Koon-Yang Lee

More Than Meets the Eye in Bacterial Cellulose: Biosynthesis, Bioprocessing, and Applications in Advanced Fiber Composites

Bacterial cellulose (BC) nanofibers are one of the stiffest organic materials produced by nature. It consists of pure cellulose without the impurities that are commonly found in plant-based cellulose. This review discusses the metabolic pathways of cellulose-producing bacteria and the genetic pathways of Acetobacter xylinum. The fermentative production of BC and the bioprocess parameters for the cultivation of bacteria are also discussed. The influence of the composition of the culture medium, pH, temperature, and oxygen content on the morphology and yield of BC are reviewed. In addition, the progress made to date on the genetic modification of bacteria to increase the yield of BC and the large-scale production of BC using various bioreactors, namely static and agitated cultures, stirred tank, airlift, aerosol, rotary, and membrane reactors, is reviewed. The challenges in commercial scale production of BC are thoroughly discussed and the efficiency of various bioreactors is compared. In terms of the application of BC, particular emphasis is placed on the utilization of BC in advanced fiber composites to manufacture the next generation truly green, sustainable and renewable hierarchical composites.

High Performance Cellulose Nanocomposites: Comparing the Reinforcing Ability of Bacterial Cellulose and Nanofibrillated Cellulose

This work investigates the surface and bulk properties of nanofibrillated cellulose (NFC) and bacterial cellulose (BC), as well as their reinforcing ability in polymer nanocomposites. BC possesses higher critical surface tension of 57 mN m(-1) compared to NFC (41 mN m(-1)). The thermal degradation temperature in both nitrogen and air atmosphere of BC was also found to be higher than that of NFC. These results are in good agreement with the higher crystallinity of BC as determined by XRD, measured to be 71% for BC as compared to NFC of 41%. Nanocellulose papers were prepared from BC and NFC. Both papers possessed similar tensile moduli and strengths of 12 GPa and 110 MPa, respectively. Nanocomposites were manufactured by impregnating the nanocellulose paper with an epoxy resin using vacuum assisted resin infusion. The cellulose reinforced epoxy nanocomposites had a stiffness and strength of approximately ∼8 GPa and ∼100 MPa at an equivalent fiber volume fraction of 60 vol.-%. In terms of the reinforcing ability of NFC and BC in a polymer matrix, no significant difference between NFC and BC was observed.

Renewable nanocomposite polymer foams synthesized from Pickering emulsion templates

Fully renewable macroporous thermosetting and UV-cured cellulose nanocomposites have been synthesized from medium and high internal phase water-in-acrylated soybean oil emulsions stabilized solely by hydrophobized bacterial cellulose nano-fibrils.

Phase behavior of medium and high internal phase water-in-oil emulsions stabilized solely by hydrophobized bacterial cellulose nanofibrils.

Water-in-oil emulsions stabilized solely by bacterial cellulose nanofibers (BCNs), which were hydrophobized by esterification with organic acids of various chain lengths (acetic acid, C2-; hexanoic acid, C6-; dodecanoic acid, C12-), were produced and characterized. When using freeze-dried C6-BCN and C12-BCN, only a maximum water volume fraction (ϕw) of 60% could be stabilized, while no emulsion was obtained for C2-BCN. However, the maximum ϕw increased to 71%, 81%, and 77% for C2-BCN, C6-BCN, and C12-BCN, respectively, 150 h after the initial emulsification, thereby creating high internal phase water-in-toluene emulsions. The observed time-dependent behavior of these emulsions is consistent with the disentanglement and dispersion of freeze-dried modified BCN bundles into individual nanofibers with time. These emulsions exhibited catastrophic phase separation when ϕw was increased, as opposed to catastrophic phase inversion observed for other Pickering emulsions.

Nanopapers for organic solvent nanofiltration

Would it not be nice to have an organic solvent nanofiltration membrane made from renewable resources that can be manufactured as simply as producing paper? Here the production of nanofiltration membranes made from nanocellulose by applying a papermaking process is demonstrated. Manufacture of the nanopapers was enabled by inducing flocculation of nanofibrils upon addition of trivalent ions.

Cross-Linked Bacterial Cellulose Networks Using Glyoxalization

In this study, we demonstrate that bacterial cellulose (BC) networks can be cross-linked via glyoxalization. The fracture surfaces of samples show that, in the dry state, less delamination occurs for glyoxalized BC networks compared to unmodified BC networks, suggesting that covalent bond coupling between BC layers occurs during the glyoxalization process. Youngs moduli of dry unmodified BC networks do not change significantly after glyoxalization. The stress and strain at failure are, however, reduced after glyoxalization. However, the wet mechanical properties of the BC networks are improved by glyoxalization. Raman spectroscopy is used to demonstrate that the stress-transfer efficiency of deformed dry and wet glyoxalized BC networks is significantly increased compared to unmodified material. This enhanced stress-transfer within the networks is shown to be a consequence of the covalent coupling induced during glyoxalization and offers a facile route for enhancing the mechanical properties of BC networks for a variety of applications.

Susceptibility of never-dried and freeze-dried bacterial cellulose towards esterification with organic acid

The susceptibility of (1) never-dried and (2) freeze-dried bacterial cellulose (BC) towards organic acid esterification is reported in this work. When never-dried BC (BC which was solvent exchanged from water through methanol into pyridine) was modified with hexanoic acid, it was found that the degree of substitution (DS) was significantly lower than that of hexanoic acid modified freeze-dried BC. The crystallinity of freeze-dried BC hexanoate was found to be significantly lower compared to neat BC and never-dried BC hexanoate. This result, along with the high DS indicates that significant bulk modification occurred during the esterification of freeze-dried BC. Such results were not observed for never-dried BC hexanoate. All these evidence point towards to fact that freeze-dried BC was more susceptible to organic acid esterification compared to never-dried BC. A few hypotheses were explored to explain the observed behaviour and further investigated to elucidate our observation; the effect of residual water in cellulose, the accessibility of hydroxyl groups and the crystal structure of never-dried and freeze-dried BC on the susceptibility of cellulose fibrils to esterification, respectively. However, the investigation of these hypotheses raised more questions and we are still left with the main question; why do BC nanofibres behave differently when modifying freeze-dried BC or never-dried BC?

Interfaces in Cross-Linked and Grafted Bacterial Cellulose/Poly(Lactic Acid) Resin Composites

This article presents approaches to maximize the mechanical performance of bacterial cellulose/poly(lactic acid) composites through chemical modification of the interface. This is achieved by both cross-linking the layered bacterial cellulose structure and by grafting maleic anhydride to the matrix material. Unmodified and glyoxalized bacterial cellulose (BC) networks have been embedded in poly(lactic acid) (PLA) resin and then in maleated resin using a compression molding method. The effect of these chemical modifications on the physical properties of these composites is reported. The tensile properties of the composites showed that Young’s moduli can be increased significantly when both BC networks and PLA were chemically modified. Interface consolidation between layers in BC networks has been achieved by glyoxalization. The effect of these modifications on both stress-transfer between the fibers and between the matrix and the fibers was quantified using Raman spectroscopy. Two competitive deformation mechanisms are identified; namely the mobility between BC layers, and between BC and PLA. The coupling strength of these interfaces could play a key role for optimization of these composites’ mechanical properties.

Bio-based macroporous polymer nanocomposites made by mechanical frothing of acrylated epoxidised soybean oil

Mechanical frothing is one of the most commonly used methods to create gas-liquid foams. Until recently, the polymerisation of mechanically frothed gas-liquid foams was limited to the synthesis of quasi two-dimensional polymer structures, such as films. In this study we show that three-dimensional bio-based polymer foams can be created by microwave curing of gas-soybean oil foams created by mechanical frothing using lauryl peroxide as the radical initiator. It was found that the introduction of air during the mechanical frothing was necessary to create the three-dimensional polymer foams. Using bacterial cellulose nanofibrils (BC) simultaneously as a foam stabiliser has potential because it obstructs the flow of liquid from the lamella region in these gas-soybean oil foams while simultaneously acting as nano-filler in the polymer foam. It was found that the stability of the gas-soybean oil foam templates and the mechanical properties of the polymer nanocomposite foams are enhanced upon the addition of BC in to the foams.

Greener Surface Treatments of Natural Fibres for the Production of Renewable Composite Materials

Natural fibres have been the prime candidate to replace synthetic fibres for the production of composite materials. Major advantages associated with natural fibres include low cost, low density, high toughness and biodegradability. However, these intriguing properties of natural fibres do come at a price. The hydrophilic nature of natural fibres often results in poor compatibility with hydrophobic polymer matrices. Various surface treatments of natural fibres using chemicals have been developed to improve the compatibility between the fibres and the matrix, but large amounts of solvents are usually involved. In this chapter, greener surface treatments without the use of hazardous chemicals are reviewed. These include plasma treatments, the use of enzymes and fungi for the extraction and surface treatment of raw fibres or natural fibres and the deposition of bacterial cellulose onto natural fibres. These treatments are aimed at improving the interfacial adhesion between the fibres and the matrix, thereby improving the stress transfer efficiency from the matrix to the fibre. The effects of these treatments on the properties of natural fibres are discussed. In addition to this, the overall impact of these treatments on the mechanical properties of the resulting natural fibre reinforced composites is also addressed.