Green composites fabricated from bacteria retted bast fiber and PLA for light weight vehicle components
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Biodegradable films based on poly(lactic acid) blends were obtained by cast extrusion. Their tensile and fracture behavior was investigated and the effect of the processing conditions through the extrusion rolling speed on this behavior was analyzed. In uniaxial tensile tests, all films presented completely ductile behavior exhibiting a defined yield point, strain softening after this point and a plateau before fracture. Fracture behavior was determined through quasi-static fracture tests on deeply double edge notched tensile specimens. The film obtained at the lowest rolling speed exhibited completely ductile behavior hence, the Essential Work of Fracture methodology was applied to characterize its fracture. The film processed at intermediate rolling speed, on the other hand, presented ductile fracture or ductile instability depending on the ligament length and the film obtained with the highest rolling speed exhibited a transition regime fracture. In order to compare the fracture behavior of the different films, the J-integral at maximum load J{sub max} was adopted. Differences in the films fracture behavior were correlated to the processing-induced morphology.
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Aqueous surfactant free emulsion grafting-through polymerization produced poly(methyl methacrylate) coated cellulose nanofibrils that retained microstructure and strengthened poly(lactic acid) composites.
Producing a valuable chemical product through diversion of wet wastes can simultaneously resolve the problems associated with increasing wastes and greenhouse gas emissions from conventional chemical production processes. In this work, we investigated the life-cycle greenhouse gas emissions, water, and fossil-fuel consumption for waste-derived polylactic acids (PLA) from three different waste feedstocks, namely wastewater sludge, food waste, and swine manure, using the Greenhouse Gases, Regulated Emissions, and Energy Use in Technologies (GREET) model. The decarbonization potential of replacing fossil-based resins with the waste-derived polymer was also investigated. The results show that swine manure-to-PLA pathway was the least carbon intensive (—1.4 kgCO 2 e/kg) among the three waste-to-PLA pathways on a cradle-to-grave basis, followed by the food waste case (—1.3 kgCO 2 e/kg) and then by the wastewater sludge case (0.6 kgCO 2 e/kg). In the baseline scenario, all three waste-to-PLA pathways were less carbon intensive than both fossil-based PET and HDPE on a cradle-to-grave basis: 66% (vs. PET) and 56% (vs. HDPE), 171 and 192%, 181 and 205% reduction in GHG emissions for wastewater sludge-, food waste-, and swine manure-to-PLA pathway, respectively. For all sensitivity cases investigated, the food waste- and swine manure-to-PLA pathways were significantly less carbon intensive than their fossil-counterparts. In terms of the annual decarbonization potential of replacing fossil-based PET or HDPE, the wastewater sludge- and food waste-pathway showed higher mitigation potential than the swine manure-pathway: i) 18–28 kilotons CO 2 e-reduction per year for wastewater sludge pathway; ii) 23–26 kTCO 2 e-reduction/yr for food waste pathway; and iii) about 5 kTCO 2 e-reduction/yr for swine manure pathway depending on the type of conventional resin replaced. However, given the abundant availability of the swine manure feedstocks across the United States, the decarbonization potential of swine manure-based pathway can also increase as the plant capacity or the number of plants grow.
Polylactic acid (PLA) and organosolv lignin were mixed at different ratios and extruded to obtain PLA-lignin composite filaments. PLA was replaced with lignin up to 20 wt%. Two plasticizers (polyethylene glycol (PEG) 2000 and struktol TR451) were added in varying concentrations to enhance the properties of PLA_L20 (20% lignin in PLA) composite filaments. Furthermore, the effect of lignin in PLA, and PEG, and struktol in PLA_L20 composites was investigated via tensile test, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, Fourier transform infrared spectroscopy of the filaments, and dynamic mechanical analysis of 3D printed samples. A 2 wt% PEG was able to enhance both tensile stress and elongation at maximum load of PLA_L20 composite by 19% and 35%, respectively, whereas struktol TR451 was able to improve elongation at maximum load by 24%.
Polylactic acid polymer (PLA) produced from renewable resources can be recycled at the end of life to constituent monomer, optically pure lactic acid (LA), by a combination of chemical and biological processes. Efficient application of this closed loop of LA-PLA plastics-LA can minimize accumulation of plastics waste that pollute land and oceans. Temperature-dependent hydrolysis of PLA in water to LA follows apparent first order decay kinetics after a short lag. A modified Gompertz equation can explain the overall hydrolysis process. Alkali increased the rate of hydrolysis of PLA and reduced the length of lag period compared to water alone. The stoichiometry of base added to LA released was 1.0. The highest lactic acid yield was 0.95 g g -1 of PLA. D-LA in the syrup obtained after hydrolysis of PLA-plastics was removed using an engineered Escherichia coli to produce a L-LA syrup with an optical purity ≥ 99%. Here, these results show that thermochemical hydrolysis of PLA-based plastics to LA with optimum amount of base followed by bio-based purification to L-LA is an effective method of recycling PLA-plastics for reuse.
The intrinsic brittleness of poly(lactic acid) (PLA) has hindered its widespread use in many structural applications. Various strategies have been developed to toughen PLA; however, most of the methods lead to a trade-off in strength or modulus. In this study, a chain end engineering strategy was developed to toughen PLA via an industry-friendly melt processing method. Green acids with multifunctional groups, such as 1,2,3,4-butanetetracarboxylic acid (BTCA), were used to modify PLA chain ends/tails via a melt reaction. We report a remarkable improvement in toughness (16×) was achieved by the addition of a minimal amount of BTCA (0.5%). At the same time, the toughened PLA samples maintained the tensile strength and Young’s modulus of neat PLA, suggesting a unique toughening mechanism that is different from the plasticizing effect. Other acid–based modifiers with different numbers of functional groups were also studied in this work. To understand the toughening, we propose a chain end engineering picture that can improve the toughness via a reduction in the number density of chain ends or defects of entanglement and the formation of long-branch topological structures. This study demonstrates a unique and cost-effective strategy for toughening PLA via scalable melt reaction without sacrificing other mechanical properties of PLA, potentially broadening the applications.
Treatment of vascular disease, from peripheral ischemia to coronary heart disease (CHD), is poised for transformation with the introduction of transient implants designed to “scaffold” regeneration of blood vessels and ultimately leave nothing behind. Improved materials could expand the use of these devices. Here, we examine one of the leading polymers for bioresorbable scaffolds (BRS), polylactide (PLA), as the matrix of nanocomposites with tungsten disulfide (WS 2 ) nanotubes (WSNT), which may provide mechanical reinforcement and enhance radio-opacity. We evaluate in vitro cytotoxicity using vascular cells, flow-induced crystallization and radio-opacity of PLA-WSNT nanocomposites at low WSNT concentration. A small amount of WSNT (0.1 wt%) can effectively promote oriented crystallization of PLA without compromising molecular weight. And radio-opacity improves significantly: as little as 0.5 to 1 wt% WSNT doubles the radio-opacity of PLA-WSNT relative to PLA at 17 keV. The results suggest that a single component, WSNT, has the potential to increase the strength of BRS to enable thinner devices and increase radio-opacity to improve intraoperative visualization. Here, the in vitro toxicity results indicate that PLA-WSNT nanocomposites are worthy of investigation in vivo. Although substantial further preclinical studies are needed, PLA-WSNT nanocomposites may provide a complement of material properties that may improve BRS and expand the range of lesions that can be treated using transient implants.
Stable and efficient X-ray scintillators are crucial for medical diagnostics, industrial, and defense applications. However, conventional scintillator technologies face a trade-off between stability, optimal performance, and sustainability. Herein, we introduce 3D-printed Cs 4 MnBi 2 Cl 12 (Pero1) and Cs 4 Cd 0.68 Mn 0.32 Bi 2 Cl 12 (Pero2) perovskite microcrystals embedded within a polylactic acid (PLA) polymer composite as X-ray scintillators, combining efficiency, stability, and sustainability. The orange luminescent perovskite powder phosphors exhibited poor water stability, which was successfully addressed through incorporation into PLA via filament extrusion and fused deposition modeling (FDM) 3D printing. The resulting composite films demonstrated remarkable water stability while maintaining uniform orange emission throughout the polymer matrix, as confirmed by 3D topography scanning and X-ray fluorescence mapping. Structural characterization revealed minimal chemical interaction between the perovskite and PLA matrix, with the composites retaining their crystalline properties. The PLA-Pero2 composite exhibited superior optical properties, with a photoluminescence quantum yield of 47%, nearly 17 times higher than that of PLA-Pero1 (2.8%), attributed to the effective suppression of non-radiative decay pathways through Cd 2+ doping. Under hard X-ray irradiation at synchrotron beamlines, both composites exhibited excellent radioluminescence, with emission peaks at 605 nm, a linear response across a wide X-ray flux range, and remarkable radiation stability, showing less than 3% intensity degradation after 600 seconds of continuous high-dose exposure. The PLA-Pero2 composite achieved a spatial resolution of 5 line pairs per millimeter and a contrast ratio of 0.255. These performance metrics, combined with the polymer's biodegradability and scalability through additive manufacturing, position PLA-based composites as a more sustainable alternative to conventional petroleum-based polymer scintillators for next-generation medical imaging, radiation monitoring, and industrial radiography applications.
Poly (lactic) acid (PLA) based nanocomposites reinforced with starch nanocrystals (SNC) extracted from high amylopectin waxy maize starch and acetylated starch nanocrystals (Ac-SNC), were prepared and their influence on the overall properties of PLA nanocomposites were studied. The two nanofillers (SNC and Ac-SNC) were incorporated in PLA at two different loadings (1 and 3 wt%) by solvent casting and evaporation technique. Surface acetylation of SNC was confirmed by Fourier Transform infra-red spectroscopy and nuclear magnetic resonance spectroscopy and the crystalline structure by X-ray diffraction. This paper reports the influence of incorporating unacetylated and surface acetylated starch nanocrystals on morphological, barrier, mechanical, and rheological properties of PLA based nanocomposites. While both nanofillers improved the properties of PLA, the PLA-Ac-SNC had superior properties to that of PLA-SNC nanocomposites, due to better filler dispersion and interaction with the polymer matrix. These sustainable nanocomposites with improved properties will expand the application of these bio-sourced starch nanocrystals. Graphical Abstract: .
Cellulose nanofibrils (CNFs) have been widely used as a nanofiller for polymer composite reinforcement due to their excellent mechanical properties. However, CNF is produced in water and needs to be dried prior to use in composite materials. The presence of hydroxyl groups on the surface of CNF creates strong hydrogen bonding that makes it difficult and costly to dry. Additionally, the hydrophilicity at the fiber surface results in agglomeration of CNFs within many polymer matrices. In this study, chitosan (CS) was co-precipitated with CNF to produce a dual-bonding filler for use in poly (lactic acid) (PLA) composites. CS promotes improved interfacial interaction within the polymer matrix by forming strong hydrogen bonds with the CNF and potential covalent bonds with the PLA. Finally, the results confirmed that the addition of a small amount of CS significantly improved the mechanical properties compared to PLA + CNF composites and neat PLA. The detailed study of the PLA + CNF/CS composites reveals the synergetic effect of the hydrogen and covalent bonding mechanism for PLA reinforcement.
Engineering of ductile, tough and thermal resistant PLA-based materials requires blending of PLA with other constituents by reactive twin-screw co-rotating extrusion to achieve compounds with adequate thermo-mechanical properties. Then, the compound of the polymeric blends must be melt processed to the final shape with an additional technology, namely the injection molding. The two-stage process the polymeric blends must undergo and the different rheological properties the blends must feature to be suitable to the different processing steps make extremely difficult to engineer the material. Extrusion compounding requires high viscous materials low melt flow index (MFI), while injection molding requires materials with low viscosity (high MFI). To overcome these shortcomings, this manuscript deals with the design of novel biodegradable PLA-based blends that rely on mixing PLA grades with different MFI (i.e. very low for extrusion and high for injection molding), each chosen to feature the rheological characteristics needed for each step of the two-stage transformation process. The ratio of the two PLA-grades inside the blends was the matter of the present investigation. The blends were subsequently tested for the manufacturing of single-use biodegradable and thermal resistant injection molded small cups, specifically designed for brewing of hot beverages. Lastly, the thermo-mechanical performance of the as-is and annealed cups were studied. Experimental evidences show blending of two-different grades of PLA is a promising route to formulate low impact polymeric materials suitable for demanding packaging solutions.
Biobased reinforcements for poly(lactic acid) (PLA) are needed for more additive manufacturing applications requiring higher strength and sustainability. Flax nanofibrils (FNFs) produced through mechanical refining were explored as a lower energy alternative to cellulose nanofibril (CNF) reinforcements. To compatibilize the FNFs for the PLA matrix, a grafting-through surfactant free emulsion polymerization (SFEP) was performed to functionalize the FNF surface with poly(methyl methacrylate) (PMMA). FNFs produced using different refining energy were functionalized under varying solid contents in suspension. Polymerizations performed at 0.7 wt% FNFs in water yielded the highest degree of PMMA functionality. These optimal conditions were scaled up and the PMMA modified FNFs melt compounded into PLA yielding a 12% increase in tensile strength and 92% increase in the modulus of elasticity as compared to the original PLA. Interestingly, the FNFs with the lowest refining energy yielded the strongest composites using these methods, surpassing the higher refining energy CNF reinforcements. This increase was attributed to improved dispersion of the FNF reinforcements in the PLA matrix that was enabled by the PMMA coating on the FNF surface preventing interfibrillar adhesion and aggregation within the PLA matrix.
The push for sustainability in all facets of manufacturing has led to an increased interest in biomass as an alternative to non-renewable materials. Hemp bast fiber mats were produced from a bacterial retting process, named BFM, as the fiber reinforcement. The objective of this study was to evaluate the feasibility of laminating BFM with polylactic acid (PLA) for a composite panel product. Since both BFM and PLA are biodegradable, the resulting BFM-PLA composites will be 100% biodegradable. PLA pallets were processed into thin polymer sheets which served as the matrix. The BFM and PLA plates were laminated in five layers and compression-molded into composite panels. Experiments were conducted on the three BFM-to-PLA ratios (35/65, 45/55, and 50/50). Mechanical properties (tensile and bending properties) and physical properties (thickness swell and water absorption) were tested and compared to the currently commercial sheet molding compound (SMC) from fiber glass. The thermal behavior of the BFM/PLA composites was characterized using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The developed BFM/PLA composite product is a sustainable alternative to existing synthetical fiber-reinforced polymer (FRP) that is biodegradable in landfill at the end of life.
When humans ascend to high altitude (ALT) their plasma volume (PV) and total blood volume (BV) decrease during the first few days. With continued residence over several weeks, the hypoxia-induced stimulation of erythropoietin increases red cell production which tends to restore BV. Because hypoxia also activates the beta-adrenergic system, which stimulates red blood cell production, we investigated the effect of adrenergic beta-receptor inhibition with propranolol on fluid volumes and the polycythemic response in 11 healthy unacclimatized men (21-33 years old exposed to an ALT of 4300 m (barometric pressure 460 Torr) for 3 weeks on Pikes Peak, Colorado. PV was determined by the Evans blue dye method (PV(sub EB)), BV by the carbon monoxide method (BV(sub CO)), red cell volume (RCV)was calculated from hematocrit (Hct) and BV(sub CO), and serum erythropoietin concentration ([EPO]) and reticulocyte count, were also determined. All determinations were made at sea level and after 9-11 (ALT-10) and 9-20 (ALT-20) days at ALT. At sea level and ALT, six men received propranolol (pro, 240 mg/day), and five received a placebo (pla). Effective beta-blockade did not modify the mean (SE) maximal values of [EPO] [pla: 24.9 (3.5) vs pro: 24.5 (1.5) mU/ml] or reticulocyte count [pla: 2.7 (0.7) vs pro: 2.2 (0.5)%]; nor changes in PV(sub EB)[pla: -15.8 (3.8) vs pro: -19.9 (2.8)%], RCV(sub CO) [pla: +7.0 (6.7) vs pro: +10.1 (6.1)%], or BV(sub CO) [pla: -7.3 (2.3) vs pro: -7.1 (3.9)%]. In the absence of weight loss, a redistribution of body water with no net loss is implied. Hence, activation of the beta-adrenergic system did not appear to affect the hypovolemic or polycythemic responses that occurred during 3 weeks at 4300 m ALT in these subjects.
Through KSC IRTD funding in 2022, this project brought a list of 18, 3D printed filaments into formal characterization testing to provide a reference for their behaviors under relevant applications. The project format set up a series of tests to expose 3D printed specimens. A total of 1,989 individual 3D printed test specimens were sent across KSC to be scrutinized by three laboratories to fulfill a multidisciplinary assessment of each material TRL. Testing started with 18 materials. Initially, seed germination assays in the PPA, sample materials were enclosed in petri dishes with lettuce seeds on damp germination paper. No significant impacts on lettuce seed germination were observed in this testing. Next, sample coupons were printed and sent for materials testing to the KSC Analysis/Mechanical and Environmental Testing Laboratory, where they were subjected to 14- and 30-day soak periods in solutions used to provide nutrients to plants or to sanitize hardware before and after use. Following a long soak typical of a 30-day plant growout in Hoagland’s solution, 14 materials gained more than 10% of their own mass. This indicated an increased potential for leaching or providing conditions that are not food safe. Materials that exceeded 15% absorption by mass were eliminated from further testing. Based off this result, the team continued with a core list of nine filaments to fulfill Tensile, Flexural, Biofilm formation, and plant growth testing. Those materials were PLA (Raise3D), ABS (Raise3D), PETG (PolyethyleneTerephthalate Glycol) (Raise3D), ASA (Acrylonitrile Styrene Acrylate) (Raise3D), PC (Polycarbonate) (Raise3D), TPU (Thermoplastic polyurethane)-95 (Raise3D), PLA Copper (Gizmodorks), PP (Polypropylene) (Braskem), and HIPS (High Impact Polystyrene) (Gizmodorks). Testing also quantified the spectral impact of using different color 3D printed surfaces in a growth chamber. The material used for spectral testing was PLA. Printing employed a standard surface texture representative of all materials. It was shown through Tensile Testing (ASTM D638-22) that the breaking force of a 3D printed part greatly varied depending on layer orientation. This is common through all materials, and demonstrates that the strength of a 3D printed component can be maximized by layering the material normal to the primary force on the part. Four-point flexural testing (ASTM D790) provided quantities of interest, Flexural modulus, Flexural strength, Flexural stress, and strain at break within a 5% strain limit from each of nine materials. Biofilm formation testing was conducted in the Molecular and Microbiological Laboratory. Testing completed on specimens from each material showed equal formation on the surface. Additional plant growth testing was conducted in the PPA beyond the initial germination testing. The final assessment documents that three materials (PLA, ABS, and PC) have reached TRL 6 through extensive testing, and ultimate end-to-end applied use in experimental or testing conditions (flight and ground). TRL 5 materials (ASA, TPU-95, PLA Copper, PP, PETG, and HIPS) have all been successfully applied in Research and Development for crop growth applications and are ready to be applied in formal testing. TRL 4 materials Nylon910, PLA Carbon Fiber, PPA CF, PPA Glass Fiber (GF), NinjaFlex, and P-filament 721 are materials that were able to be printed and tested, but have yet to show data meeting applied requirements. TRL 3 NylonX, Flex TPE-185, and Nylon were unable to be reliably printed to fulfill testing. These results provide researchers with reference for materials to use during plant growth experimentation, and also set a standard for future characterization work applying 3D printing and materials to testing, research, and experimentation.
In Fused Filament Fabrication (FFF) 3D printing a part is made by extruding material layer by layer. Benefits of FFF are the ability to print complex shapes quickly and at a lower cost compared to other manufacturing methods. In this work, filaments composed of either silicon carbide (SiC) or zirconium silicate ceramic particulates in a polylactic-acid (PLA) matrix were used to print specimens for microstructural analysis and mechanical testing. Pure PLA samples were also printed and tested as a baseline for comparison. A Design of Experiments approach was used to test the interactions between three different parameters and their effect on ultimate strength, Young’s modulus, and yield strength. For compression test specimens, these parameters were infill percentage, number of shells, and print orientation angle. For tensile test specimens, the parameters were layer height, number of shells, and infill orientation angle. Pre- and post-compression test samples were evaluated by scanning electron microscopy for microstructural analysis. Infill percentage had the greatest effect on mechanical properties while number of shells and print orientation angle had minor effects. When changing the layer lines from perpendicular to parallel, relative to the loading direction, SiC-PLA had higher mechanical properties while pure PLA properties had decreased, and zirconium silicate-PLA had mix results.