Mechanical Recycling of PLA Filled with a High Level of Cellulose Fibres

Composites consisting of 30 vol% PLA and 70 vol% cellulose fibres were prepared with compression moulding. In the first part of the study, the recyclability of this composite material was investigated by grinding the material and using the recyclate obtained as a filler for PLA. Thus, the recyclate was compounded with PLA in loadings ranging from 20 to 50 wt%. The composites obtained were characterised by tensile tests, Charpy impact tests, DMTA, and SEM. Tests showed that the recyclate had a relatively good reinforcing effect. Stress at break increased from about 50 to 77 MPa and the modulus increased from 3.6 to 8.5 GPa. In the second part of the study, the ability to mechanically recycle the composites obtained was evaluated by repeated processing. Composite with two loadings of the recyclate (20 wt% and 50 %) was injection moulded repeatedly, six times. Tests showed that the composite material with 20 wt% recyclate could withstand six cycles relatively well, while the composite with the higher load degraded much more quickly. For the composites with 50 wt% recyclate, signs of polymer degradation could be seen already after reprocessing the composite once.     

Kinetic Study of Biopolymer (PHB) Synthesis in <Emphasis Type="Italic">Alcaligenes</Emphasis> sp. in Submerged Fermentation Process Using TEM

Poly-β-hydroxybuyrate (PHB) is a carbon—energy storage material which is accumulated as intracellular granule in variety of microorganism under nutrient starved conditions. Solid PHB is a biodegradable thermoplastic polymer and is utilizable in various ways similar to many conventional plastics. Ralstonia eutropha (Alcaligenes sp.), a gram negative bacteria accumulates PHB as insoluble granules inside the cells when nutrients other than carbon are limited. In this report effort has been made to analyze PHB granule synthesis inside Alcaligenes sp. NCIM 5085 by transmission electron microscopy and qualitative estimation of PHB was carried out by fourier transform infrared spectroscopy which provide better precision compared to other conventional techniques previously applied for PHB determination. Maximum PHB concentration of 2.20 ± 0.40 g/L and cell biomass of 3.42 ± 0.20 g/L was obtained after 48.0 h of fermentation. Leudking-Piret equation deduced mixed growth associated product formation which varies from earlier reports.     

Comparison of Polylactic Acid/Kenaf and Polylactic Acid/Rise Husk Composites: The Influence of the Natural Fibers on the Mechanical, Thermal and Biodegradability Properties

This paper investigates and compares the performances of polylactic acid (PLA)/kenaf (PLA-K) and PLA/rice husk (PLA-RH) composites in terms of biodegradability, mechanical and thermal properties. Composites with natural fiber weight content of 20% with fiber sizes of less than 100 μm were produced for testing and characterization. A twin-screw extrusion was used to compound PLA and natural fibers, and extruded composites were injection molded to test samples. Flexural and Izod impact test, TGA, soil burial test and SEM were used to investigate properties. All results were compared to a pure PLA matrix sample. The flexural modulus of the PLA increased with the addition of natural fibers, while the flexural strength decreased. The highest impact strength (34 J m⁻¹), flexural modulus (4.5 GPa) and flexural strength (90 MPa) were obtained for the composite made of PLA/kenaf (PLA-K), which means kenaf natural fibers are potential to be used as an alternative filler to enhance mechanical properties. On the other hand PLA-RH composite exhibits lower mechanical properties. The impact strength of PLA has decreased when filled with natural fibers; this decrease is more pronounced in the PLA-RH composite. In terms of thermal stability it has been found that the addition of natural fibers decreased the thermal stability of virgin PLA and the decrement was more prominent in the PLA-RH composite. Biodegradability of the composites slightly increased and reached 1.2 and 0.8% for PLA-K and PLA-RH respectively for a period of 90 days. SEM micrographs showed poor interfacial between the polymer matrix and natural fibers.     

A Novel Affinity Chromatographic Material for the Purification of Extracellular Polyhydroxybutyrate Depolymerases

A novel affinity chromatographic material, which is composed of silica matrix, coated with polyhydroxybutyrate (PHB) powder, suitable for the purification of PHB depolymerases, was developed. The surface morphology of the PHB-silica coated particles (silica-PHB composite particles) was examined by scanning electron microscopy and revealed a successful uniform coating of silica particles with PHB. Moreover, the complex of these materials retained its homogeneity even after incubation at 80 °C for 6 h, whereas the strong binding of PHB on silica surface was further verified by thermal gravimetric analysis and by PHB extraction- from silica surface- experiments. This novel material was demonstrated to be suitable for both, the one-step on-batch and on-column purification of Thermus thermophilus extracellular PHB depolymerase. The enzyme exhibited higher affinity against the composite of silica-PHB particles than PHB powder, since the one-step purification-fold and the overall recovery of the enzyme were 2.8 and 4 times higher respectively, in the first case. Reusability of the silica-PHB composites particles was examined by determining the recoveries of PHB depolymerase. The enzyme recoveries were ranged from 30 to 35% for the first five uses, whereas for further uses recoveries gradually dropped to 15–18% indicating that the particles could be used repeatedly for five times. This material could be also a suitable support for lipases or other proteins that exhibit strong affinity to hydrophobic materials.     

A Processing,Characterization and Marine Biodegradation Study of Melt-Extruded Polyhydroxyalkanoate (PHA) Films

A series of polyhydroxyalkanoates (PHA), all containing 1% nucleating agent but varying in structure, were melt-processed into films through single screw extrusion techniques. This series consisted of three polyhydroxybutyrate (PHB) and three polyhydroxybutyrate-valerate (PHBV) resins with varying valerate content. Processing parameters of temperature in the barrel (165–173 °C) and chill rolls (60 °C) were optimized to obtain cast films. The gel-permeation chromatography (GPC) results showed a loss of 8–19% of the polymer’s initial molecular weight due to extrusion processing. Modulated differential scanning calorimetry (MDSC) displayed glass transition temperatures of the films ranging from −4.6 to 6.7 °C depending on the amount of crystallinity in the film. DSC data were also used to calculate the percent crystallinity of each sample and slightly higher crystallinity was observed in the PHBV series of samples. X-ray diffraction patterns did not vary significantly for any of the samples and crystallinity was confirmed with X-ray data. Dynamic mechanical analysis (DMA) verified the glass transition trends for the films from DSC while loss modulus (E′) reported at 20 °C showed that the PHBV (3,950–3,600 MPa) had the higher E′ values than the PHB (3,500–2,698 MPa) samples. The Young’s modulus values of the PHB and PHBV samples ranged from 700 to 900 MPa and 900 to 1,500 MPa, respectively. Polarized light microscopy images revealed gel particles in the films processed through single-screw extrusion, which may have caused diminished Young’s modulus and tensile strength of these films. The PHBV film samples exhibited the greatest barrier properties to oxygen and water vapor when compared to the PHB film samples. The average oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) for the PHBV samples was 247 (cc-mil/m²-day) and 118 (g-mil/m²-day), respectively; while the average OTR and WVTR for the PHB samples was 350 (cc-mil/m²-day) and 178 (g-mil/m²-day), respectively. Biodegradation data of the films in the marine environment demonstrated that all PHA film samples achieved a minimum of 70% mineralization in 40 days when run in accordance with ASTM 6691. For static and dynamic incubation experiments in seawater, microbial action resulting in weight loss as a function of time showed all samples to be highly biodegradable and correlated with the ASTM 6691 biodegradation data.     

Degradation Kinetics of Biodegradable Fiber Composites

In a composite, fast degradable fibers determine the degradation of the slowly degradable matrix. Such biodegradable composites consisting of degummed hemp fibers and a polyester amide matrix were produced with fiber mass fractions between 0 and 0.48. The hot-pressed plates, 1-mm thick, were incubated in a standard soil. The degradation kinetics was quantified by the measurement of CO₂ production. Furthermore, after termination of experiment, the carbon balance was uncovered. The results were fitted to an exponential law taking into account the degradation of fibers. The increased amount of pores realized by high fiber contents induces pronounced degradation. The degradation is fully characterized by the time constant , which is correlated to the fiber mass fraction. The model allows to predict the degradation kinetics of composites with a few well-defined experiments.     

High compressive strength of home waste and polyvinyl acetate composites containing silica nanoparticle filler

Simple mixing and hot pressing methods were used to make composites from home waste—in particular, paper and dry leaves—using polyvinyl acetate (PVAc) as an adhesive and silica nanoparticles as filler. The optimum composition for the strongest composites, in terms of compressive strength, had a mass ratio of silica nanoparticles/PVAc/(paper + dry leaves) of 3:80:280. With this mass ratio, a compressive strength of 68.50 MPa was obtained for samples prepared at a pressing temperature of 150°C, pressing pressure of 100 MPa, and pressing time of 20 min. The addition of silica nanoparticles increased the compressive strength by about 50%, compared with composites made without the addition of nanosilica (45.60 MPa). Higher compressive strength was obtained at a higher pressing pressure. At a pressing pressure of 120 MPa, pressing temperature of 150°C, and pressing time of 20 min, a compressive strength of 69.10 MPa was obtained. When the pressing time was increased to 45 min at a pressing pressure of 120 MPa, a compressive strength of 84.37 MPa was measured. A model was also proposed to explain the effects of pressing pressure and pressing time on compressive strength. The model predictions were in good agreement with the experimental data.     

Purification and Properties of a Poly (β-hydroxybutyrate) Depolymerase From Penicillium sp.

An extracellular poly (β-hydroxybutyrate) (PHB) depolymerase was purified from a Penicillium sp. DS9701-09a by centrifugation, ultrafiltration, precipitation and gel filtration chromatography. The specific activity of the purified enzyme was 37.9-folds higher than that of the culture supernatant and the recovery yield was 11.8%. The PHB deploymerase molecular mass was 44.8 kDa from analysis of both Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and Matrix-assisted laser desorption-time-of-flight (MALDI-TOF) mass spectrometer. The isoelectric point of 6.7 for the enzyme was determined by a two-dimensional electrophoresis. The optimum enzyme activity was observed at a temperature of 50 °C and pH 5.0. The apparent K _m of the enzyme was found to be 1.35 mg/mL. The PHB depolymerase consisted of 16 kinds of normal amino acids. The secondary structure of the enzyme was determined by CD spectrum. α-helix and β-turn were found to be 66% and 34% for the enzyme without ammonium sulphite. Chemical inhibition on the PHB depolymerase activity was examined and EDTA was found to have a significantly inhibitory effect.     

Compatibilization Improves Performance of Biodegradable Biopolymer Composites Without Affecting UV Weathering Characteristics

With growing interest in the use of eco-friendly composite materials, biodegradable polymers and composites from renewable resources are gaining popularity for use in commercial applications. However, the long-term performance of these composites and the effect of compatibilization on their weathering characteristics are unknown. In this study, five types of biodegradable biopolymer/wood fiber (WF) composites were compatibilized with maleic anhydride (MA), and the effect of accelerated UV weathering on their performance was evaluated against composites without MA and neat biopolymers. The composite samples were prepared with 30 wt% wood fiber and one of the five biodegradable biobased polymer: poly(lactic) acid (PLA), polyhydroxybutyrate (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), Bioflex (PLA blend), or Solanyl (starch based). Neat and composite samples were UV weathered for 2000 h (hours), and characterized for morphological, physical, thermal, and mechanical properties before and after weathering. Compared to composites without MA, composites containing MA grafted polymers exhibited improved properties due to increased interfacial adhesion between the fiber and matrix. Upon accelerated weathering, thermal and mechanical properties of 70% of the samples substantially decreased. Surfaces of all the samples were roughened, and drastic color changes were observed. Water absorption of all the samples increased after weathering exposure. Even though the compatibilization is shown to improve composite properties before weathering, it did not affect weathering of samples, as there were no considerable differences in properties exhibited by the composites with MA and without MA after weathering. The results suggest that compatibilization improves properties of biodegradable biobased composites without affecting its UV degradation properties.     

Mechanical Properties of Poly (Lactic Acid)/Hemp Fiber Composites Prepared with a Novel Method

This research dealt with a novel method of fabricating green composites with biodegradable poly (lactic acid) (PLA) and natural hemp fiber. The new preparation method was that hemp fibers were firstly blending-spun with a small amount of PLA fibers to form compound fiber pellets, and then the traditional twin-screw extruding and injection-molding method were applied for preparing the composites containing 10–40 wt% hemp fibers with PLA pellets and compound fiber pellets. This method was very effective to control the feeding and dispersing of fibers uniformly in the matrix thus much powerful for improving the mechanical properties. The tensile strength and modulus were improved by 39 and 92 %, respectively without a significant decrease in elongation at break, and the corresponding flexural strength and modulus of composites were also improved by 62 and 90 %, respectively, when the hemp fiber content was 40 wt%. The impact strength of composite with 20 wt% hemp fiber was improved nearly 68 % compared with the neat PLA. The application of the silane coupling agent promoted further the mechanical properties of composites attributed to the improvement of interaction between fiber and resin matrix.     

PHB/V in Extrusion Coating of Paper and Paperboard: Part I: Study of Functional Properties

Extrusion-coating experiments were carried out in the pilot line at Tampere Univesity of Technology (Institute of Paper Converting). Typical paper and paperboard substrates were coated with commercially produced 3-hydroxybutyrate/3-hydroxyvalerate. The resulting physical properties of extrusion-coated composite structures were studied. Adhesion between PHB/V and a fiber-based substrate was rather poor, regardless of typically used pretreatments (corona and flame). On the other hand, adhesion was sufficient (mode of failure was fiber tear as the materials were separated) when the substrate was primed with an acrylic-based primer. The surface energy and polarity of PHB/V were much higher than the respective ones of LDPE. Curling of PHB/V was reduced by the addition of wax or tall oil rosin into the base polymer.     

Aromatic/Aliphatic Polyester Blends

Blends of poly(3-hydroxybutyrate) (PHB) and poly(ethylene terephthalate-co-1,4-cyclohexenedimethanol terephthalate) (PETG) were prepared in a batch mixer and in a twin screw extruder and characterized by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), field emission scanning electron microscopy (FE SEM), flexural tests, biodegradation tests in soil compost and in an enzymatic medium. The torque data showed that the addition of PETG to PHB improved its processability. DSC, DMA and FE SEM showed that the polymers are immiscible with morphology dependent on the processing conditions. A fine dispersion of PETG in the PHB matrix was observed for extruded and injection molded blends. Flexural modulus for blends was higher for blends in comparison with PHB, while the impact resistance of blends containing 20 wt% and 30 wt% of PETG is comparable to the value for PHB. PHB is biodegradable, while PETG did not degrade either in simulated soil or in the α-amylase medium. On the other hand, the PHB phase of the blends degrades under these aging conditions. Thus, the addition of PETG to PHB results in advantage such as improving of processability and Young′s modulus without significant changes in the impact resistance while keeping the biodegradability of PHB.     

End-Of-Life Textiles as Reinforcements in Biocomposites

A number of attempts have been made to recycle cotton/polyester blend woven fabrics after use; however, most of these fabrics are disposed of in landfills. Major part of these blend fabrics are not recycled due to complexity of the fibre arrangement and cannot be separated economically. This study shows that these discarded woven fabrics could be directly used as reinforcements in composites without fibre separation. Uniform alignment in the woven fabric provided consistent properties to the composites. The fabrics were reinforced by soybean-based-bioresins to produce biocomposites. The composites were analysed for mechanical, thermal, viscoelastic and morphological properties. Porosity and wettability of the composites were also evaluated. Results demonstrate that the tensile strength and modulus of over 100 and 10 MPa, respectively, can be obtained without any fibre treatment. Furthermore, impact strength over 70 kJ/m² was obtained without any chemical treatment on fibres. The porosity of the composites produced was less than 9 vol%. Additionally, the fabrics were treated with alkali in order to improve the fibre–matrix interface and the composite properties were studied. From the economical perspective, these composites can be produced at a low cost as the major component is available for free or low cost.     

Cellulose Fiber/Bentonite Clay/Biodegradable Thermoplastic Composites

Adding cellulose fiber reinforcement can improve mechanical properties of biodegradable plastics, but fiber must be well dispersed to achieve any benefit. The approach to dispersing fiber in this study was to use aqueous gels of sodium bentonite clay. These clay-fiber gels were combined with powdered compostable thermoplastics and calcium carbonate filler. The composite was dried, twin-screw extruded, and injection molded to make thin parts for tensile testing. An experimental design was used to determine the effect of fiber concentration, fiber length, and clay concentration. Polybutylene adipate/terephthalate copolymer (PBAT) and 70/30 polylactic acid (PLA)/PBAT blend were the biodegradable plastics studied. The composite strength decreased compared to the thermoplastics (13 vs. 19 MPa for PBAT, 27 vs. 38 MPa for the PLA/PBAT blend). The composite elongation to break decreased compared to the thermoplastics (170% vs. 831% for PBAT, 4.9% vs. 8.7% for the PLA/PBAT blend). The modulus increased for the composites compared to the thermoplastic standards (149 vs. 61 MPa for PBAT, 1328 vs. 965 MPa for the PLA/PBAT blend). All composite samples had good water resistance.     

Biodegradability of Thermally Aged PHB,PHB-V,and PCL in Soil Compostage

The biodegradability of poly--hydroxybutyrate (PHB), poly--hydroxybutyrate-co-valerate (PHB-V) and poly--caprolactone (PCL) were examined following thermal aging in an oven for 192, 425 and 600 h. Different temperatures, 100, 120 and 140°C for PHB and PHB-V and 30, 40 and 50^oC for PCL were used to assess the influence of this parameter on biodegradation. The biodegradability tests were done in soil compostage at pH 11.0 and involved measuring the residual mass of polymer. Thermal analysis of the polymers was done using a differential scanning calorimeter (DSC). The melting temperature and crystallinity were also determined. Thermal ageing increased the biodegradability only for PHB at 120 and 140^oC, and there was no correlation between crystallinity and the biodegradation of the polymers.     

Characterization of oily sludge from a wastewater treatment plant flocculation-flotation unit in a petroleum refinery and its treatment implications

Partly due to the complex and variable composition of oily sludge generated by the petroleum industry, cost-effective treatment and proper disposal pose considerable challenges worldwide. In this study, an extended component-based analysis of the oily sludge from a flocculation-flotation unit of a wastewater treatment system in a refinery in Sweden was carried out over 1 year. The heterogeneity of the oily sludge is illustrated by the wide ranges of concentrations found for different chemical components, particularly metals. Among the petroleum hydrocarbons, the most abundant compounds were nonpolar aliphatic hydrocarbons (63.7 ± 16.7 g kg⁻¹); from the benzene, toluene, ethylbenzene, and xylene group, xylenes (91–240 mg kg⁻¹) were most abundant; and among polycyclic aromatic hydrocarbons, naphthalene (25.7 ± 21.4), fluorene (27.25 ± 10.0), and phenanthrene (43.8 ± 18.4 mg kg⁻¹) were most abundant (all results in terms of dry matter). Based on the EU guidelines and the mean concentration values for metals found in the oily sludge, e.g., Pb (135.4 ± 125.8), Cu (105.2 ± 79.1), Hg (42.8 ± 31.3), Ni (320 ± 267.4), and Zn (1321.7 ± 529.9 mg kg⁻¹), disposal of oily sludge even in landfills for hazardous waste is not allowed. The organic content of the sludge can be reduced through biotreatment, but not the metal content. A multistep component-based treatment scheme is therefore needed.     

Biopolymers Based Green Composites: Mechanical, Thermal and Physico-chemical Characterization

Natural cellulosic fibers are one of the smartest materials for use as reinforcement in polymers possessing a number of applications. Keeping in mind the immense advantages of the natural fibers, in present work synthesis of natural cellulosic fibers reinforced polymer composites through compression molding technique have been reported. Scanning Electron microscopy (SEM), Thermo gravimetric/Differential thermal/Derivative Thermogravimetry (TGA/DTA/DTG), absorption in different solvents, moisture absorbance, water uptake and chemical resistance measurements were used as characterization techniques for evaluating the different behaviour of cellulosic natural fibers reinforced polymer composites. Effect of fiber loading on mechanical properties like tensile strength, flexural strength, compressive strength and wear resistances has also been determined. Reinforcing of the polymer matrix with natural fibers was done in the form of short fiber. Present work indicates that green composites can be successfully fabricated with useful mechanical properties. These composites may be used in secondary structural applications in automotive, housing etc.     

Sustainable Bio-Composites from Renewable Resources: Opportunities and Challenges in the Green Materials World

Sustainability, industrial ecology, eco-efficiency, and green chemistry are guiding the development of the next generation of materials, products, and processes. Biodegradable plastics and bio-based polymer products based on annually renewable agricultural and biomass feedstock can form the basis for a portfolio of sustainable, eco-efficient products that can compete and capture markets currently dominated by products based exclusively on petroleum feedstock. Natural/Biofiber composites (Bio-Composites) are emerging as a viable alternative to glass fiber reinforced composites especially in automotive and building product applications. The combination of biofibers such as kenaf, hemp, flax, jute, henequen, pineapple leaf fiber, and sisal with polymer matrices from both nonrenewable and renewable resources to produce composite materials that are competitive with synthetic composites requires special attention, i.e., biofiber–matrix interface and novel processing. Natural fiber–reinforced polypropylene composites have attained commercial attraction in automotive industries. Natural fiber—polypropylene or natural fiber—polyester composites are not sufficiently eco-friendly because of the petroleum-based source and the nonbiodegradable nature of the polymer matrix. Using natural fibers with polymers based on renewable resources will allow many environmental issues to be solved. By embedding biofibers with renewable resource–based biopolymers such as cellulosic plastics; polylactides; starch plastics; polyhydroxyalkanoates (bacterial polyesters); and soy-based plastics, the so-called green bio-composites are continuously being developed.     

Tailor Made Thin Film Composite Membranes: Potentiality Towards Removal of Hydroquinone from Water

The study investigated the use of thin film composite membrane (TFC) as a potential candidate for hydroquinone removal from water. Thin film composite membranes were prepared by polyamide coating on Polysulfone asymmetric membrane. FTIR study was performed to verify the Polysulfone as well as polyamide functionality. TFC membrane was characterized by contact angle, zeta potential, scanning electron microscopy studies. The salt rejection trend was seen from 500 to 1000 mg/L. The membrane is marked by permeability co-efficient B based on solution diffusion studies. The value is 0.98 × 10^?6 m/s for NaCl solution at 1.4 MPa. The separation performance was 88.87% for 5 mg/L hydroquinone at 1.4 MPa. The separation was little bit lowered in acid medium because of the nature of the membrane and feed solute chemistry. The ‘pore swelling’ and ‘salting out’ influenced hydroquinone separation in the presence of NaCl. The hydroquinone separation was 80.63% in 1000 mg/L NaCl solution. In acidic pH, NaCl separation was influenced much more compared to hydroquinone. The separation is influenced by field water matrix.     

Fabrication Mechanical Properties of Unidirectional Jute/PP Composites Using Jute Yarns by Film Stacking Method

This paper mainly focuses on the fabrication process of long fibre reinforced unidirectional thermoplastic composites made using both natural (untreated) treated jute yarns. Jute yarns were wound in layers onto a metallic frame. Polypropylene films were inserted between these layers and compression moulded to fabricate unidirectional jute/PP composite specimens. Static mechanical properties were evaluated from tensile three point bending tests. Pre- post-failure examination were carried out on the test specimens using optical scanning electron microscopy to analyse the test results and investigate the correlations between their impregnation state, processing conditions, mechanical performances and fracture morphologies. For the unidirectional jute/PP film-stacked composites, the results indicated that the processing condition at the moulding temperature of 160°C and moulding pressure of 2.0 MPa for 15 min was ideally suited to obtain optimized properties. Improved wettability of resin melts due to complete matrix fusion at this processing condition facilitated thorough impregnation with minimum microstructural imperfections (microvoids) being generated. Jute/PP composites that contained treated jute yarns have shown superiority in tensile bending properties. Jute yarns polished or coated with PVA/PP (polyvinyl alcohol/polypropylene) must have contributed positively to fibre/matrix interfacial interactions leading to matrix to fibre effective stress transfer, thereby improving their reinforcing effects. Tensile strength and modulus of PP resin increased by approximately 285% and 388%, respectively, due to 50 wt% reinforcement by natural jute yarns. Further improvements in strength and modulus were achieved by approximately 14% and 10%, respectively, when treated yarns were used . The maximum bending stress modulus of jute/PP composites containing untreated yarns were approximately 190% and 460% higher than those of the virgin PP materials, and bending properties were improved by further 11% and 23%, respectively, due to coating treatments on the yarn surface.