In-situ monitoring of changes in ultrastructure and mechanical properties of flax cell walls during controlled heat treatment.

Plant fibres are increasingly used as reinforcements, especially in thermoplastic composites. Understanding the impact of temperature on the properties of these fibres is an important issue for the manufacturing of high-performance materials with minimal defects. In this work, the structural evolution and mechanical behaviour of flax fibre cell walls were dynamically monitored by temperature-controlled X-ray diffraction and nanoindentation from 25 to 230 °C; detailed biochemical analysis was also conducted on fibre samples after each heating step. With increasing temperature up to 230 °C, a decrease in the local mechanical performance of the flax cell walls, of about -72 % for the indentation modulus and -35 % for the hardness, was measured. This was associated with a decrease in the packing of the cellulose crystal lattice (increase in d-spacing d200), as well as significant mass losses measured by thermogravimetric analysis and changes in the biochemical composition, i.e. non-cellulosic polysaccharides attributed to the middle lamellae but also to the cell walls. This work, which proposes for the first time an in-situ investigation of the dynamic temperature evolution of the flax cell wall properties, highlights the reversible behaviour of their crystalline structure (i.e. cellulose) and local mechanical properties after cooling to room temperature, even after exposure to high temperatures.

In Situ Tensile Testing under High-Speed Optical Recording to Determine Hierarchical Damage Kinetics in Polymer Layers of Flax Fibre Elements.

This study aims at better understanding the damage and fracture kinetics in flax fibre elements at both the unitary and bundle scales, using an experimental setup allowing optical observation at high recording rate in the course of tensile loading. Defects and issues from flax unitary fibre extraction are quantitated using polarized light microscopy. Tensile loading is conducted according to a particular setup, adapted to fibres of 10 to 20 µm in diameter and 10 mm in length. Optical recording using a high-speed camera is performed during loading up to the failure at acquisition, with speed ranging from 108,000 to 270,000 frames per second. Crack initiation in polymer layers of fibre elements, propagation as well as damage mechanisms are captured. The results show different failure scenarios depending on the fibre element's nature. In particular, fractured fibres underline either a fully transverse failure propagation or a combination of transverse and longitudinal cracking with different balances. Image recordings with high time resolution of down to 3.7 µs suggest an unstable system and transverse crack speed higher than 4 m/s and a slower propagation for longitudinal crack deviation. Failure propagation monitoring and fracture mechanism studies in individual natural fibre or bundles, using tensile load with optical observation, showed contrasted behaviour and the importance of the structural scale exanimated. This study can help in tailoring the eco-design of flax-based composites, in terms of toughness and mechanical performances, for both replacement of synthetic fibre materials and innovative composites with advanced properties.

A Circular Approach for the Valorization of Tomato By-Product in Biodegradable Injected Materials for Horticulture Sector.

This study focuses on the use of tomato (Solanum lycopersicum L.) by-product biomass from industrial plants as reinforcement for designing a range of new degradable and biobased thermoplastic materials. As a novel technique, this fully circular approach enables a promising up-cycling of tomato wastes. After an in-depth morphological study of the degree of reinforcement through SEM and dynamic analysis, mechanical characterization was carried out. Our mechanical results demonstrate that this circular approach is of interest for composite applications. Despite their moderate aspect ratio values (between 1.5 and 2), the tomato by-product-reinforced materials can mechanically compete with existing formulations; PBS-Tomato fiber, for example, exhibits mechanical performance very close to that of PP-flax, especially regarding strength (+11%) and elongation at break (+6%). According to the matrix and particle morphology, a large range of products-biobased and/or degradable, depending on the targeted application-can be designed from tomato cultivation by-products.

Evolution of the ultrastructure and polysaccharide composition of flax fibres over time: When history meets science.

Flax fibres have been used by humans for approximately 10,000 years. With time, the geographic area of production and cultivation has changed, as have the applications of flax fibres; from clothing to sails and paintings from antiquity, to automotive, fashion, and design applications in the contemporary era. The degradation process of flax fibres is the same for both ancient and modern objects made from this polysaccharidic material. This review, focusing on the cultural heritage field, after a brief description of flax plants and fibres, retraces the history of their use through Europe and the Near East, and discusses the evolution of extraction methods with human progress. Furthermore, the most important mechanisms of flax fibre degradation and the characterisation techniques currently in use are described. This study highlights the constructive interchange between engineering and cultural heritage that can be realised through a continuous comparison of antiquity and the contemporary era.

Impact of cell wall non-cellulosic and cellulosic polymers on the mechanical properties of flax fibre bundles.

Fibre bundles are groups of elementary fibres glued together thanks to the middle lamella, and are the main fraction in plant fibre composites. In this study, relationship between the mechanical properties of flax fibre bundles, chemical composition and cellulose structure were investigated. To do so, a sequential biopolymer extraction was implemented. Fibre bundles were first depectinated by oxalate extraction, and then the hemicelluloses were extracted by LiCl/dimethyl sulfoxide (DMSO) and KOH. The oxalate extract consisted of homogalacturonans and type I rhamnogalacturonans, while the LiCl extract was composed mainly of glucomannans and the KOH extract of xyloglucans. The KOH stage resulted in the appearance of cellulose II in flax bundles. The extraction of pectin and hemicelluloses led to the disappearance of the middle lamella concomitant with a decrease in the tensile Young's modulus and maximum strength. Finally, the fibre bundle composition, ultrastructure and mechanical properties are discussed together in view of the thin middle lamella.

Lessons on textile history and fibre durability from a 4,000-year-old Egyptian flax yarn.

Flax has a long and fascinating history. This plant was domesticated around 8,000 BCE1 in the Fertile Crescent area2, first for its seeds and then for its fibres1,3. Although its uses existed long before domestication, residues of flax yarn dated 30,000 years ago have been found in the Caucasus area4. However, Ancient Egypt laid the foundations for the cultivation of flax as a textile fibre crop5. Today flax fibres are used in high-value textiles and in natural actuators6 or reinforcements in composite materials7. Flax is therefore a bridge between ages and civilizations. For several decades, the development of non- or micro-destructive analysis techniques has led to numerous works on the conservation of ancient textiles. Non-destructive methods, such as optical microscopy8 or vibrational techniques9,10, have been largely used to investigate archaeological textiles, principally to evaluate their degradation mechanisms and state of conservation. Vibrational spectroscopy studies can now benefit from synchrotron radiation11 and X-ray diffraction measurement in the archaeometric study of historical textiles12,13. Conservation of mechanical performance and the ultrastructural differences between ancient and modern flax varieties have not been examined thus far. Here we examine the morphological, ultrastructural and mechanical characteristics of a yarn from an Egyptian mortuary linen dating from the early Middle Kingdom (Eleventh Dynasty, ca. 2033-1963 BCE) and compare them with a modern flax yarn to assess the quality and durability of ancient flax fibres and relate these to their processing methods. Advanced microscopy techniques, such as nano-tomography, multiphoton excitation microscopy and atomic force microscopy were used. Our findings reveal the cultural know-how of this ancient civilization in producing high-fineness fibres, as well as the exceptional durability of flax, which is sometimes questioned, demonstrating their potential as reinforcements in high-technology composites.

Investigations by AFM of Ageing Mechanisms in PLA-Flax Fibre Composites during Garden Composting.

PLA-flax non-woven composites are promising materials, coupling high performance and possible degradation at their end of life. To explore their ageing mechanisms during garden composting, microstructural investigations were carried out through scanning electron microscopy (SEM) and atomic force microscopy (AFM). We observe that flax fibres preferentially degrade 'inwards' from the edge to the core of the composite. In addition, progressive erosion of the cell walls occurs within the fibres themselves, 'outwards' from the central lumen to the periphery primary wall. This preferential degradation is reflected in the decrease in indentation modulus from around 23 GPa for fibres located in the preserved core of the composite to 3-4 GPa for the remaining outer-most cell wall crowns located at the edge of the sample that is in contact with the compost. Ageing of the PLA matrix is less drastic with a relatively stable indentation modulus. Nevertheless, a change in the PLA morphology, a significant decrease in its roughness and increase of porosity, can be observed towards the edge of the sample, in comparison to the core. This work highlights the important role of intrinsic fibre porosity, called lumen, which is suspected to be a major variable of the compost ageing process, providing pathways of entry for moisture and microorganisms that are involved in cell wall degradation.

A Review of Permeability and Flow Simulation for Liquid Composite Moulding of Plant Fibre Composites.

Liquid composite moulding (LCM) of plant fibre composites has gained much attention for the development of structural biobased composites. To produce quality composites, better understanding of the resin impregnation process and flow behaviour in plant fibre reinforcements is vital. By reviewing the literature, we aim to identify key plant fibre reinforcement-specific factors that influence, if not govern, the mould filling stage during LCM of plant fibre composites. In particular, the differences in structure (physical and biochemical) for plant and synthetic fibres, their semi-products (i.e., yarns and rovings), and their mats and textiles are shown to have a perceptible effect on their compaction, in-plane permeability, and processing via LCM. In addition to examining the effects of dual-scale flow, resin absorption, (subsequent) fibre swelling, capillarity, and time-dependent saturated and unsaturated permeability that are specific to plant fibre reinforcements, we also review the various models utilised to predict and simulate resin impregnation during LCM of plant fibre composites.

The Middle Lamella of Plant Fibers Used as Composite Reinforcement: Investigation by Atomic Force Microscopy.

Today, plant fibers are considered as an important new renewable resource that can compete with some synthetic fibers, such as glass, in fiber-reinforced composites. In previous works, it was noted that the pectin-enriched middle lamella (ML) is a weak point in the fiber bundles for plant fiber-reinforced composites. ML is strongly bonded to the primary walls of the cells to form a complex layer called the compound middle lamella (CML). In a composite, cracks preferentially propagate along and through this layer when a mechanical loading is applied. In this work, middle lamellae of several plant fibers of different origin (flax, hemp, jute, kenaf, nettle, and date palm leaf sheath), among the most used for composite reinforcement, are investigated by atomic force microscopy (AFM). The peak-force quantitative nanomechanical property mapping (PF-QNM) mode is used in order to estimate the indentation modulus of this layer. AFM PF-QNM confirmed its potential and suitability to mechanically characterize and compare the stiffness of small areas at the micro and nanoscale level, such as plant cell walls and middle lamellae. Our results suggest that the mean indentation modulus of ML is in the range from 6 GPa (date palm leaf sheath) to 16 GPa (hemp), depending on the plant considered. Moreover, local cell-wall layer architectures were finely evidenced and described.

Flax (Linum usitatissimum L.) Fibers for Composite Reinforcement: Exploring the Link Between Plant Growth, Cell Walls Development, and Fiber Properties.

Due to the combination of high mechanical performances and plant-based origin, flax fibers are interesting reinforcement for environmentally friendly composite materials. An increasing amount of research articles and reviews focuses on the processing and properties of flax-based products, without taking into account the original key role of flax fibers, namely, reinforcement elements of the flax stem (Linum usitatissimum L.). The ontogeny of the plant, scattering of fiber properties along the plant, or the plant growth conditions are rarely considered. Conversely, exploring the development of flax fibers and parameters influencing the plant mechanical properties (at the whole plant or fiber scale) could be an interesting way to control and/or optimize fiber performances, and to a greater extent, flax fiber-based products. The first part of the present review synthesized the general knowledge about the growth stages of flax plants and the internal organization of the stem biological tissues. Additionally, key findings regarding the development of its fibers, from elongation to thickening, are reviewed to offer a piece of explanation of the uncommon morphological properties of flax fibers. Then, the slenderness of flax is illustrated by comparison of data given in scientific research on herbaceous plants and woody ones. In the second section, a state of the art of the varietal selection of several main industrial crops is given. This section includes the different selection criteria as well as an overview of their impact on plant characteristics. A particular interest is given to the lodging resistance and the understanding of this undesired phenomenon. The third section reviews the influence of the cultural conditions, including seedling rate and its relation with the wind in a plant canopy, as well as the impact of main tropisms (namely, thigmotropism, seismotropism, and gravitropism) on the stem and fiber characteristics. This section illustrates the mechanisms of plant adaptation, and how the environment can modify the plant biomechanical properties. Finally, this review asks botanists, breeders, and farmers' knowledge toward the selection of potential flax varieties dedicated to composite applications, through optimized fiber performances. All along the paper, both fibers morphology and mechanical properties are discussed, in constant link with their use for composite materials reinforcement.

Evolution of flax cell wall ultrastructure and mechanical properties during the retting step.

Flax retting is a major bioprocess in the cultivation and extraction cycle of flax fibres. The aim of the present study is to improve the understanding of the evolution of fibre properties and ultrastructure caused by this process at the plant cell wall scale. Initially, investigations of the mechanical performances of the flax cell walls by Atomic Force Microscopy (AFM) in Peak Force mode revealed a significant increase (+33%) in the cell wall indentation modulus with retting time. Two complementary structural studies are presented here, namely using X-Ray Diffraction (XRD) and solid state Nuclear Magnetic Resonance (NMR). An estimation of the cellulose crystallinity index by XRD measurements, confirmed by NMR, shows an increase of 8% in crystallinity with retting mainly due to the disappearance of amorphous polymer. In addition, NMR investigations show a compaction of inaccessible cell wall polymers, combined with an increase in the relaxation times of the C4 carbon. This densification provides a structural explanation for the observed improvement in mechanical performance of the secondary wall of flax fibres during the field retting process.

Flax stems: from a specific architecture to an instructive model for bioinspired composite structures.

The present paper proposes to carefully study and describe the reinforcement mechanisms within a flax stem, which is an exceptional natural model of composite structure. Thanks to accurate microscopic investigations, with both optical and SEM method, we finely depicted the flax stem architecture, which can be view as a composite structure with an outer protection, a unidirectional ply on the periphery and a porous core; each component has a specific function, such as mechanical reinforcement for the unidirectional ply and the porous core. The significant mechanical role of fibres was underlined, as well as their local organisation in cohesive bundles, obtained because of an intrusive growth and evidenced in this work through nanomechanical AFM measurement and 3D reconstruction. Following a biomimetic approach, these data provide a source of inspiration for the composite materials of tomorrow.