Interests in the use of biodegradable polymers as biomaterials have grown. Among the different polymeric composites currently available, the blend of starch and polycaprolactone (PCL) has received the most attention since the 1980s. Novamont is the first company that manufactured a PCL/starch (SPCL) composite under the trademark Mater-Bi®. The properties of PCL (a synthetic, hydrophobic, flexible, expensive polymer with a low degradation rate) and starch (a natural, hydrophilic, stiff, abundant polymer with a high degradation rate) blends are interesting because of the composite components have completely different structures and characteristics. PCL can adjust humidity sensitivity of starch as a biomaterial; while starch can enhance the low biodegradation rate of PCL. Thus, by appropriate blending, SPCL can overcome important limitations of both PCL and starch components and promote controllable behavior in terms of mechanical properties and degradation which make it suitable for many biomedical applications. This article reviewed the different fabrication and modification methods of the SPCL composite; different properties such as structural, physical, and chemical as well as degradation behavior; and different applications as biomaterials.
The present study addressed the synthesis of a bi-layered nanostructured fluorine-doped hydroxyapatite (nFHA)/polycaprolactone (PCL) coating on Mg-2Zn-3Ce alloy via a combination of electrodeposition (ED) and dip-coating methods. The nFHA/PCL composite coating is composed of a thick (70-80 μm) and porous layer of PCL that uniformly covered the thin nFHA film (8-10 μm) with nanoneedle-like microstructure and crystallite size of around 70-90 nm. Electrochemical measurements showed that the nFHA/PCL composite coating presented a high corrosion resistance (R(p)=2.9×10(3) kΩ cm(2)) and provided sufficient protection for a Mg substrate against galvanic corrosion. The mechanical integrity of the nFHA/PCL composite coatings immersed in SBF for 10 days showed higher compressive strength (34% higher) compared with the uncoated samples, indicating that composite coatings can delay the loss of compressive strength of the Mg alloy. The nFHA/PCL coating indicted better bonding strength (6.9 MPa) compared to PCL coating (2.2 MPa). Immersion tests showed that nFHA/PCL composite-coated alloy experienced much milder corrosion attack and more nucleation sites for apatite compared with the PCL coated and uncoated samples. The bi-layered nFHA/PCL coating can be a good alternative method for the control of corrosion degradation of biodegradable Mg alloy for implant applications.
A new class of biocomposites based on oil palm empty fruit bunch fiber and poly(butylene adipate-co-terephthalate) (PBAT), which is a biodegradable aliphatic aromatic co-polyester, were prepared using melt blending technique. The composites were prepared at various fiber contents of 10, 20, 30, 40 and 50 wt% and characterized. Chemical treatment of oil palm empty fruit bunch (EFB) fiber was successfully done by grafting succinic anhydride (SAH) onto the EFB fiber surface, and the modified fibers were obtained in two levels of grafting (low and high weight percentage gain, WPG) after 5 and 6 h of grafting. The FTIR characterization showed evidence of successful fiber esterification. The results showed that 40 wt% of fiber loading improved the tensile properties of the biocomposite. The effects of EFB fiber chemical treatments and various organic initiators content on mechanical and thermal properties and water absorption of PBAT/EFB 60/40 wt% biocomposites were also examined. The SAH-g-EFB fiber at low WPG in presence of 1 wt% of dicumyl peroxide (DCP) initiator was found to significantly enhance the tensile and flexural properties as well as water resistance of biocomposite (up to 24%) compared with those of untreated fiber reinforced composites. The thermal behavior of the composites was evaluated from thermogravimetric analysis (TGA)/differential thermogravimetric (DTG) thermograms. It was observed that, the chemical treatment has marginally improved the biocomposites' thermal stability in presence of 1 wt% of dicumyl peroxide at the low WPG level of grafting. The improved fiber-matrix surface enhancement in the chemically treated biocomposite was confirmed by SEM analysis of the tensile fractured specimens.
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-4-hydroxybutyrate) [P(3HB-co-3HV-co-4HB)] terpolymer was produced using Cupriavidus sp. USMAA2-4 via one-step cultivation process through combination of various carbon sources such as 1,4-butanediol or γ-butyrolactone with either 1-pentanol, valeric acid, or 1-propanol. Oleic acid was added to increase the biomass production. The composition of 3HV and 4HB monomers were greatly affected by the concentration of 1,4-butanediol and 1-pentanol. Terpolymers with 3HV and 4HB molar fractions ranging from 2 to 41 mol.% and 5 to 31 mol.%, respectively, were produced by varying the concentration of carbon precursors. The thermal and mechanical properties of the terpolymers containing different proportions of the constituent monomers were characterized using gel permeation chromatography (GPC), DSC, and tensile machine. GPC analysis showed that the molecular weights (M (w)) of the terpolymer produced were within the range of 346 to 1,710 kDa. The monomer compositions of 3HV and 4HB were also found to have great influences on the thermal and mechanical properties of the terpolymer P(3HB-co-3HV-co-4HB) produced.
The development and characterization of environmentally friendly bilayer films from sugar palm starch (SPS) and poly(lactic acid) (PLA) were conducted in this study. The SPS-PLA bilayer films and their individual components were characterized for their physical, mechanical, thermal and water barrier properties. Addition of 50% PLA layer onto 50% SPS layer (SPS50-PLA50) increased the tensile strength of neat SPS film from 7.74 to 13.65MPa but reduced their elongation at break from 46.66 to 15.53%. The incorporation of PLA layer significantly reduced the water vapor permeability as well as the water uptake and solubility of bilayer films which was attributed to the hydrophobic characteristic of the PLA layer. Furthermore, scanning electron microscopy (SEM) image of SPS50-PLA50 revealed lack of strong interfacial adhesion between the SPS and PLA. Overall, the incorporation of PLA layer onto SPS films enhances the suitability of SPS based films for food packaging.
catena-Poly[dicyclohexylammonium [tributyltin-mu-(4-oxo-4H-pyran-2,6-dicarboxylato-O(2):O( 6))]], (C(12)H(24)N)[Sn(C(7)H(2)O(6))(C(4)H(9))(3)], consists of 4-oxo-4H-pyran-2,6-dicarboxylato groups that axially link adjacent tributyltin units into a linear polyanionic chain. The ammonium counter-ions surround the chain, and each cation forms a pair of hydrogen bonds to the double-bond carbonyl O atoms of the same dianionic group. The chain propagates in a zigzag manner along the c axis of the monoclinic cell. In catena-poly[methyl(phenyl)ammonium [tributyltin-mu-(pyridine-2,6-dicarboxylato-O(2):O(6))]], (C(7)H(10)N)[Sn(C(7)H(3)NO(4))(C(4)H(9))(3)], the pyridine-2, 6-dicarboxylato groups also link the tributyltin groups into a chain, but the hydrogen-bonded chain propagates linearly on the ac face of the monoclinic cell.
The utilization of nanocellulose has increasingly gained attentions from various research fields, especially the field of polymer nanocomposites owing to the growing environmental hazardous of petroleum based fiber products. Meanwhile, the searching of alternative cellulose sources from different plants has become the interests for producing nanocellulose with varying characterizations that expectedly suit in specific field of applications. In this content the long and strong bast fibers from plant species was gradually getting its remarkable position in the field of nanocellulose extraction and nanocomposites fabrications. This review article intended to present an overview of the chemical structure of cellulose, different types of nanocellulose, bast fibers compositions, structure, polylactic acid (PLA) and the most probable processing techniques on the developments of nanocellulose from different bast fibers especially jute, kenaf, hemp, flax, ramie and roselle and its nanocomposites. This article however more focused on the fabrication of PLA based nanocomposites due to its high firmness, biodegradability and sustainability properties in developed products towards the environment. Along with this it also explored a couple of issues to improve the processing techniques of bast fibers nanocellulose and its reinforcement in the PLA biopolymer as final products.
The current research discusses the development of poly (lactic acid) (PLA) and poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) reinforced nanocrystalline cellulose bionanocomposites. The nanocrystalline cellulose was derived from waste oil palm empty fruit bunch fiber by acid hydrolysis process. The resulting nanocrystalline cellulose suspension was then surface functionalized by TEMPO-mediated oxidation and solvent exchange process. Furthermore, the PLA/PHBV/nanocrystalline cellulose bionanocomposites were produced by solvent casting method. The effect of the addition of nanocrystalline cellulose on structural, morphology, mechanical and barrier properties of bionanocomposites was investigated. The results revealed that the developed bionanocomposites showed improved mechanical properties and decrease in oxygen permeability rate. Therefore, the developed bio-based composite incorporated with an optimal composition of nanocrystalline cellulose exhibits properties as compared to the polymer blend.
Global awareness of material sustainability has increased the demand for bio-based polymers like poly(lactic acid) (PLA), which are seen as a desirable alternative to fossil-based polymers because they have less environmental impact. PLA is an aliphatic polyester, primarily produced by industrial polycondensation of lactic acid and/or ring-opening polymerization of lactide. Melt processing is the main technique used for mass production of PLA products for the medical, textile, plasticulture, and packaging industries. To fulfill additional desirable product properties and extend product use, PLA has been blended with other resins or compounded with different fillers such as fibers, and micro- and nanoparticles. This paper presents a review of the current status of PLA mass production, processing techniques and current applications, and also covers the methods to tailor PLA properties, the main PLA degradation reactions, PLA products' end-of-life scenarios and the environmental footprint of this unique polymer.
A packaging material that is environment-friendly with excellent mechanical and physicochemical properties, biodegradable and ultraviolet (UV) protection and thermal stability was prepared to reduce plastic waste. Six different concentrations of Pennisetum purpureum/Napier cellulose nanowhiskers (NWCs) (i.e. 0, 0.5, 1.0, 1.5, 2.0, and 3.0 wt%) were used to reinforce polylactic acid (PLA) by a solvent casting method. The resulting bionanocomposite film samples were characterised in terms of their morphology, chemical structure, crystallinity, thermal degradation and stability, light transmittance, water absorption, biodegradability, and physical and mechanical properties. Field-emission scanning electron microscopy showed the excellent dispersion of NWC in the PLA matrix occurred with NWC concentrations of 0.5-1.5 wt%. All the bionanocomposite film samples exhibited good thermal stability at approximately 343-359 °C. The highest water absorption was 1.94%. The lowest transparency at λ800 was 16.16% for the PLA/3.0% NWC bionanocomposite film, which also has the lowest UVA and UVB transmittance of 7.49% and 4.02%, respectively, making it suitable for packaging materials. The PLA/1.0% NWC film exhibited the highest crystallinity of 50.09% and high tensile strength and tensile modulus of 21.22 MPa and 11.35 MPa, respectively.
Poly(lactic acid) (PLA), a bio-based polyester, has been extensively investigated in the recent past owing to its excellent mechanical properties. Several studies have been conducted on PLA blends, with a focus on improving the brittleness of PLA to ensure its suitability for various applications. However, the increasing use of PLA has increased the contamination of PLA-based products in the environment because PLA remains intact even after three years at sea or in soil. This review focuses on analyzing studies that have worked on improving the degradation properties of PLA blends and studies how other additives affect degradation by considering different degradation media. Factors affecting the degradation properties, such as surface morphology, water uptake, and crystallinity of PLA blends, are highlighted. In natural, biotic, and abiotic media, water uptake plays a crucial role in determining biodegradation rates. Immiscible blends of PLA with other polymer matrices cause phase separation, increasing the water absorption. The susceptibility of PLA to hydrolytic and enzymatic degradation is high in the amorphous region because it can be easily penetrated by water. It is essential to study the morphology, water absorption, and structural properties of PLA blends to predict the biodegradation properties of PLA in the blends.
Polyhydroxybutyrate (PHB)/polycaprolactone (PCL)/stearate Mg-Al layered double hydroxide (LDH) nanocomposites were prepared via solution casting intercalation method. Coprecipitation method was used to prepare the anionic clay Mg-Al LDH from nitrate salt solution. Modification of nitrate anions by stearate anions between the LDH layers via ion exchange reaction. FTIR spectra showed the presence of carboxylic acid (COOH) group which indicates that stearate anions were successfully intercalated into the Mg-Al LDH. The formation of nanocomposites only involves physical interaction as there are no new functional groups or new bonding formed. X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated that the mixtures of nanocomposites are intercalated and exfoliated types. XRD results showed increasing of basal spacing from 8.66 to 32.97 Å in modified stearate Mg-Al LDH, and TEM results revealed that the stearate Mg-Al LDH layers are homogeneously distributed in the PHB/PCL polymer blends matrix. Enhancement in 300% elongation at break and 66% tensile strength in the presence of 1.0 wt % of the stearate Mg-Al LDH as compare with PHB/PCL blends. Scanning electron microscopy (SEM) proved that clay improves compatibility between polymer matrix and the best ratio 80PHB/20PCL/1stearate Mg-Al LDH surface is well dispersed and stretched before it breaks.
Bio-composites of oil palm empty fruit bunch (OPEFB) fibres and polycaprolactones (PCL) with a thickness of 1 mm were prepared and characterized. The composites produced from these materials are low in density, inexpensive, environmentally friendly, and possess good dielectric characteristics. The magnitudes of the reflection and transmission coefficients of OPEFB fibre-reinforced PCL composites with different percentages of filler were measured using a rectangular waveguide in conjunction with a microwave vector network analyzer (VNA) in the X-band frequency range. In contrast to the effective medium theory, which states that polymer-based composites with a high dielectric constant can be obtained by doping a filler with a high dielectric constant into a host material with a low dielectric constant, this paper demonstrates that the use of a low filler percentage (12.2%OPEFB) and a high matrix percentage (87.8%PCL) provides excellent results for the dielectric constant and loss factor, whereas 63.8% filler material with 36.2% host material results in lower values for both the dielectric constant and loss factor. The open-ended probe technique (OEC), connected with the Agilent vector network analyzer (VNA), is used to determine the dielectric properties of the materials under investigation. The comparative approach indicates that the mean relative error of FEM is smaller than that of NRW in terms of the corresponding S21 magnitude. The present calculation of the matrix/filler percentages endorses the exact amounts of substrate utilized in various physics applications.
Presently, plant oils which contain high percentage of linoleic acid 1 are perceived to be a viable alternative to mineral oil for biolubricant applications due to their biodegradability and technical properties. In order to get biodegradable lubricant, triester derivatives compounds (1-5) were synthesized and characterized. The processes involved were monoepoxidation of linoleic acid 2, oxirane ring opening 3, esterification 4 and acylation 5. The structures of the products were confirmed by FTIR, 1H and 13C-NMR and LC-MS. The results that showed lowest temperature properties were obtained for triester 5, with a pour point value (PP) of -73°C, highest onset temperature (260°C) and lowest volatility at 0.30%. Viscosity index (VI) increased for the ester's synthetic compounds (2, 3, 4, 5), while the PP decreased. This behavior is the result of the increase of the chain length of the branching agents. Triester based linoleic acid has improved properties such as low-temperature and tribological properties. These results will make it feasible for plant oil to be used for biolubricants, fuels in chain saws, transmission oil and brake fluid.
Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [(P(3HB-co-4HB)] copolymer receives attention as next generation biomaterial in medical application. However, the exploitation of the copolymer is still constrained since such copolymer has not yet successfully been performed in industrial scale production. In this work, we intended to establish pilot production system of the copolymer retaining the copolymer quality which has recently discovered to have novel characteristic from lab scale fermentation. An increase of agitation speed has significantly improved the copolymer accumulation efficiency by minimizing the utilization of substrates towards cell growth components. This is evidenced by a drastic increase of PHA content from 28 wt% to 63 wt% and PHA concentration from 3.1 g/L to 6.5 g/L but accompanied by the reduction of residual biomass from 8.0 g/L to 3.8 g/L. Besides, fermentations at lower agitation and aeration have resulted in reduced molecular weight and mechanical strength of the copolymer, suggesting the role of sufficient oxygen supply efficiency in improving the properties of the resulting copolymers. The KLa-based scale-up fermentation was performed successfully in maintaining the yield and the quality of the copolymers produced without a drastic fluctuation. This suggests that the scale-up based on the KLa values supported the fermentation system of P(3HB-co-4HB) copolymer production in single-stage using mixed-substrate cultivation strategy.
Long carbon chain alkanediols are used in the production of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)], however these substrates possess high toxicity towards bacterial cells. This study demonstrated the effective utilisation of a long carbon chain alkanediol, namely 1,8-octanediol, to enhance the yield and production of a copolymer with a high molecular weight of over 1000 kDa, which is desirable for novel applications in medical and biopharmaceuticals. The increased PHA content (47-61 wt%) and concentration (1.7-4.5 g/L) was achieved by additional feeding of a combination of C4 substrates at C/N 10, with 1,8-octanediol + γ-butyrolactone producing P(3HB-co-22 mol% 4HB) with a high molecular weight (1060 kDa) and elongation at break of 970%. The DO-stat feeding strategy of C/N 10 has shown an increment of PHA concentration for both carbon combination, 0.45-4.27 g/L and 0.32-3.36 g/L for 1,8-octanediol + sodium 4-hydroxybutyrate (4HB-Na) and 1,8-octanediol + γ-butyrolactone, but with a slight reduction on molecular weight and mechanical strength. Nonetheless, further study revealed that a nitrogen-absence feeding strategy could retain the high molecular weight and elongation at break of the copolymer, and simultaneously improving the overall P(3HB-co-4HB) production.
The in vitro degradation and mechanical properties of a 3D porous Pennisetum purpureum (PP)/polylactic acid (PLA)-based scaffold were investigated. In this study, composite scaffolds with PP to PLA ratios of 0%, 10%, 20%, and 30% were immersed in a PBS solution at 37°C for 40 days. Compression tests were conducted to evaluate the compressive strength and modulus of the scaffolds, according to ASTM F451-95. The compression strength of the scaffolds was found to increase from 1.94 to 9.32MPa, while the compressive modulus increased from 1.73 to 5.25MPa as the fillers' content increased from 0wt% to 30wt%. Moreover, field emission scanning electron microscopy (FESEM) and X-ray diffraction were employed to observe and analyse the microstructure and fibre-matrix interface. Interestingly, the degradation rate was reduced for the PLA/PP20scaffold, though insignificantly, this could be attributed to the improved mechanical properties and stronger fibre-matrix interface. Microstructure changes after degradation were observed using FESEM. The FESEM results indicated that a strong fibre-matrix interface was formed in the PLA/PP20scaffold, which reflected the addition of P. purpureum into PLA decreasing the degradation rate compared to in pure PLA scaffolds. The results suggest that the P. purpureum/PLA scaffold degradation rate can be altered and controlled to meet requirements imposed by a given tissue engineering application.
Two-stage fermentation was normally employed to achieve a high poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] productivity with higher 4HB molar fraction. Here, we demonstrated single-stage fermentation method which is more industrial feasible by implementing mixed-substrate cultivation strategy. Studies on bioreactor scale show a remarkably high PHA accumulation of 73 wt%, contributing to a high PHA concentration and product yield of 8.6 g/L and 2.7 g/g, respectively. This fermentation strategy has resulted in copolymers with wider range of 4HB monomer composition, which ranges from 12 to 55 mol%. These copolymers show a broad range of weight average molecular weight (M w ) from 119.5 to 407.0 kDa. The copolymer characteristics were found to be predominantly affected by the nature of the substrates and the mixture strategies, regardless of the 4HB monomer compositions. This was supported by the determination of copolymer randomness using (13)C-NMR analysis. The study warrants significantly in the copolymer scale-up and modeling at industrial level.
Polymer composites are fabricated by incorporating fillers into a polymer matrix. The intent for addition of fillers is to improve the physical, mechanical, chemical and rheological properties of the composite. This study reports on a unique polymer composite using hydrochar, synthesised by microwave-assisted hydrothermal carbonization of rice husk, as filler in polylactide matrix. The polylactide/hydrochar composites were fabricated by incorporating hydrochar in polylactide at 5%, 10%, 15% and 20 wt% by melt processing in a Haake rheomix at 170 °C. Both the neat polylactide and polylactide/hydrochar composite were characterized for mechanical, structural, thermal and rheological properties. The tensile modulus of polylactide/hydrochar composites was improved from 2.63 GPa (neat polylactide) to 3.16 GPa, 3.33 GPa, 3.54 GPa, and 4.24 GPa after blending with hydrochar at 5%, 10%, 15%, and 20%, respectively. Further, the incorporation of hydrochar had little effect on storage modulus (G') and loss modulus (G″). The findings of this study reported that addition of hydrochar improves some characteristics of polylactide composites suggesting the potential of hydrochar as filler for polymer/hydrochar composites.
Copolyesters of 3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB) were produced by Cupriavidus sp. (USMAA2-4) (DSM 19379) from carbon sources of 1,4-butanediol and gamma-butyrolactone. The composition of copolyesters produced varied from 0 to 45 mol% 4HB, depending on the combination of carbon sources supplied. The P(3HB-co-4HB) films containing Mitragyna speciosa crude extract were prepared with the ratio varying from 10 to 40% (w/w). The in vitro crude extract release of the films was studied in 0.1M phosphate buffer (pH 7.4) at 37 degrees C. Although the release rate was slow, it was maintained at a constant rate. This suggests that the crude extract release was due to the polymer degradation because the amount of crude extract released was consistent. The amount of degradation was based on the films' dry weight loss, decrease in molecular weight and surface morphology changes. The degradation rate increased with the 4HB content. This showed that the polymer degradation is dependant on the molecular weight, crystallinity, thermal properties and water permeability. The different drug loading ratio which led to surface morphology changes also gave an effect on polymer degradation.