new composite systems is limited. Cellulose is hydrophilic and polar as opposed to most of common thermoplastics, which are non-polar. This results in complications in addition of cellulose crystals to polymer matrices, and as a result in achieving sufficient dispersion levels, which directly affects the mechanical properties of the composites. As in other composite materials, the properties of cellulose-polymer composites depend on the volume fraction and the properties of individual phases (the reinforcement and the polymer matrix), the dispersion quality of the reinforcement through the matrix and the interaction between CNCs themselves and CNC and the matrix (interphase). In order to develop economical cellulose-polymer composites with superior qualities, the properties of individual cellulose crystals, as well as the effect of dispersion of reinforcements and the interphase on the properties of the final composites should be understood. In this research, the mechanical properties of CNC polymer composites were characterized at the macro and nano scales. A direct correlation was made between: Dispersion quality and macro-mechanical properties Nanomechanical properties at the surface and tensile properties CNC diameter and interphase thickness Lastly, individual CNCs from different sources were characterized and for the first time size-scale effect on their nanomechanical properties were reported. Then the effect of CNC surface modification on the mechanical properties was studied and correlated to the crystalline structure of these materials

Plant micro- and nanomechanics: experimental techniques for plant cell-wall analysis

In the last few decades, micro- and nanomechanical methods have become increasingly important analytical techniques to gain deeper insight into the nanostructure and mechanical design of plant cell walls. The objective of this article is to review the most common micro- and nanomechanical approaches that are utilized to study primary and secondary cell walls from a biomechanics perspective. In light of their quite disparate functions, the common and opposing structural features of primary and secondary cell walls are reviewed briefly. A significant part of the article is devoted to an overview of the methodological aspects of the mechanical characterization techniques with a particular focus on new developments and advancements in the field of nanomechanics. This is followed and complemented by a review of numerous studies on the mechanical role of cellulose fibrils and the various matrix components as well as the polymer interactions in the context of primary and secondary cell-wall functio

In situ nanoindentation: probing nanoscale multifunctionality

Nanoindentation is the leading technique for evaluating nanoscale mechanical properties of materials. Consistent developments in instrumentation and their capabilities are transforming nanoindentation into a powerful tool for characterization of multifunctionality at the nanoscale. This review outlines the integration of nanoindentation with real-time electron imaging, high temperature measurements, electrical characterization, and a combination of these. In situ nanoindentation measurements have enabled the real-time study of the interplay between mechanical, thermal, and electrical effects at the nanoscale. This review identifies previous reviews in this area, traces developments and pinpoints significant recent advances (post-2007), with emphasis on the applications of in situ nanoindentation techniques to materials systems, and highlighting the new insights gained from these in situ techniques. Based on this review, future directions and applications of in situ nanoindentation are identified, which highlight the potential of this suite of techniques for materials scientists from all disciplines

Atomic force microscopy techniques for nanomechanical characterization : a polymer case study

Atomic force microscopy (AFM) is a versatile tool to perform mechanical characterization of surface samples at the nanoscale. In this work, we review two of such methods, namely contact resonance AFM (CR-AFM) and torsional harmonics AFM (TH-AFM). First, such techniques are illustrated and their applicability on materials with elastic moduli in different ranges are discussed, together with their main advantages and limitations. Then, a case study is presented in which we report the mechanical characterization using both CR-AFM and TH-AFM of polyaniline and polyaniniline doped with nanodiamond particles tablets prepared by a pressing process. We determined the indentation modulus values of their surfaces, which were found in fairly good agreement, thus demonstrating the accuracy of the techniques. Finally, the determined surface elastic moduli have been compared with the bulk ones measured through standard indentation testing. INTRODUCTION In the field of nanotechnology, the development of innovative and nondestructive characterization techniques plays a crucial role. Indeed, the characterization of nanostructured hybrid materials (e.g., thin films and nanocomposites) and devices requires the capability of acquiring maps of the local mechanical properties at the nanoscale. Nanoindentation is the most common method for determining the mechanical properties of thin films. However, its applicability is strictly limited by the thickness of the sample. Furthermore, its poor spatial resolution does not allow the reconstruction of an accurate distribution of the sample surface mechanical properties. For this reason, alternative methods, based on atomic force microscopy (AFM), have been developed. By exploiting the high resolution of the AFM, maps of the surface mechanical properties (i.e., indentation modulus) can be achieved. Among these techniques, AFM nanoindentation1 is the simplest method used to evaluate the local mechanical properties o

Fabrication and characterization of shape memory polymers at small scales

The objective of this research is to thoroughly investigate the shape memory effect in polymers, characterize, and optimize these polymers for applications in information storage systems. Previous research effort in this field concentrated on shape memory metals for biomedical applications such as stents. Minimal work has been done on shape memory poly- mers; and the available work on shape memory polymers has not characterized the behaviors of this category of polymers fully. Copolymer shape memory materials based on diethylene glycol dimethacrylate (DEGDMA) crosslinker, and tert butyl acrylate (tBA) monomer are designed. The design encompasses a careful control of the backbone chemistry of the materials. Characterization methods such as dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC); and novel nanoscale techniques such as atomic force microscopy (AFM), and nanoindentation are applied to this system of materials. Designed experiments are conducted on the materials to optimize spin coating conditions for thin films. Furthermore, the recovery, a key for the use of these polymeric materials for information storage, is examined in detail with respect to temperature. In sum, the overarching objectives of the proposed research are to: (i) design shape memory polymers based on polyethylene glycol dimethacrylate (PEGDMA) and diethylene glycol dimethacrylate (DEGDMA) crosslinkers, 2-hydroxyethyl methacrylate (HEMA) and tert-butyl acrylate monomer (tBA). (ii) utilize dynamic mechanical analysis (DMA) to comprehend the thermomechanical properties of shape memory polymers based on DEGDMA and tBA. (iii) utilize nanoindentation and atomic force microscopy (AFM) to understand the nanoscale behavior of these SMPs, and explore the strain storage and recovery of the polymers from a deformed state. (iv) study spin coating conditions on thin film quality with designed experiments. (iv) apply neural networks and genetic algorithms to optimize these systems.Ph.D.Committee Chair: Gall, Ken; Committee Chair: May, Gary S; Committee Member: Brand, Oliver; Committee Member: Degertekin, F Levent; Committee Member: Milor, Linda

Influence of fluoride on the mineralization of collagen via the polymer-induced liquid-precursor (PILP) process.

ObjectiveThe polymer-induced liquid-precursor (PILP) mineralization process has been shown to remineralize artificial dentin lesions to levels consistent with those of native dentin. However, nanoindentation revealed that the moduli of those remineralized lesions were only ∼50% that of native dentin. We hypothesize that this may be due to the PILP process having been previously optimized to obtain high amounts (∼70wt%) of intrafibrillar crystals, but without sufficient interfibrillar mineral, another significant component of dentin.MethodsFluoride was added to the PILP-mineralization of collagen from rat tail tendon at varying concentrations to determine if a better balance of intra- versus inter-fibrillar mineralization could be obtained, as determined by electron microscopy. Nanoindentation was used to determine if fluoridated apatite could improve the mechanical properties of the composites.ResultsFluoride was successfully incorporated into the PILP-mineralization of rat tail tendon and resulted in collagen-mineral composite systems with the mineral phase of hydroxyapatite containing various levels of fluoridation. As the fluoride concentration increased, the crystals became larger and more rod-like, with an increasing tendency to form on the fibril surfaces rather than the interior. Nanomechanical testing of the mineralized tendons revealed that fluoride addition did not increase modulus over PILP mineralization alone. This likely resulted from the separated nature of collagen fibrils that comprise tendon, which does not provide lateral reinforcement and therefore may not be suited for the compressive loads of nanoindentation.SignificanceThis work contributes to the development of minimally invasive approaches to caries treatment by determining if collagen can be functionally mineralized

INVESTIGATION OF THE MECHANICAL PROPERTIES OF POLY (ETHYLENE GLYCOL) DIACRYLATE BY NANOINDENTATION USING ATOMIC FORCE MICROSCOPY

Poly (ethylene glycol) (PEG) hydrogel based polymers are among the most widely used synthetic materials for biomedical applications. Because of their biocompatibility, and ease of fabrication, hydrogels are highly suitable for use as constructs to engineer tissues as well as for cell transplantation. A critical parameter of importance for PEG hydrogels is their mechanical properties which are highly dependent on the environmental conditions. Properties of PEG-based hydrogels can be engineered to resemble scaffolds composed of extracellular matrix molecules, which provide structural support, adhesive sites and mechanical as well as biomechanical signals to most cells. The mechanical properties of these synthetic scaffolds can affect the migration, proliferation and differentiation of the cells. Accordingly, it is important to investigate the mechanical properties of these hydrogels and observe their effect on cell behavior as PEG-based scaffolds for example. In this research, the objective is to measure the mechanical properties such as the elastic modulus (Ec) and the stiffness (S) of polyethylene glycol diacrylate (PEGDA) hydrogel matrices at the nanoscale. The effect of varying parameters in the fabrication of PEGDA hydrogels including monomer molecular weight, initiator concentration and rates of hydration were investigated via nanoindentation using an atomic force microscope (AFM). Two different silicon nitride based cantilevers were used to study the effect of varying loading rates on the mechanical properties of these materials. Indentation parameters such as loads applied and indent depths were varied for each hydrogel sample. Different models were used to fit the experimental data to obtain the parameters of interest for the material (Ec and S). In particular, the data was best described using the model of Oliver-Pharr to analyze and fit the nanoindentation curves. Scanning electron microscope was used to image and confirm the geometry of the tip before and after the indentation experiments. Under high load and displacement modes, the indentation analysis was relatively easy and the elastic modulus and stiffness values were obtained for all dry PEGDA hydrogel sample. The variation of the initiator concentration has been analyzed as well. The mechanical properties of the hydrogel increase as the amount of the initiator increase in the precursor. The degree of hydration dramatically affects the mechanical behavior of the PEGDA. The presence of water within the hydrogel network weakens the internal as well the external mechanical properties, leading to smaller values of elastic modulus and stiffness compared with the dry condition. The mechanical properties of the indenter (cantilever tips) have significant impact on the results. It is important to study carefully the indenter properties before and after the indentation experiments. Since little work has been done on investigating the mechanical properties of PEGDA hydrogels at the nanoscale via AFM, the analysis of the mechanical behavior of this type of hydrogel using this strategy is of great importance

Characterization of polyaniline-detonation nanodiamond nanocomposite fibers by atomic force microscopy based technique

Polyaniline (PANI) fibers were synthesized in presence of detonantion nanodiamond (DND) particles by precipitation polymerization technique. Morphological, electrical and mechanical characterizations of the obtained PANI/DND nanocomposited have been performed by different either standard or advanced atomic force microscopy (AFM) based techniques. Morphological characterization by tapping mode AFM supplied information about the structure of fibers and ribbons forming the PANI/DND network. An AFM based technique that takes advantage of an experimental configuration specifically devised for the purpose was used to assess the electrical properties of the fibers, in particular to verify their conductivity. Finally, mechanical characterization was carried out synergically using two different and recently proposed AFM based techniques, one based on AFM tapping mode and the other requiring AFM contact mode, which probed the nanocomposited nature of PANI/DND fiber sample down to different depths. © 2013 Elsevier Ltd. All rights reserved