Jörg Müssig

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.

Fibre matrix adhesion of natural fibres cotton, flax and hemp in polymeric matrices analyzed with the single fibre fragmentation test

In this research the adhesion and the resulting interfacial shear strength (IFFS) between the natural fibres flax, hemp and cotton and the polymer matrices polypropylene with coupling agent (MAPP) and polylactide acid (PLA) was surveyed with the single fibre fragmentation test (SFFT). The adhesion between MAPP and the fibres was good enough to produce fragments, whereas the adhesion between PLA and flax was too weak to transmit enough tension for fibre cracks which is clearly visible on SEM-photographs. Comparing the IFFS values of the fibres in MAPP with an equal fibre diameter shows that the IFFS value of flax is highest with 7.09 N/mm2 followed by hemp 6.13 N/mm2. The IFFS of cotton is a lot smaller (0.664 N/mm2). The critical fragmentation or fragmentation length of the bast fibres flax (3.16 mm) and hemp (3.20 mm) in MAPP is smaller than the critical fragmentation length of cotton (5.03 mm). The adhesion between the lignocellulosic fibres and MAPP is much better than between the lignin and pectin free cellulose fibre and MAPP. Possible reasons for this — the surface structure of the cotton fibre and its different chemical composition being made up of only cellulose, hemi-cellulose and wax with no pectin or lignin present — are discussed.

Functional plant cell wall design revealed by the Raman imaging approach

Using the Raman imaging approach, the optimization of the plant cell wall design was investigated on the micron level within different tissue types at different positions of a Phormium tenax leaf. Pectin and lignin distribution were visualized and the cellulose microfibril angle (MFA) of the cell walls was determined. A detailed analysis of the Raman spectra extracted from the selected regions, allowed a semi-quantitative comparison of the chemical composition of the investigated tissue types on the micron level. The cell corners of the parenchyma revealed almost pure pectin and the cell wall an amount of 38–49% thereof. Slight lignification was observed in the parenchyma and collenchyma in the top of the leaf and a high variability (7–44%) in the sclerenchyma. In the cell corners and in the cell wall of the sclerenchymatic fibres surrounding the vascular tissue, the highest lignification was observed, which can act as a barrier and protection of the vascular tissue. In the sclerenchyma high variable MFA (4°–40°) was detected, which was related with lignin variability. In the primary cell walls a constant high MFA (57°–58°) was found together with pectin. The different plant cell wall designs on the tissue and microlevel involve changes in chemical composition as well as cellulose microfibril alignment and are discussed and related according to the development and function.

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.

Enhancing the Fibre Matrix Adhesion of Natural Fibre Reinforced Polypropylene by Electron Radiation Analyzed with the Single Fibre Fragmentation Test

The effects of electron radiation on natural fibre reinforced polypropylene have been analyzed with the single fibre fragmentation test. Specimens of single hemp, flax, ramie and cotton fibres/fibre bundles embedded in a polypropylene sheet were irradiated with electron radiation of 10 MeV with intensities of 5, 15 and 33 kGy. The radiation led to a strain reduction of the polypropylene but did also improve the adhesion between polymer and flax, hemp and cotton fibres/fibre bundles. The critical fragmentation length and the interfacial shear strength (IFSS) of the composite specimens have been determined showing a clear increase of the IFSS of up to 50% compared to specimens with applied coupling agents. Due to the high strain reduction of the PP at intensities of 15 and 33 kGy the different fibres could only be compared at 5 kGy. The ramie fibre specimens could be analyzed at 5 and 15 kGy intensity showing higher IFSS values at the higher intensity. A possible explanation for the improvement is the forming of radicals with the cellulose chains of the natural fibres and the polypropylene molecules leading to crosslinking and, therefore, better adhesion between the different components.

Combination of biological mechanisms for a concept study of a fracture-tolerant bio-inspired ceramic composite material

The biological materials nacre and wood are renowned for their impressive combination of toughness and strength. The key mechanisms of these highly complex structures are crack deflection at weak interfaces, crack bridging, functional gradients and reinforcing elements. These principles were applied to a more fracture-tolerant model material which combined porous stiff ceramic layers, manufactured by freeze casting, infiltrated and bonded by a polymer phase reinforced with fabric layers. In the hybrid composites, crack deflection occurred at the ceramic–fabric interface and the intact fabric layers served as crack-bridging elements. Fabric-reinforced epoxy layers stabilized the fracture behaviour and delayed catastrophic failure of the material. The influence of the different components was analysed by varying the ceramic, fabric and interface properties. More ductile fabrics lead to larger strain to failure and more crack bridging but reduced the composite strength and stiffness after initial cracking. Higher elastic mismatch between the components improved crack deflection and bridging but resulted in deterred load transfer and a lower strength. The stiffness and strength of the ceramic layers influenced the elastic properties of the laminar composite and the initial crack resistance. Flaw tolerance was increased with polymer infiltration. We show with our hybrid ceramic–fabric composite as a bio-inspired concept study how fracture toughness, work of fracture and tolerance for cracking can be tailored when the contributing factors, i.e. the ceramic, the fabric and their interface, are modified.

Impact and hardness optimisation of composite materials inspired by the babassu nut (Orbignya speciosa)

The babassu nut is the fruit of the babassu palm Orbignya speciosa. The combination of hardness and impact strength is difficult to acquire for artificial materials, making the babassu nut a promising source for biomimetic inspiration. Unnotched Charpy impact tests, Shore D hardness tests and scanning electron microscopy were used for mechanical and microscopical analysis of the pericarp. Four major principles were found for a biomimetic approach: a hard core ((1); endocarp) is embedded in a soft outer layer of high impact strength ((2); epicarp) and is reinforced with fibres of variable fineness (3), some of which are oriented radial to the core (4). Biomimetic fibre-reinforced composites were produced using abstracted mechanisms of the babassu nut based on regenerated cellulose fibres (lyocell, L) with two different fineness values as reinforcement embedded in a polylactide (PLA) core matrix and polypropylene (PP) based outer layers. The biomimetic fibre composite reaches a significantly higher impact strength that is 1.6 times higher than the reference sample produced from a PLA/PP/L-blend. At the same time the hardness is slightly increased compared to PP/L.

Spunlaced Flax/Polypropylene Nonwoven as Auto Interior Material: Mechanical Performance:

The spunlacing technique for producing auto interior nonwovens is examined. A 50/50 flax/polypropylene nonwoven is processed using an AquaJet spunlace system with two different spunlacing settings. The spunlaced nonwovens are thermally bonded into 2D and 3D interior parts by a panel press and a stamp-forming press. Physical properties, mechanical properties, and moldability of the nonwovens after spunlacing and molding are evaluated in accordance with relevant European and German industrial standards. The statistical method of variance analysis and image analysis method are used for data process. The research work finds that the spunlacing process brings some technical merits for the flax/polypropylene nonwoven in auto interior applications, in particular, an enhancement of tensile and flexural strengths, a large thickness reduction with controlled ultimate weight, and a competitive moldability. The experimental data also reveals that using a setting of lower water-jet pressure on the spunlacing process line is more suitable for entangling flax/polypropylene nonwovens to produce high performance auto interior composites.

Cellulose Fiber-Reinforced PLA versus PP

The present study focuses on a comparison between different cellulose fiber-reinforced thermoplastics. Composites were produced with 30 mass-% lyocell fibers and a PLA or PP matrix with either an injection (IM) or compression molding (CM) process. Significant reinforcement effects were achieved for tensile strength, Young’s modulus, and Shore D hardness by using lyocell as reinforcing fiber. These values are significantly higher for PLA and its composites compared to PP and PP-based composites. Investigations of the fiber/matrix adhesion show a better bonding for lyocell in PLA compared to PP, resulting in a more effective load transfer from the matrix to the fiber. However, PLA is brittle while PP shows a ductile stress-strain behavior. The impact strength of PLA was drastically improved by adding lyocell while the impact strength of PP decreased. CM and IM composites do not show significant differences in fiber orientation. Despite a better compaction of IM composites, higher tensile strength values were achieved for CM samples due to a higher fiber length.

Three-dimensional braiding of continuous regenerated cellulose fibres

A growing interest in biocomposites leads to the extension of commonly used three-dimensional braiding processes for composite preforming to cellulose-based fibres. A rayon fibre (Cordenka™) is processed on an Institut für Textiltechnik 3D rotary braiding machine, generally used for the processing of stronger and stiffer glass and carbon fibres. A rectangular profile was produced from 32 yarns and the braiding angle of the yarn was analysed. Analysis of the fibre tensile properties during the different processing steps revealed only a minor reduction in fibre strain. The fibre strength and Young’s modulus were unaffected by the braiding process showing that 3D rotary braiding can be extended to biobased fibres without any required changes.