ABSTRACT
Biodegradable biopolymers such as polylactic acid and polybutylene succinate are sustainable alternatives to traditional petroleum-based plastics. However, the factors affecting their degradation must be characterized in detail to enable successful utilization. Here we compared the extruder dwell time at three different melt-spinning scales and its influence on the degradation of both polymers. The melt temperature was the same for all three processes, but the shear stress and dwell time were key differences, with the latter being the easiest to measure. Accelerated degradation tests, including quick weathering and disintegration, were used to evaluate the influence of dwell time on the structural, mechanical, and thermal properties of the resulting fibers. We found that longer dwell times accelerated degradation. Quick weathering by UV pre-exposure before the disintegration trial, however, had a more significant effect than dwell time, indicating that degradation studies with virgin material in a laboratory-scale setting only show the theoretical behavior of a product in the laboratory. A weathered fiber from an industrial-scale spinning line more accurately predicts the behavior of a product placed on the market before ending up in the environment. This highlights the importance of optimizing process parameters such as the dwell time to adapt the degradability of biopolymers for specific applications and environmental requirements. By gaining a deeper insight into the relationship between manufacturing processes and fiber degradability, products can be adapted to meet suitable performance criteria for different applications.
ABSTRACT
The COVID-19 pandemic led to a huge demand for disposable facemasks. Billions were manufactured from nonbiodegradable petroleum-derived polymers, and many were discarded in the environment where they contributed to plastic pollution. There is an urgent need for biobased and biodegradable facemasks to avoid environmental harm during future disease outbreaks. Melt electrospinning is a promising alternative technique for the manufacturing of filter layers using sub-microfibers prepared from biobased raw materials such as polybutylene succinate (PBS). However, it is not yet possible to produce sub-micrometer PBS fibers or uniform nonwoven-like samples at the pilot scale, which hinders their investigation as filter layers. Further optimization of pilot-scale PBS melt electrospinning is therefore required. Here, we tested the effect of different parameters such as electric field strength, nozzle-to-collector distance and throughput on the final fiber diameter and sample uniformity during PBS melt electrospinning on a pilot-scale device. We also studied the effect of a climate chamber and an additional infrared heater on the solidification of PBS fibers and their final diameter and uniformity. In addition, a post-processing step, including a hot air stream of 90 °C for 30 s has been studied and successfully lead to a nonwoven-like structure including filaments that weld together without changing their structure. The finest fibers (1.7 µm in diameter) were produced at an applied electric field strength of -40 kV, a nozzle-to-collector distance of 5.5 cm, and a spin pump speed of 2 rpm. Three uniform nonwoven-like samples were tested as filter layers in a medical face mask by measuring their ability to prevent the transfer of bacteria, but the pore size was too large for effective retention. Our results provide insight into the process parameters influencing the suitability of melt-electrospun nonwoven-like samples as biobased and biodegradable filter materials and offer guidance for further process optimization.
ABSTRACT
Manufacturers of technical polymers must increasingly consider the degradability of their products due to the growing public interest in topics such as greenhouse gas emissions and microplastic pollution. Biobased polymers are part of the solution, but they are still more expensive and less well characterized than conventional petrochemical polymers. Therefore, few biobased polymers with technical applications have reached the market. Polylactic acid (PLA) is the most widely-used industrial thermoplastic biopolymer and is mainly found in the areas of packaging and single-use products. It is classed as biodegradable but only breaks down efficiently above the glass transition temperature of ~60 °C, so it persists in the environment. Some commercially available biobased polymers can break down under normal environmental conditions, including polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT) and thermoplastic starch (TPS), but they are used far less than PLA. This article compares polypropylene, a petrochemical polymer and benchmark for technical applications, with the commercially available biobased polymers PBS, PBAT and TPS, all of which are home-compostable. The comparison considers processing (using the same spinning equipment to generate comparable data) and utilization. Draw ratios ranged from 29 to 83, with take-up speeds from 450 to 1000 m/min. PP achieved benchmark tenacities over 50 cN/tex with these settings, while PBS and PBAT achieved over 10cN/tex. By comparing the performance of biopolymers to petrochemical polymers in the same melt-spinning setting, it is easier to decide which polymer to use in a particular application. This study shows the possibility that home-compostable biopolymers are suitable for products with lower mechanical properties. Only spinning the materials on the same machine with the same settings produces comparable data. This research, therefore, fills the niche and provides comparable data. To our knowledge, this report is the first direct comparison of polypropylene and biobased polymers in the same spinning process with the same parameter settings.
ABSTRACT
The color of textile fibers is typically imparted by submersion in a high-temperature dye bath. However, the treatment of the effluent is challenging and the textile industry is therefore a major source of water pollution. Current fashion trends favor biobased polymers such as polylactic acid (PLA) but exhaust dyeing at high temperatures causes hydrolytic degradation, reducing the crystallinity and tenacity of the yarn. To preserve the mechanical properties of PLA-based textiles, an alternative to exhaust dyeing called dope dyeing can be used, wherein colorants are incorporated into the polymer matrix during melt spinning. We evaluated this process by dope dyeing PLA with several colorants, then testing the thermal, physical, and mechanical properties of the yarn and the physical properties of circular-knitted fabrics. Although the colorants affected the crystallization behavior at lower cooling rates, during the melt-spinning process, the drawing speed had a greater effect on the crystallinity and mechanical properties of the dyed yarn. Scanning electron microscopy revealed that the colorants were well dispersed in the PLA matrix. We found that the colorants did not affect the physical properties of the knitted fabric. Our results can be used to develop more environmentally beneficial dope-dyed PLA yarn with improved mechanical properties.
ABSTRACT
Melt electrospinning is a simple, versatile, and widely used technique for the production of microfibers and sub-microfibers. Polybutylene succinate (PBS) is a promising raw material for the preparation of melt-electrospun fibers at the laboratory scale. The inclusion of additives in the PBS melt can reduce the final fiber diameter, but economically feasible larger-scale processes remain challenging. The fiber diameter can also be reduced by machine optimization, although this is expensive due to the complexity of melt-electrospinning devices. Changes in electrical field polarity have provided a low-cost strategy to reduce the diameter of fibers produced by solution-electrospinning, but there is little information about the effect of this parameter on the final diameter of melt-electrospun fibers. We therefore determined the effect of field polarity on the diameter of melt-electrospun PBS fibers at the laboratory scale and investigated the transferability of these results to our 600-nozzle pilot-scale device. Changing the polarity achieved a significant reduction in fiber diameter of ~50% at the laboratory scale and ~30% at the pilot scale, resulting in a minimum average fiber diameter of 10.88 µm. Although the effect of field polarity on fiber diameter was similar at both scales, the fibers in the web stuck together at the laboratory scale but not at the pilot scale. We have developed an inexpensive method to reduce the diameter of melt-electrospun PBS fibers and our data provide insight into the transferability of melt electrospinning from the laboratory to a pilot-scale machine.
ABSTRACT
Fibers with diameters in the lower micrometer range have unique properties suitable for applications in the textile and biomedical industries. Such fibers are usually produced by solution electrospinning, but this process is environmentally harmful because it requires the use of toxic solvents. Melt electrospinning is a sustainable alternative but the high viscosity and low electrical conductivity of molten polymers produce thicker fibers. Here, we used multifunctional biobased dyes as additives to improve the spinnability of polylactic acid (PLA), improving the spinnability by reducing the electrical resistance of the melt, and incorporating antibacterial activity against Staphylococcus aureus. Spinning trials using our 600-nozzle pilot-scale melt-electrospinning device showed that the addition of dyes produced narrower fibers in the resulting fiber web, with a minimum diameter of ~9 µm for the fiber containing 3% (w/w) of curcumin. The reduction in diameter was low at lower throughputs but more significant at higher throughputs, where the diameter reduced from 46 µm to approximately 23 µm. Although all three dyes showed antibacterial activity, only the PLA melt containing 5% (w/w) curcumin retained this property in the fiber web. Our results provide the basis for the development of environmentally friendly melt-electrospinning processes for the pilot-scale manufacturing of microfibers.
ABSTRACT
The nucleating agent N,N'-bis(2-hydroxyethyl)-terephthalamide (BHET) has promising effects on poly(l-lactide) (PLA) under quiescent conditions and for injection molding applications, but its suitability for industrial-scale fiber melt spinning is unclear. We therefore determined the effects of 1% and 2% (w/w) BHET on the crystallinity, tenacity, and elongation at break of PLA fibers compared to pure PLA and PLA plus talc as a reference nucleating agent. Fibers were spun at take-up velocities of 800, 1400 and 2000 m/min and at drawing at ratios of 1.1-4.0, reaching a final winding speed of 3600 m/min. The fibers were analyzed by differential scanning calorimetry, wide-angle X-ray diffraction, gel permeation chromatography and tensile testing. Statistical analysis of variance was used to determine the combined effects of the spin-line parameters on the material properties. We found that the fiber draw ratio and take-up velocity were the most important factors affecting tenacity and elongation, but the addition of BHET reduced the mechanical performance of the fibers. The self-organizing properties of BHET were not expressed due to the rapid quenching of the fibers, leading to the formation of α'-crystals. Understanding the behavior of BHET in the PLA matrix provides information on the performance of nucleation agents during high-speed processing that will allow processing improvements in the future.
ABSTRACT
Melt electrospinning is a polymer processing technology for the manufacture of microfibers and nanofibers. Additives are required to reduce the melt viscosity and increase its conductivity in order to minimize the fiber diameter, and can also impart additional beneficial properties. We investigated the preparation of polybutylene succinate (PBS) microfibers incorporating different weight percentages of two multifunctional additives (the organic dye curcumin and inorganic silver nanoparticles) using a single-nozzle laboratory-scale device. We determined the influence of these additives on the polymer melt viscosity, electrical conductivity, degradation profile, thermal behavior, fiber diameter, and antibacterial activity. The formation of a Taylor cone followed by continuous fiber deposition was observed for compounds containing up to 3% (w/w) silver nanoparticles and up to 10% (w/w) curcumin, the latter achieving the minimum average fiber diameter of 12.57 µm. Both additives reduced the viscosity and increased the electrical conductivity of the PBS melt, and also retained their specific antibacterial properties when compounded and spun into fibers. This is the first report describing the effect of curcumin and silver nanoparticles on the properties of PBS fibers manufactured using a single-nozzle melt-electrospinning device. Our results provide the basis to develop environmentally benign antibacterial melt-electrospun PBS fibers for biomedical applications.
ABSTRACT
Textile engineering can offer a multi-scale toolbox via various fiber or textile fabrication methods to obtain woven or nonwoven aerogels with different structural and mechanical properties to overcome the current limitations of polysaccharide-based aerogels, such as poor mechanical properties and undeveloped shaping techniques. Hereby, a high viscous solution of microcrystalline cellulose and zinc chloride hydrate was wet spun to produce mono and multi-filament alcogel microfibers. Subsequently, cellulose aerogel fibers (CAF) were produced and impregnated with model drugs using supercritical CO2 processes. Fibers were characterized in terms of morphology and textural properties, thermal stability, mechanical properties, and in vitro biological and drug release assessments. Loaded and non-loaded CAFs proved to have a macro-porous outer shell and a nano-porous inner core with interconnected pore structure and a specific area in the range of 100-180 m2/g. The CAFs with larger diameter (d ~ 235 µm) were able to form knitted mesh while lower diameter fibers (d ~ 70 µm) formed needle punched nonwoven textiles. Humidity and water uptake assessments indicated that the fibrous structures were highly moisture absorbable and non-toxic with immediate drug release profiles due to the highly open interconnected porous structure of the fibers. Finally, CAFs are propitious to be further developed for biomedical applications such as drug delivery and wound care.
Subject(s)
Cellulose , Drug Delivery Systems , Drug Liberation , Gels , PorosityABSTRACT
Melt electrospinning is widely used to manufacture fibers with diameters in the low micrometer range. Such fibers are suitable for many biomedical applications, including sutures, stents and tissue engineering. We investigated the preparation of polybutylene succinate microfibers using a single-nozzle laboratory-scale device, while varying the electric field strength, process throughput, nozzle-to-collector distance and the temperature of the polymer melt. The formation of a Taylor cone followed by continuous fiber deposition was observed for all process parameters, but whipping behavior was enhanced when the electric field strength was increased from 50 to 60 kV. The narrowest fibers (30.05 µm) were produced using the following parameters: electric field strength 60 kV, melt temperature 235 °C, throughput 0.1 mL/min and nozzle-to-collector distance 10 cm. Statistical analysis confirmed that the electric field strength was the most important parameter controlling the average fiber diameter. We therefore report the first production of melt-electrospun polybutylene succinate fibers in the low micrometer range using a laboratory-scale device. This offers an economical and environmentally sustainable alternative to conventional solution electrospinning for the preparation of safe fibers in the micrometer range suitable for biomedical applications.
ABSTRACT
Clothing is one of the primary human needs, and the demand is met by the global production of thousands of tons of textile fibers, fabrics and garments every day. Polyester clothing manufactured from oil-based polyethylene terephthalate (PET) is the market leader. Conventional PET creates pollution along its entire value chain-during the production, use and end-of-life phases-and also contributes to the unsustainable depletion of resources. The consumption of PET garments thus compromises the quality of land, water and air, destroys ecosystems, and endangers human health. In this article, we discuss the different stages of the value chain for polyester clothing from the perspective of sustainability, describing current environmental challenges such as pollution from textile factory wastewater, and microfibers released from clothing during the laundry cycle. We also consider potential solutions such as enhanced reuse and recycling. Finally, we propose a series of recommendations that should be applied to polyester clothing at all stages along the value chain, offering the potential for meaningful and effective change to improve the environmental sustainability of polyester textiles on a global scale.
ABSTRACT
The demand is rising for colorants that are obtained from natural resources, tolerant to industrial processing methods, and meet color quality demands. Herein, we report how relevant properties such as thermal stability and photostability of the natural colorant alizarin can be improved by grafting it onto ZnO nanoparticles (NPs), allowing application in a warm extrusion process for the fabrication of polyamide fibers. For this study, ZnO NPs (diameter 2.0 ± 0.6 nm) were synthesized and subsequently functionalized with alizarin. The alizarin-coated ZnO NPs (i.e., dyed nanoparticles, DNPs) were characterized. Thermogravimetric analysis and ultraviolet-visible (UV-vis) studies revealed that alizarin coating accounts for â¼65% (w/w) of the total mass of the DNPs. A subsequent detailed characterization with Fourier transform infrared (FT-IR), 1H nuclear magnetic resonance (NMR), 13C cross-polarization magic angle spinning (CP-MAS) NMR, X-ray photoelectron spectroscopy (XPS), and quantum chemistry studies using various density functional theory (DFT) functionals and basis sets indicated that binding onto the ZnO NPs occurred predominantly via the catechol moiety of alizarin. Importantly, this grafting increased the thermal stability of alizarin with >100 °C, which allowed the processing of the DNPs into polyamide fibers by warm extrusion at 260 °C. Evaluation of the lightfastness of the DNP-dyed nylon fibers revealed that the changes in color quantified via the distance metric ΔE* of alizarin when embedded in a hybrid material were 2.6-fold better compared to nylon fibers that were directly dyed with alizarin. This reveals that the process of immobilization of a natural dye onto ZnO nanoparticles indeed improves the dye properties significantly and opens the way for a wide range of further studies into surface-immobilized dyes.
ABSTRACT
To improve sustainability of polymers and to reduce carbon footprint, polymers from renewable resources are given significant attention due to the developing concern over environmental protection. The renewable materials are progressively used in many technical applications instead of short-term-use products. However, among other applications, the flame retardancy of such polymers needs to be improved for technical applications due to potential fire risk and their involvement in our daily life. To overcome this potential risk, various flame retardants (FRs) compounds based on conventional and non-conventional approaches such as inorganic FRs, nitrogen-based FRs, halogenated FRs and nanofillers were synthesized. However, most of the conventional FRs are non-biodegradable and if disposed in the landfill, microorganisms in the soil or water cannot degrade them. Hence, they remain in the environment for long time and may find their way not only in the food chain but can also easily attach to any airborne particle and can travel distances and may end up in freshwater, food products, ecosystems, or even can be inhaled if they are present in the air. Furthermore, it is not a good choice to use non-biodegradable FRs in biodegradable polymers such as polylactic acid (PLA). Therefore, the goal of this review paper is to promote the use of biodegradable and bio-based compounds for flame retardants used in polymeric materials.
Subject(s)
Flame Retardants/chemical synthesis , Halogens/chemistry , Nitrogen/chemistry , Polymers/chemistry , Biodegradation, Environmental , Carbon Footprint , Flame Retardants/pharmacologyABSTRACT
Electrospinning is widely used for the manufacture of fibers in the low-micrometer to nanometer range, allowing the fabrication of flexible materials with a high surface area. A distinction is made between solution and melt electrospinning. The former produces thinner fibers but requires hazardous solvents; whereas the latter is more environmentally sustainable because solvents are not required. However, the viscous melt requires high process temperatures and its low conductivity leads to thicker fibers. Here, we describe the first use of the biobased dyes alizarin; hematoxylin and quercetin as conductive additives to reduce the diameter of polylactic acid (PLA) fibers produced by melt electrospinning; combined with a biobased plasticizer to reduce the melt viscosity. The formation of a Taylor cone followed by continuous fiber deposition was observed for all PLA compounds; reducing the fiber diameter by up to 77% compared to pure PLA. The smallest average fiber diameter of 16.04 µm was achieved by adding 2% (w/w) hematoxylin. Comparative analysis revealed that the melt-electrospun fibers had a low degree of crystallinity compared to drawn filament controls-resembling partially oriented filaments. Our results form the basis of an economical and environmentally friendly process that could ultimately, provide an alternative to industrial solution electrospinning.
ABSTRACT
The objective of this study is to examine the effect of intumescent flame-retardants (IFR's) on the spinnability of sheath/core bicomponent melt-spun fibers, produced from Polylactic acid (PLA) single polymer composites, as IFR's have not been tested in bicomponent fibers so far. Highly crystalline PLA-containing IFR's was used in the core component, while an amorphous PLA was tested in the sheath component of melt-spun bicomponent fibers. Ammonium polyphosphate and lignin powder were used as acid, and carbon source, respectively, together with PES as a plasticizing agent in the core component of bicomponent fibers. Multifilament fibers, with sheath/core configurations, were produced on a pilot-scale melt spinning machine, and the changes in fibers mechanical properties and crystallinity were recorded in response to varying process parameters. The crystallinity of the bicomponent fibers was studied by differential scanning calorimetry and thermal stabilities were analyzed by thermogravimetric analysis. Thermally bonded, non-woven fabric samples, from as prepared bicomponent fibers, were produced and their fire properties, such as limiting oxygen index and cone calorimetry values were measured. However, the ignitability of fabric samples was tested by a single-flame source test. Cone calorimetry showed a 46% decline in the heat release rate of nonwovens, produced from FR PLA bicomponent fibers, compared to pure PLA nonwovens. This indicated the development of an intumescent char by leaving a residual mass of 34% relative to the initial mass of the sample. It was found that the IFRs can be melt spun into bicomponent fibers by sheath/core configuration, and the enhanced functionality in the fibers can be achieved with suitable mechanical properties.
ABSTRACT
Sub-microfibers and nanofibers have a high surface-to-volume ratio, which makes them suitable for diverse applications including environmental remediation and filtration, energy production and storage, electronic and optical sensors, tissue engineering, and drug delivery. However, the use of such materials is limited by the low throughput of established manufacturing technologies. This short report provides an overview of current production methods for sub-microfibers and nanofibers and then introduces a new melt-electrospinning prototype based on a spinneret with 600 nozzles, thereby providing an important step towards larger-scale production. The prototype features an innovative collector that achieves the optimal spreading of the fiber due to its uneven surface, as well as a polymer inlet that ensures even polymer distribution to all nozzles. We prepared a first generation of biobased fibers with diameters ranging from 1.000 to 7.000 µm using polylactic acid and 6% (w/w) sodium stearate, but finer fibers could be produced in the future by optimizing the prototype and the composition of the raw materials. Melt electrospinning using the new prototype is a promising method for the production of high-quality sub-microfibers and nanofibers.
ABSTRACT
The objective of this study is to assess the efficiency of biobased carbonization agent in intumescent formulations (IFRs) to examine the flame retardant properties of polylactic acid (PLA) composites and to investigate their melt-spinnability. We used phosphorous-based halogen free flame retardant (FR) and kraft lignin (KL) as bio-based carbonization agent. After melt compounding and molding into sheets by hot pressing various fire related characteristics of IFR composites were inspected and were characterized by different characterization methods. It was fascinating to discover that the introduction of 5-20 wt% FR increased the limiting oxygen index (LOI) of PLA composites from 20.1% to 23.2-33.5%. The addition of KL with content of 3-5 wt% further increased the LOI up to 36.6-37.8% and also endowed PLA/FR/KL composites with improved anti-dripping properties. Cone calorimetry revealed a 50% reduction in the peak heat release rate of the IFR composites in comparison to 100% PLA and confirmed the development of an intumescent char structure containing residue up to 40%. For comparative study, IFR composites containing pentaerythritol (PER) as a carbonization agent were also prepared and their FR properties were compared. IFR composites were melt spun and mechanical properties of multifilament yarns were tested. The analysis of char residues by energy dispersive X-ray spectrometry (EDS) and SEM images confirmed that PLA/FR/KL composites developed a thicker and more homogeneous char layer with better flame retardant properties confirming that the fire properties of PLA can be enhanced by using KL as a carbonization agent.
Subject(s)
Flame Retardants/analysis , Lignin/chemistry , Polyesters/chemistry , Propylene Glycols/chemistryABSTRACT
Starch, being a polyhydric compound with its natural charring ability, is an ideal candidate to serve as a carbonization agent in an intumescent system. This charring ability of starch, if accompanied by an acidic source, can generate an effective intumescent flame retardant (IFR) system, but the performance of starch-based composites in an IFR system has not been tested in detail. Here, we describe a PLA-based IFR system consisting of ammonium polyphosphate (APP) as acidic source and cornstarch as carbon source. We prepared different formulations by melt compounding followed by molding into sheets by hot pressing. The thermal behavior and surface morphology of the composites was investigated by thermogravimetric analysis and scanning electron microscopy respectively. We also conducted limiting oxygen index (LOI), UL-94, and cone calorimetry tests to characterize the flame-retardant properties. Cone calorimetry revealed a 66% reduction in the peak heat release rate of the IFR composites compared to pure PLA and indicated the development of an intumescent structure by leaving a residual mass of 43% relative to the initial mass of the sample. A mechanism of char formation has also been discussed in detail.
ABSTRACT
The structural properties of novel melt-spun polymer optical fibers (POFs) are investigated by small-angle X-ray scattering. The amorphous PMMA POFs were subjected to a rapid cooling in a water quench right after extrusion in order to obtain a radial refractive index profile. Four fiber samples were investigated with small-angle X-ray scattering (SAXS). The resulting distance-distribution functions obtained from the respective equatorial and meridional SAXS data exhibit a real-space correlation peak indicative of periodic cross-sectional and axial variations in the scattering density contrast. Simple model calculations demonstrate how the structural information contained particularly in the equatorial distance distribution function can be interpreted. The respective results are qualitatively verified for one of the fiber samples by comparison of the model curve with the measured SAXS data. Eventually, the study confirms that the cross-sectional variation of the (scattering-) density is the main reason for the formation of radial refractive-index profiles in the POFs.
ABSTRACT
Electroconductive fibers composed of cellulose and carbon nanotubes (CNTs) were spun using aqueous alkaline/urea solution. The microstructure and physical properties of the resulting fibers were investigated by scanning electron microscopy, Raman microscopy, wide-angle X-ray diffraction, tensile tests, and electrical resistance measurements. We found that these flexible composite fibers have sufficient mechanical properties and good electrical conductivity, with volume resistivities in the range of about 230-1 Ohm cm for 2-8 wt % CNT loading. The multifunctional sensing behavior of these fibers to tensile strain, temperature, environmental humidity, and liquid water was investigated comprehensively. The results show that these novel CNT/cellulose composite fibers have impressive multifunctional sensing abilities and are promising to be used as wearable electronics and for the design of various smart materials.