Mark P. Staiger

Ionic Liquids and Their Interaction with Cellulose

Sustainability, industrial ecology, eco-efficiency, and green chemistry are directing the development of the next generation of materials, products, and processes. Biodegradable plastics and biocompatible composites generated from renewable biomass feedstock are regarded as promising materials that could replace synthetic polymers and reduce global dependence on fossil fuel sources.1 It is estimated that the world is currently consuming petroleum at a rate 100 000 times faster than nature can replace it.2 The growing global environmental awareness and societal concern, high rate of depletion of petroleum resources, concepts of sustainability, and new environmental regulations have triggered the search for new products and processes that are more compatible with the environment. The most abundant natural polymer in our environment is cellulose. It has an estimated annual biosphere production of 90 × 109 metric tons and, consequently, represents the most obvious renewable resource for producing biocomposites.3 Its highly ordered structure is responsible for its desirable mechanical properties but makes it a challenge to find suitable solvents for its dissolution.4 The first attempts to dissolve cellulose date back to the early 1920s.5 Several aqueous and nonaqueous cellulose solvents have been discovered since then, but all of these solvents suffer either from high environmental toxicity or from insufficient solvation power.6 In general, the traditional cellulose dissolution processes require relatively harsh conditions and the use of expensive and uncommon solvents, which usually cannot be recovered after the process.6-10 However, a new class of solvents was opened to the cellulose research community, when in 2002 Swatloski et al. reported the use of an ionic liquid as solvent for cellulose both for the regeneration of cellulose and for the chemical modification of the polysaccharide.7 In 1934, Graenacher had discovered a solvent system with the ability to dissolve cellulose, but this was thought to be of little practical value at the time.11,12 Ionic liquids are a group of salts that exist as liquids at relatively low temperatures (<100 °C). They have many attractive properties, including chemical and thermal stability, nonflammability, and immeasurably low vapor pressure.12 First discovered in 1914 by Walden, their huge potential in industry and research was only realized within the last few decades.13,14 This review aims to provide a summary of our current state of knowledge on the structural features of wood * To whom correspondence should be addressed. E-mail: ken.marsh@ canterbury.ac.nz. Tel.: +64 3364 2140. Fax: +64 3364 2063. † Department of Chemical and Process Engineering. ‡ Department of Mechanical Engineering. Andre Pinkert was born in Schwabach, Germany, in 1981. He studied Chemistry at the University of Erlangen-Nurnberg, Germany, and received his prediploma and diploma degrees in 2004 and 2008, respectively. During 2005, he joined the Marine Natural Products Group, lead by Murray H. Munro and John W. Blunt, at the University of Canterbury (UoC), New Zealand, working on the isolation and characterization of bioactive metabolites. In early 2006, he returned to Germany and resumed his studies at the University of Erlangen-Nurnberg, finishing his degree under the supervision of Rudi van Eldik. Associated with his studies, during 2007, he worked for AREVA NP on radio-nuclear chemistry and computer modeling. Since 2008, he is studying towards a Ph.D. degree at UoC under the supervision of Shusheng Pang, Ken Marsh, and Mark Staiger. His research focuses on biocomposites from natural fibers, processed via ionic liquids. Chem. Rev. 2009, 109, 6712–6728 6712

Assessing the corrosion of biodegradable magnesium implants: a critical review of current methodologies and their limitations.

Magnesium (Mg) and its alloys have been intensively studied as biodegradable implant materials, where their mechanical properties make them attractive candidates for orthopaedic applications. There are several commonly used in vitro tests, from simple mass loss experiments to more complex electrochemical methods, which provide information on the biocorrosion rates and mechanisms. The various methods each have their own unique benefits and limitations. Inappropriate test setup or interpretation of in vitro results creates the potential for flawed justification of subsequent in vivo experiments. It is therefore crucial to fully understand the correct usages of each experiment and the factors that need to be considered before drawing conclusions. This paper aims to elucidate the main benefits and limitations for each of the major in vitro methodologies that are used in examining the biodegradation behaviour of Mg and its alloys.

A critical review of all-cellulose composites

Cellulose is a fascinating biopolymer of almost inexhaustible quantity. While being a lightweight material, it shows outstanding values of strength and stiffness when present in its native form. Unsurprisingly, cellulose fibre has been rigorously investigated as a reinforcing component in biocomposites. In recent years, however, a new class of monocomponent composites based on cellulosic materials, so-called all-cellulose composites (ACCs) have emerged. These new materials promise to overcome the critical problem of fibre–matrix adhesion in biocomposites by using chemically similar or identical cellulosic materials for both matrix and reinforcement. A number of papers scattered throughout the polymer, composites and biomolecular science literature have been published describing non-derivatized and derivatized ACCs. Exceptional mechanical properties of ACCs have been reported that easily exceed those of traditional biocomposites. Several different processing routes have been applied to the manufacture of ACCs using a broad range of different solvent systems and raw materials. This article aims to provide a comprehensive review of the background chemistry and various cellulosic sources investigated, various synthesis routes, phase transformations of the cellulose, and mechanical, viscoelastic and optical properties of ACCs. The current difficulties and challenges of ACCs are clearly outlined, pointing the way forward for further exploration of this interesting subcategory of biocomposites.

Magnesium alloys: Predicting in vivo corrosion with in vitro immersion testing†

Magnesium (Mg) and its alloys have been proposed as degradable replacements to commonly used orthopedic biomaterials such as titanium alloys and stainless steel. However, the corrosion of Mg in a physiological environment remains a difficult characteristic to accurately assess with in vitro methods. The aim of this study was to identify a simple in vitro immersion test that could provide corrosion rates similar to those observed in vivo. Pure Mg and five alloys (AZ31, Mg-0.8Ca, Mg-1Zn, Mg-1Mn, Mg-1.34Ca-3Zn) were immersed in either Earles balanced salt solution (EBSS), minimum essential medium (MEM), or MEM-containing 40 g/L bovine serum albumin (MEMp) for 7, 14, or 21 days before removal and assessment of corrosion by weight loss. This in vitro data was compared to in vivo corrosion rates of the same materials implanted in a subcutaneous environment in Lewis rats for equivalent time points. The results suggested that, for the alloys investigated, the EBSS buffered with sodium bicarbonate provides a rate of degradation comparable to those observed in vivo. In contrast, the addition of components such as (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid) (HEPES), vitamins, amino acids, and albumin significantly increased corrosion rates. Based on these findings, it is proposed that with this in vitro protocol, immersion of Mg alloys in EBSS can be used as a predictor of in vivo corrosion.

Magnesium biomaterials for orthopedic application: A review from a biological perspective

Magnesium (Mg) has a long history of investigation as a degradable biomaterial. Physicians first began using Mg for biomedical applications in the late 19th century. Experimentation continued with varying levels of success until the mid-20th century when interest in the metal waned. In recent years the field of Mg-based biomaterials has once again become popular, likely due to advancements in technology allowing improved control of corrosion. Although this has led to success in vascular applications, continued difficulties in predicting and controlling the corrosion rate of Mg in an intraosseous environment has impeded the development of Mg-based biomaterials for orthopedic applications. In this review, an initial summary of the basic properties and the physiological role of Mg are followed by a discussion of the physical characteristics of the metal which lend it to use as a degradable biomaterial. A description of the historical and modern applications for Mg in the medical field is followed by a discussion of the methods used to control and assess Mg corrosion, with an emphasis on alloying. The second part of this review concentrates on the methods used to assess the corrosion and biocompatibility of Mg-based orthopedic biomaterials. This review provides a summary of Mg as a biomaterial from a biological perspective.

Electrospun single-walled carbon nanotube/polyvinyl alcohol composite nanofibers: structure?property relationships

Polyvinyl alcohol (PVA) nanofibers and single-walled carbon nanotube (SWNT)/PVA composite nanofibers have been produced by electrospinning. An apparent increase in the PVA crystallinity with a concomitant change in its main crystalline phase and a reduction in the crystalline domain size were observed in the SWNT/PVA composite nanofibers, indicating the occurrence of a SWNT-induced nucleation crystallization of the PVA phase. Both the pure PVA and SWNT/PVA composite nanofibers were subjected to the following post-electrospinning treatments: (i) soaking in methanol to increase the PVA crystallinity, and (ii) cross-linking with glutaric dialdehyde to control the PVA morphology. Effects of the PVA morphology on the tensile properties of the resultant electrospun nanofibers were examined. Dynamic mechanical thermal analyses of both pure PVA and SWNT/PVA composite electrospun nanofibers indicated that SWNT-polymer interaction facilitated the formation of crystalline domains, which can be further enhanced by soaking the nanofiber in methanol and/or cross-linking the polymer with glutaric dialdehyde.

Buffer-regulated biocorrosion of pure magnesium

Magnesium (Mg) alloys are being actively investigated as potential load-bearing orthopaedic implant materials due to their biodegradability in vivo. With Mg biomaterials at an early stage in their development, the screening of alloy compositions for their biodegradation rate, and hence biocompatibility, is reliant on cost-effective in vitro methods. The use of a buffer to control pH during in vitro biodegradation is recognised as critically important as this seeks to mimic pH control as it occurs naturally in vivo. The two different types of in vitro buffer system available are based on either (i) zwitterionic organic compounds or (ii) carbonate buffers within a partial-CO2 atmosphere. This study investigated the influence of the buffering system itself on the in vitro corrosion of Mg. It was found that the less realistic zwitterion-based buffer did not form the same corrosion layers as the carbonate buffer, and was potentially affecting the behaviour of the hydrated oxide layer that forms on Mg in all aqueous environments. Consequently it was recommended that Mg in vitro experiments use the more biorealistic carbonate buffering system when possible.

Natural-fibre composites in structural applications

Publisher Summary A change that has been readily apparent in materials science is the increased interest in and usage of natural fibres extracted from wood or from plants such as hemp, flax, jute, kenaf, ramie and sisal. Natural fibres offer biodegradability, appropriate mechanical properties attributed to their high cellulose content and sustainability, making them attractive alternatives to synthetic reinforcing fibres used in polymer composites. Hence, there has been a strong resurgence in interest in natural fibres over the past decade or so, particularly for reinforcing polymeric materials. Natural fibres, if used in combination with a degradable polymer matrix, also serve as an inexpensive, renewable and less toxic alternative to synthetic fibres, while offering high specific strength and stiffness. This chapter focuses on the current use of biocomposites in semi-structural and structural applications in which they face their greatest challenges to be able to compete against synthetic fibre polymer composites in a wider range of load-bearing applications. Structural applications are loosely defined as those that play a major or principal role in supporting the structure of the final designed component.

Solvent infusion processing of all-cellulose composite materials

Continuous fibre-reinforced all-cellulose composite (ACC) laminates were produced in the form of a dimensionally thick (>1 mm) laminate using an easy-to-use processing pathway termed solvent infusion processing (SIP) from a rayon (Cordenka™) textile using the ionic liquid 1-butyl-3-methylimidazolium acetate. SIP facilitates the infusion of a solvent through a dry cellulose fibre preform with the aim of partially dissolving the outer surface of the cellulose fibres. The dissolved cellulose is then regenerated by solvent exchange to form a matrix phase in situ that acts to bond together the undissolved portion of the fibres. SIP is capable of producing thick, dimensionally stable ACC laminates with high volume fractions of continuous fibres (>70 vol.%) due to the combination of two factors: (i) homogeneous and controlled partial dissolution of the fibres and (ii) the application of pressure during regeneration and drying that provides a high level of fibre compaction, thereby overcoming void formation associated with material shrinkage. The effect of inlet and outlet positioning, and applied pressure on the macro- and microstructure of all-cellulose composites is examined. Finally, SIP expands the applications for ACCs by enabling the production of thick ACC laminates to overcome the limitations of conventional thin-film ACCs.

Effects of the molecular format of collagen on characteristics of electrospun fibres

Electrospinning is a process that is used to create nanofibres, which have the potential to be used in many medical and industrial applications. The molecular structure of the raw material is an important factor in determining the structure and quality of the electrospun fibres. In this study, we extracted collagen from a cold water fish species, hoki (Macruronus novaezelandiae), and prepared it in several different molecular formats (native triple helical collagen, denatured whole chains, denatured atelocollagen chains and gelatin) for electrospinning. Low molecular weight gelatin and atelocollagen did not form fibres. Treatment with 1,1,1,3,3,3 hexafluoro-2-propanol or 40% acetic acid denatured collagen molecules into intact α-chains prior to the electrospinning process. When using intact denatured collagen chains, 10% acetic acid was an effective aqueous-based solvent for producing uniform fibres. This information will be useful for the development of a non-toxic, aqueous solvent system suitable for industrial scale-up of the electrospinning process. Our results show that this low imino marine collagen is a suitable biopolymer for producing electrospun fibres.