A Comparison of Laboratory and Industrial Processes Reveals the Effect of Dwell Time and UV Pre-Exposure on the Behavior of Two Polymers in a Disintegration Trial.

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.

Performance Spectrum of Home-Compostable Biopolymer Fibers Compared to a Petrochemical Alternative.

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.

Pilot-Scale Melt Electrospinning of Polybutylene Succinate Fiber Mats for a Biobased and Biodegradable Face Mask.

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.

The Effect of Electrical Polarity on the Diameter of Biobased Polybutylene Succinate Fibers during Melt Electrospinning.

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.

Effect of Colorants and Process Parameters on the Properties of Dope-Dyed Polylactic Acid Multifilament Yarns.

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.

Pilot-Scale Electrospinning of PLA Using Biobased Dyes as Multifunctional Additives.

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.

Curcumin and Silver Doping Enhance the Spinnability and Antibacterial Activity of Melt-Electrospun Polybutylene Succinate Fibers.

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.

Detailed Process Analysis of Biobased Polybutylene Succinate Microfibers Produced by Laboratory-Scale Melt Electrospinning.

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.