Alginate-Based Bio-Composites and Their Potential Applications.

Over the last two decades, bio-polymer fibers have attracted attention for their uses in gene therapy, tissue engineering, wound-healing, and controlled drug delivery. The most commonly used bio-polymers are bio-sourced synthetic polymers such as poly (glycolic acid), poly (lactic acid), poly (e-caprolactone), copolymers of polyglycolide and poly (3-hydroxybutyrate), and natural polymers such as chitosan, soy protein, and alginate. Among all of the bio-polymer fibers, alginate is endowed with its ease of sol-gel transformation, remarkable ion exchange properties, and acid stability. Blending alginate fibers with a wide range of other materials has certainly opened many new opportunities for applications. This paper presents an overview on the modification of alginate fibers with nano-particles, adhesive peptides, and natural or synthetic polymers, in order to enhance their properties. The application of alginate fibers in several areas such as cosmetics, sensors, drug delivery, tissue engineering, and water treatment are investigated. The first section is a brief theoretical background regarding the definition, the source, and the structure of alginate. The second part deals with the physico-chemical, structural, and biological properties of alginate bio-polymers. The third part presents the spinning techniques and the effects of the process and solution parameters on the thermo-mechanical and physico-chemical properties of alginate fibers. Then, the fourth part presents the additives used as fillers in order to improve the properties of alginate fibers. Finally, the last section covers the practical applications of alginate composite fibers.

Piezoresistive Properties of 3D-Printed Polylactic Acid (PLA) Nanocomposites.

An increasing interest is focused on the application of 3D printing for sensor manufacturing. Using 3D printing technology offers a new approach to the fabrication of sensors that are both geometrically and functionally complex. This work presents the analysis of the 3D-printed thermoplastic nanocomposites compress under the applied force. The response for the corresponding resistance changes versus applied load is obtained to evaluate the effectiveness of the printed layer as a pressure/force sensor. Multi-walled carbon nanotubes (MWNT) and high-structured carbon black (Ketjenblack) (KB) in the polylactic acid (PLA) matrix were extruded to develop 3D-printable filaments. The electrical and piezoresistive behaviors of the created 3D-printed layers were investigated. The percolation threshold of MWNT and KB 3D-printed layers are 1 wt.% and 4 wt.%, respectively. The PLA/1 wt.% MWNT 3D-printed layers with 1 mm thickness exhibit a negative pressure coefficient (NPC) characterized by a decrease of about one decade in resistance with increasing compressive loadings up to 18 N with a maximum strain up to about 16%. In the cyclic mode with a 1 N/min force rate, the PLA/1 wt.% MWNT 3D-printed layers showed good performance with the piezoresistive coefficient or gauge factor (G) of 7.6 obtained with the amplitude of the piezoresistive response (Ar) of about -0.8. KB composites could not show stable piezoresistive responses in a cyclic mode. However, under high force rate compression, the PLA/4 wt.% KB 3D-printed layers led to responses of large sensitivity (Ar = -0.90) and were exempt from noise with a high value of G = 47.6 in the first cycle, which is a highly efficient piezoresistive behavior.

Nano-Structured Ridged Micro-Filaments (≥100 µm Diameter) Produced Using a Single Step Strategy for Improved Bone Cell Adhesion and Proliferation in Textile Scaffolds.

Textile scaffolds that are either 2D or 3D with tunable shapes and pore sizes can be made through textile processing (weaving, knitting, braiding, nonwovens) using microfilaments. However, these filaments lack nano-topographical features to improve bone cell adhesion and proliferation. Moreover, the diameter of such filaments should be higher than that used for classical textiles (10−30 µm) to enable adhesion and the efficient spreading of the osteoblast cell (>30 µm diameter). We report, for the first time, the fabrication of biodegradable nanostructured cylindrical PLLA (poly-L-Lactic acid) microfilaments of diameters 100 µm and 230 µm, using a single step melt-spinning process for straightforward integration of nano-scale ridge-like structures oriented in the fiber length direction. Appropriate drawing speed and temperature used during the filament spinning allowed for the creation of instabilities giving rise to nanofibrillar ridges, as observed by AFM (Atomic Force Microscopy). These micro-filaments were hydrophobic, and had reduced crystallinity and mechanical strength, but could still be processed into 2D/3D textile scaffolds of various shapes. Biological tests carried out on the woven scaffolds made from these nano-structured micro filaments showed excellent human bone cell MG 63 adhesion and proliferation, better than on smooth 30 µm- diameter fibers. Elongated filopodia of the osteoblast, intimately anchored to the nano-structured filaments, was observed. The filaments also induced in vitro osteogenic expression, as shown by the expression of osteocalcin and bone sialoprotein after 21 days of culture. This work deals with the fabrication of a new generation of nano-structured micro-filament for use as scaffolds of different shapes suited for bone cell engineering.

Study of the Influence of PCL on the In Vitro Degradation of Extruded PLA Monofilaments and Melt-Spun Filaments.

This work presents the effect of a melt-spinning process on the degradation behavior of bioresorbable and immiscible poly(d,l-lactide) (PLA) and polycaprolactone (PCL) polymer blends. A large range of these blends, from PLA90PCL10 (90 wt% PLA and 10 wt% PCL) to PLA60PCL40 in increments of 10%, was processed via extrusion (diameter monofilament: ∅ ≈ 1 mm) and melt spinning (80 filaments: 50 to 70 µm each) to evaluate the impact of the PCL ratio and then melt spinning on the hydrolytic degradation of PLA, which allowed for highlighting the potential of a textile-based scaffold in bioresorbable implants. The morphologies of the structures were investigated via extracting PCL with acetic acid and scanning electron microscopy observations. Then, they were immersed in a Dulbecco's Modified Eagle Medium (DMEM) media at 50 °C for 35 days and their properties were tested in order to evaluate the relation between the morphology and the evolution of the crystallinity degree and the mechanical and physical properties. As expected, the incorporation of PCL into the PLA matrix slowed down the hydrolytic degradation. It was shown that the degradation became heterogeneous with a small ratio of PCL. Finally, melt spinning had an impact on the morphology, and consequently, on the other properties over time.

Antibacterial Textile Based on Hydrolyzed Milk Casein.

Antimicrobial textile structures are developed based on polypropylene (PP) and a natural material, hydrolyzed casein. The casein, from bovine milk, is subjected to acid hydrolysis in aqueous media, then blended into the PP matrix in the melt phase by extrusion. The obtained blend, containing 5 wt.% of hydrolyzed casein, is then processed by a melt spinning process to get multifilaments, leading to the production knitting structures. Thanks to the addition of the hydrolyzed casein, the obtained textile showed a strong antibacterial activity towards both Gram (+) and Gram (-) bacterial strains. The addition of 5 wt.% hydrolyzed casein does not significantly impact the mechanical properties of PP in the dumbbells form, but a small decrease was observed in the tenacity of the filaments. No moisture retention was observed after the addition of hydrolyzed casein, but the rheological behavior was slightly affected. The obtained results can contribute to addressing concerns regarding nonrenewable antibacterial agents used in textile materials, particularly their effects on the environment and human health, by offering antibacterial agents from a biobased and edible substance with high efficiency. They are also promising to respond to issues of wasting dairy products and recycling them, in addition to the advantages of using melt processes.

Melt Spinning of Flexible and Conductive Immiscible Thermoplastic/Elastomer Monofilament for Water Detection.

In many textile fields, such as industrial structures or clothes, one way to detect a specific liquid leak is the electrical conductivity variation of a yarn. This yarn can be developed using melt spun of Conductive Polymer Composites (CPCs), which blend insulating polymer and electrically conductive fillers. This study examines the influence of the proportions of an immiscible thermoplastic/elastomer blend for its implementation and its water detection. The thermoplastic polymer used for the detection property is the polyamide 6.6 (PA6.6) filled with enough carbon nanotubes (CNT) to exceed the percolation threshold. However, the addition of fillers decreases the polymer fluidity, resulting in the difficulty to implement the CPC. Using an immiscible polymers blend with an elastomer, which is a propylene-based elastomer (PBE) permits to increase this fluidity and to create a flexible conductive monofilament. After characterizations (morphology, rheological and mechanical) of this blend (PA6.6CNT/PBE) in different proportions, two principles of water detection are established and carried out with the monofilaments: the principle of absorption and the short circuit. It is found that the morphology of the immiscible polymer blend had a significant role in the water detection.

In Situ Detection of Water Leakage for Textile-Reinforced Composites.

By incorporating electrically conductive yarns into a waterproof membrane, one can detect epoxy resin cracking or liquid leakage. Therefore, this study examined the electrical conductivity variations of several yarns (metallic or carbon-based) for cracking and water detection. The first observations concerned the detectors' feasibility by investigating their conductivity variations during both their resin implementation processes and their resin cracking. Throughout this experiment, two phenomena were detected: the compression and the separation of the fibres by the resin. In addition, the resin cracking had an important role in decreasing the yarns' conductivity. The second part of this study concerned water detection. Two principles were established and implemented, first with yarns and then with yarns incorporated into the resin. First, the principle of absorption was based on the conductivity variation with the yarns' swelling after contact with water. A short circuit was established by the creation of a conductive path when a drop of water was deposited between two conductive, parallel yarns. Through the influence of the yarns' properties, this study explored the metallic yarns' capacity to better detect water with a short circuit and the ability of the carbon-based yarns to detect water by the principle of absorption.

Development of Novel Polyamide 11 Multifilaments and Fabric Structures Based on Industrial Lignin and Zinc Phosphinate as Flame Retardants.

Biobased lignin represents one of the possible materials for next-generation flame retardant additives due to its sustainability, environmental benefits and comparable efficiency to other flame retardant (FR) additives. In this context, this study presents the development of FR polyamide 11 (PA11) multifilament yarns and fabric structures containing different industrial lignins (i.e., lignosulfonate lignin (LL), and Kraft lignin (KL)) and zinc phosphinate (ZnP). The combination of ZnP and lignin (KL or LL) at different weight ratios were used to prepare flame retarded PA11 blends by melt mixing using a twin-screw extruder. These blends were transformed into continuous multifilament yarns by the melt-spinning process even at a high concentration of additives as 20 wt%. The mechanical test results showed that the combination of KL and ZnP achieved higher strength and filaments showed regularity in structure as compared to the LL and ZnP filaments. Thermogravimetric (TG) analysis showed the incorporation of lignin induces the initial decomposition (T5%) at a lower temperature; at the same time, maximum decomposition (Tmax) shifts to a higher temperature region and a higher amount of char residue is reported at the end of the test. Further, the TGA-FTIR study revealed that the ternary blends (i.e., the combination of LL or KL, ZnP, and PA11) released mainly the phosphinate compound, hydrocarbon species, and a small amount of phosphinic acid during the initial decomposition stage (T5%), while hydrocarbons, carbonyls, and phenolic compounds along with CO2 are released during main decomposition stage (Tmax). The analysis of decomposition products suggests the stronger bonds formation in the condensed phase and the obtainment of a stable char layer. Cone calorimetry exploited to study the fire behavior on sheet samples (polymer bulk) showed an improvement in flame retardant properties with increasing lignin content in blends and most enhanced results were found when 10 wt% of LL and ZnP were combined such as a reduction in heat release rate (HRR) up to 64% and total heat release (THR) up to 22%. Besides, tests carried out on knitted fabric structure showed less influence on HRR and THR but the noticeable effect on postponing the time to ignition (TTI) and reduction in the maximum average rate of heat emission (MARHE) value during combustion.

Development of Flexible and Conductive Immiscible Thermoplastic/Elastomer Monofilament for Smart Textiles Applications Using 3D Printing.

3D printing utilized as a direct deposition of conductive polymeric materials onto textiles reveals to be an attractive technique in the development of functional textiles. However, the conductive fillers-filled thermoplastic polymers commonly used in the development of functional textiles through 3D printing technology and most specifically through Fused Deposition Modeling (FDM) process-are not appropriate for textile applications as they are excessively brittle and fragile at room temperature. Indeed, a large amount of fillers is incorporated into the polymers to attain the percolation threshold increasing their viscosity and stiffness. For this reason, this study focuses on enhancing the flexibility, stress and strain at rupture and electrical conductivity of 3D-printed conductive polymer onto textiles by developing various immiscible polymer blends. A phase is composed of a conductive polymer composite (CPC) made of a carbon nanotubes (CNT) and highly structured carbon black (KB)- filled low-density polyethylene (LDPE) and another one of propylene-based elastomer (PBE) blends. Two requirements are essential to create flexible and highly conductive monofilaments for 3D-printed polymers onto textile materials applications. First, the co-continuity of both the thermoplastic and the elastomer phases and the location of the conductive fillers in the thermoplastic phase or at the interface of the two immiscible polymers are necessary to preserve the flexibility of the elastomer while decreasing the global amount of charges in the blends. In the present work based on theoretical models, when using a two-step melt process, the KB and CNT particles are found to be both preferentially located at the LDPE/PBE interface. Moreover, in the case of the two-step extrusion, SEM characterization showed that the KB particles were located in the LDPE while the CNT were mainly at the LDPE/PBE interface and TEM analysis demonstrated that KB and CNT nanoparticles were in LDPE and at the interface. For one-step extrusion, it was found that both KB and CNT are in the PBE and LDPE phases. These selective locations play a key role in extending the co-continuity of the LDPE and PBE phases over a much larger composition range. Therefore, the melt flow index and the electrical conductivity of monofilament, the deformation under compression, the strain and stress and the electrical conductivity of the 3D-printed conducting polymer composite onto textiles were significantly improved with KB and CNT-filled LDPE/PBE blends compared to KB and CNT-filled LDPE separately. The two-step extrusion processed 60%(LDPE16.7% KB + 4.2% CNT)/40 PBE blends presented the best properties and almost similar to the ones of the textile materials and henceforth, could be a better material for functional textile development through 3D printing onto textiles.

Impacts of organic matter digestion protocols on synthetic, artificial and natural raw fibers.

As microplastic studies grow, environmental concerns of all kinds of fibers are currently investigated. However, there is a gap in data regarding the impacts of digestion protocols on fibers integrity. This work focuses on the impact of five commonly used digestion protocols on the seven most produced fibers in traditional textile: three synthetics (polyamide 6.6 (PA 6.6), polyethylene terephthalate (PET) and polyacrylonitrile (acrylic)), one artificial (viscose), two vegetal natural (cotton and flax) and one animal natural (wool). The protocols to be tested were selected based on the literature: 10% KOH at 40 °C for 24 h; 10% KOH at 60 °C for 24 h; diluted NaClO at room temperature (~20 °C) for 15 h; 30% H2O2 at 40 °C for 48 h; Fenton's reagent with 30% H2O2 for 2 h at room temperature (~20 °C). The fibers were characterized before and after digestion. The effects of those protocols on fibers integrity have been assessed using several of their performance parameters. High degradations were observed for PET with 10% KOH 60 °C whereas almost no impact was observed at 40 °C. H2O2 digestion affects mechanical properties of different fibers, particularly PA 6.6. Both protocols should be avoided for synthetic fibers analyses. NaClO digestion mainly affected flax and viscose. Diluted NaClO at room temperature for 15 h, 10% KOH at 40 °C for 24 h and Fenton's reagent are more appropriate to maintain fibers integrity.

Study of the Wear Resistance of Conductive Poly Lactic Acid Monofilament 3D Printed onto Polyethylene Terephthalate Woven Materials.

Wear resistance of conductive Poly Lactic Acid monofilament 3D printed onto textiles, through Fused Deposition Modeling (FDM) process and their electrical conductivity after abrasion are important to consider in the development of smart textiles with preserved mechanical and electrical properties. The study aims at investigating the weight loss after abrasion and end point of such materials, understanding the influence of the textile properties and 3D printing process parameters and studying the impact of the abrasion process on the electrical conductivity property of the 3D printed conductive polymers onto textiles. The effects of the 3D printing process and the printing parameters on the structural properties of textiles, such as the thickness of the conductive Poly Lactic Acid (PLA) 3D printed onto polyethylene terephthalate (PET) textile and the average pore sizes of its surface are also investigated. Findings demonstrate that the textile properties, such as the pattern and the process settings, for instance, the printing bed temperature, impact significantly the abrasion resistance of 3D printed conductive Poly Lactic Acid (PLA) onto PET woven textiles. Due to the higher capacity of the surface structure and stronger fiber-to-fiber cohesion, the 3D printed conductive polymer deposited onto textiles through Fused Deposition Modeling process have a higher abrasion resistance and lower weight loss after abrasion compared to the original fabrics. After printing the mean pore size, localized at the surface of the 3D-printed PLA onto PET textiles, is five to eight times smaller than the one of the pores localized at the surface of the PET fabrics prior to 3D printing. Finally, the abrasion process did considerably impact the electrical conductivity of 3D printed conductive PLA onto PET fabric.

Selection of Immiscible Polymer Blends Filled with Carbon Nanotubes for Heating Applications.

In many application fields, such as medicine or sports, heating textiles use electrically conductive multifilaments. This multifilament can be developed from conductive polymer composites (CPC), which are blends of an insulating polymer filled with electrically conductive particles. However, this multifilament must have filler content above the percolation threshold, which leads to an increase of the viscosity and problems during the melt spinning process. Immiscible blends between two polymers (one being a CPC) can be used to allow the reduction of the global filler content if each polymer is co-continuous with a selective localization of the fillers in only one polymer. In this study, three immiscible blends were developed between polypropylene, polyethylene terephthalate, or polyamide 6 and a filled polycaprolactone with carbon nanotubes. The morphology of each blend at different ratios was studied using models of co-continuity and prediction of fillers localization according to viscosity, interfacial energy, elastic modulus, and loss factor of each polymer. This theoretical approach was compared to experimental values to find out differences between methods. The electrical properties (electrical conductivity and Joule effect) were also studied. The co-continuity, the selective localization in the polycaprolactone, and the Joule effect were only exhibited by the polypropylene/filled polycaprolactone 50/50 wt.%.

Stress, strain and deformation of poly-lactic acid filament deposited onto polyethylene terephthalate woven fabric through 3D printing process.

Although direct deposition of polymeric materials onto textiles through 3D printing is a great technique used more and more to develop smart textiles, one of the main challenges is to demonstrate equal or better mechanical resistance, durability and comfort than those of the textile substrates before deposition process. This article focuses on studying the impact of the textile properties and printing platform temperature on the tensile and deformations of non-conductive and conductive poly lactic acid (PLA) filaments deposited onto polyethylene terephthalate (PET) textiles through 3D printing process and optimizing them using theoretical and statistical models. The results demonstrate that the deposition process affects the tensile properties of the printed textile in comparison with the ones of the textiles. The stress and strain at rupture of the first 3D printed PLA layer deposited onto PET textile material reveal to be a combination of those of the printed layer and the PET fabric due to the lower flexibility and diffusion of the polymeric printed track through the textile fabric leading to a weak adhesion at the polymer/textile interface. Besides, printing platform temperature and textile properties influence the tensile and deformation properties of the 3D printed PLA on PET textile significantly. Both, the washing process and the incorporation of conductive fillers into the PLA do not affect the tensile properties of the extruded polymeric materials. The elastic, total and permanent deformations of the 3D-printed PLA on PET fabrics are lower than the ones of the fabric before polymer deposition which demonstrates a better dimensional stability, higher stiffness and lower flexibility of these materials.

Valorization of Industrial Lignin as Biobased Carbon Source in Fire Retardant System for Polyamide 11 Blends.

In this study, two different types of industrial lignin (i.e., lignosulphonate lignin (LL) and kraft lignin (DL)) were exploited as charring agents with phosphorus-based flame retardants for polyamide 11 (PA11). The effect of lignins on the thermal stability and fire behavior of PA11 combined with phosphinate additives (namely, aluminum phosphinate (AlP) and zinc phosphinate (ZnP)) has been studied by thermogravimetric analysis (TGA), UL 94 vertical flame spread, and cone calorimetry tests. Various blends of flame retarded PA11 were prepared by melt process using a twin-screw extruder. Thermogravimetric analyses showed that the LL containing ternary blends are able to provide higher thermal stability, as well as a developed char residue. The decomposition of the phosphinates led to the formation of phosphate compounds in the condensed phase, which promotes the formation of a stable char. Flammability tests showed that LL/ZnP ternary blends were able to achieve self-extinction and V-1 classification; the other formulations showed a strong melt dripping and higher burning. In addition to this, cone calorimetry results showed that the most enhanced behavior was found when 10 wt % of LL and AlP were combined, which strongly reduced PHRR (-74%) and THR (-22%), due to the interaction between LL and AlP, which not only promotes char formation but also confers the stability to char in the condensed phase.

Influence of Ammonium Polyphosphate/Lignin Ratio on Thermal and Fire Behavior of Biobased Thermoplastic: The Case of Polyamide 11.

Flame retardancy of polymers is a recurring obligation for many applications. The development trend of biobased materials is no exception to this rule, and solutions of flame retardants from agro-resources give an advantage. Lignin is produced as a waste by-product from some industries, and can be used in the intumescent formation development as a source of carbon combined with an acid source. In this study, the flame retardancy of polyamide 11 (PA) is carried out by extrusion with a kraft lignin (KL) and ammonium polyphosphate (AP). The study of the optimal ratio between the KL and the AP makes it possible to optimize the fire properties as well as to reduce the cost and facilitates the implementation of the blend by a melting process. The properties of thermal decomposition and the fire reaction have been studied by thermogravimetric analyzes, pyrolysis combustion flow calorimetry (PCFC) and vertical flame spread tests (UL94). KL permits a charring effect delaying thermal degradation and decreases by 66% the peak of heat release rate in comparison with raw PA. The fire reaction of the ternary blends is improved even if KL-AP association does not have a synergy effect. The 25/75 and 33/67 KL/AP ratios in PA give an intumescence behavior under flame exposure.

Microstructure Evolution of Immiscible PP-PVA Blends Tuned by Polymer Ratio and Silica Nanoparticles.

Composites of polypropylene (PP) and water soluble poly(vinyl alcohol) (PVA) can become an environmentally friendly precursor in preparing porous material, and their biphasic morphology needs to be manipulated. In this work, PP-PVA extrudates were prepared with a twin-screw extruder, and different PP/PVA ratios were employed to manipulate the morphology of the blends. Afterwards, different silicas were imbedded within the blends to further regulate the biphasic microstructure. PVA continuity, as a vital parameter in obtaining porous material, was determined by selective extraction measurement, and PP-PVA biphasic morphology was characterized by scanning microscopy analyses (SEM). Rheological measurement was also performed to correlate the microstructure evolution of the blends. First, it was found that with the increment of PVA proportion, PVA continuity is raised gradually, and the microstructure of blends containing 40⁻50 wt % of PVA is approaching co-continuous. Second, the localization of silicas was predicted based on the wettability of silica and polymers, and it was also confirmed by TEM that different silicas showed selective distribution. It is inspiring that R972 nanoparticles were found mainly distributed at the interface, which gives a possibility in preparing a surface-modified porous material. The shape distribution and average size of PVA nodules were examined by analyzing the SEM images. It is indicated that silicas with different wettabilities play disparate roles in tuning the biphasic microstructures, leading to heterogeneous PVA continuity.

PLA with Intumescent System Containing Lignin and Ammonium Polyphosphate for Flame Retardant Textile.

Using bio-based polymers to replace of polymers from petrochemicals in the manufacture of textile fibers is a possible way to improve sustainable development for the textile industry. Polylactic acid (PLA) is one of the available bio-based polymers. One way to improve the fire behavior of this bio-based polymer is to add an intumescent formulation mainly composed of acid and carbon sources. In order to optimize the amount of bio-based product in the final material composition, lignin from wood waste was selected as the carbon source. Different formulations of and/or ammonium polyphosphate (AP) were prepared by melt extrusion and then hot-pressed into sheets. The thermal properties (thermogravimetric analyses (TGA) and differential scanning calorimetry (DSC)) and fire properties (UL-94) were measured. The spinnability of the various composites was evaluated. The mechanical properties and physical aspect (microscopy) of PLA multifilaments with lignin (LK) were checked. A PLA multifilament with up to 10 wt % of intumescent formulation was processed, and the fire behavior of PLA fabrics with lignin/AP formulation was studied by cone calorimeter.