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Keywords = polyhydroxybutyrate-valerate (PHBV)

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14 pages, 9593 KiB  
Article
Brewers’ Spent Grain-Derived Arabinoxylan as a Sustainable Filler for Enhanced PHBV Biocomposites
by Ilary Belardi, Fabrizio Sarasini, Jacopo Tirillò, Pietro Russo, Giovanni De Francesco, Ombretta Marconi and Assunta Marrocchi
Polymers 2025, 17(1), 114; https://doi.org/10.3390/polym17010114 - 5 Jan 2025
Cited by 1 | Viewed by 1387
Abstract
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a highly promising biodegradable and bio-based thermoplastic recognized for its environmental benefits and potential versatility. However, its industrial adoption has been limited due to its inherent brittleness and suboptimal processability. Despite these challenges, PHBV’s performance can be tailored for a [...] Read more.
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a highly promising biodegradable and bio-based thermoplastic recognized for its environmental benefits and potential versatility. However, its industrial adoption has been limited due to its inherent brittleness and suboptimal processability. Despite these challenges, PHBV’s performance can be tailored for a wide range of applications through strategic modifications, particularly by blending it with other biodegradable polymers or reinforcing it with natural fibers and bio-based fillers. This study explores the potential of brewers’ spent grain (BSG) as a sustainable source for the development of PHBV biocomposites. The biocomposites were synthesized by incorporating arabinoxylan-bound benzoate, which can be derived from BSG, as a sustainable filler at concentrations of 4% and 10% w/w. The resulting materials were characterized using tensile testing, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The findings demonstrate that the incorporation of functionalized arabinoxylan significantly enhances the mechanical properties of PHBV, preserves its thermal stability, and increases its crystallinity (from 59.9% to 67.6%), highlighting a positive impact on both material performance and processing characteristics. Full article
(This article belongs to the Special Issue Biobased and Biodegradable Polymer Blends and Composites II)
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24 pages, 11240 KiB  
Article
Study of the Interplay Among Melt Morphology, Rheology and 3D Printability of Poly(Lactic Acid)/Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) Blends
by Marco Costantini, Flavio Cognini, Roberta Angelini, Sara Alfano, Marianna Villano, Andrea Martinelli, David Bolzonella, Marco Rossi and Andrea Barbetta
J. Funct. Biomater. 2025, 16(1), 9; https://doi.org/10.3390/jfb16010009 - 1 Jan 2025
Viewed by 1738
Abstract
Polymeric materials made from renewable sources that can biodegrade in the environment are attracting considerable attention as substitutes for petroleum-based polymers in many fields, including additive manufacturing and, in particular, Fused Deposition Modelling (FDM). Among the others, poly(hydroxyalkanoates) (PHAs) hold significant potential as [...] Read more.
Polymeric materials made from renewable sources that can biodegrade in the environment are attracting considerable attention as substitutes for petroleum-based polymers in many fields, including additive manufacturing and, in particular, Fused Deposition Modelling (FDM). Among the others, poly(hydroxyalkanoates) (PHAs) hold significant potential as candidates for FDM since they meet the sustainability and biodegradability standards mentioned above. However, the most utilised PHA, consisting of the poly(hydroxybutyrate) (PHB) homopolymer, has a high degree of crystallinity and low thermal stability near the melting point. As a result, its application in FDM has not yet attained mainstream adoption. Introducing a monomer with higher excluded volume, such as hydroxyvalerate, in the PHB primary structure, as in poly(hydroxybutyrate-co-valerate) (PHBV) copolymers, reduces the degree of crystallinity and the melting temperature, hence improving the PHA printability. Blending amorphous poly(lactic acid) (PLA) with PHBV enhances further PHA printability via FDM. In this work, we investigated the printability of two blends characterised by different PLA and PHBV weight ratios (25:75 and 50:50), revealing the close connection between blend microstructures, melt rheology and 3D printability. For instance, the relaxation time associated with die swelling upon extrusion determines the diameter of the extruded filament, while the viscoelastic properties the range of extrusion speed available. Through thoroughly screening printing parameters such as deposition speed, nozzle diameter, flow percentage and deposition platform temperature, we determined the optimal printing conditions for the two PLA/PHBV blends. It turned out that the blend with a 50:50 weight ratio could be printed faster and with higher accuracy. Such a conclusion was validated by replicating with remarkable fidelity high-complexity objects, such as a patient’s cancer-affected iliac crest model. Full article
(This article belongs to the Special Issue Advanced Technologies for Processing Functional Biomaterials)
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20 pages, 9578 KiB  
Article
Valorization of Agricultural Waste Lignocellulosic Fibers for Poly(3-Hydroxybutyrate-Co-Valerate)-Based Composites in Short Shelf-Life Applications
by Kerly Samaniego-Aguilar, Estefanía Sánchez-Safont, Andreina Rodríguez, Anna Marín, María V. Candal, Luis Cabedo and Jose Gamez-Perez
Polymers 2023, 15(23), 4507; https://doi.org/10.3390/polym15234507 - 23 Nov 2023
Cited by 7 | Viewed by 1716
Abstract
Biocircularity could play a key role in the circular economy, particularly in applications where organic recycling (composting) has the potential to become a preferred waste management option, such as food packaging. The development of fully biobased and biodegradable composites could help reduce plastic [...] Read more.
Biocircularity could play a key role in the circular economy, particularly in applications where organic recycling (composting) has the potential to become a preferred waste management option, such as food packaging. The development of fully biobased and biodegradable composites could help reduce plastic waste and valorize agro-based residues. In this study, extruded films made of composites of polyhydroxybutyrate-co-valerate (PHBV) and lignocellulosic fibers, namely almond shell (AS) and Oryzite® (OR), a polymer hybrid composite precursor, have been investigated. Scanning electron microscopy (SEM) analysis revealed a weak fiber–matrix interfacial interaction, although OR composites present a better distribution of the fiber and a virtually lower presence of “pull-out”. Thermogravimetric analysis showed that the presence of fibers reduced the onset and maximum degradation temperatures of PHBV, with a greater reduction observed with higher fiber content. The addition of fibers also affected the melting behavior and crystallinity of PHBV, particularly with OR addition, showing a decrease in crystallinity, melting, and crystallization temperatures as fiber content increased. The mechanical behavior of composites varied with fiber type and concentration. While the incorporation of AS results in a reduction in all mechanical parameters, the addition of OR leads to a slight improvement in elongation at break. The addition of fibers improved the thermoformability of PHBV. In the case of AS, the improvement in the processing window was achieved at lower fiber contents, while in the case of OR, the improvement was observed at a fiber content of 20%. Biodisintegration tests showed that the presence of fibers promoted the degradation of the composites, with higher fiber concentrations leading to faster degradation. Indeed, the time of complete biodisintegration was reduced by approximately 30% in the composites with 20% and 30% AS. Full article
(This article belongs to the Special Issue Advanced Biopolymers and Biocomposites)
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14 pages, 6488 KiB  
Article
Biodegradation Studies of Polyhydroxybutyrate and Polyhydroxybutyrate-co-Polyhydroxyvalerate Films in Soil
by Jihyeon Kim, Nevin S. Gupta, Lindsey B. Bezek, Jacqueline Linn, Karteek K. Bejagam, Shounak Banerjee, Joseph H. Dumont, Sang Yong Nam, Hyun Woo Kang, Chi Hoon Park, Ghanshyam Pilania, Carl N. Iverson, Babetta L. Marrone and Kwan-Soo Lee
Int. J. Mol. Sci. 2023, 24(8), 7638; https://doi.org/10.3390/ijms24087638 - 21 Apr 2023
Cited by 35 | Viewed by 5843
Abstract
Due to increased environmental pressures, significant research has focused on finding suitable biodegradable plastics to replace ubiquitous petrochemical-derived polymers. Polyhydroxyalkanoates (PHAs) are a class of polymers that can be synthesized by microorganisms and are biodegradable, making them suitable candidates. The present study looks [...] Read more.
Due to increased environmental pressures, significant research has focused on finding suitable biodegradable plastics to replace ubiquitous petrochemical-derived polymers. Polyhydroxyalkanoates (PHAs) are a class of polymers that can be synthesized by microorganisms and are biodegradable, making them suitable candidates. The present study looks at the degradation properties of two PHA polymers: polyhydroxybutyrate (PHB) and polyhydroxybutyrate-co-polyhydroxyvalerate (PHBV; 8 wt.% valerate), in two different soil conditions: soil fully saturated with water (100% relative humidity, RH) and soil with 40% RH. The degradation was evaluated by observing the changes in appearance, chemical signatures, mechanical properties, and molecular weight of samples. Both PHB and PHBV were degraded completely after two weeks in 100% RH soil conditions and showed significant reductions in mechanical properties after just three days. The samples in 40% RH soil, however, showed minimal changes in mechanical properties, melting temperatures/crystallinity, and molecular weight over six weeks. By observing the degradation behavior for different soil conditions, these results can pave the way for identifying situations where the current use of plastics can be replaced with biodegradable alternatives. Full article
(This article belongs to the Collection Frontiers in Polymeric Materials)
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21 pages, 4214 KiB  
Article
In Service Performance of Toughened PHBV/TPU Blends Obtained by Reactive Extrusion for Injected Parts
by Kerly Samaniego-Aguilar, Estefanía Sánchez-Safont, Alex Arrillaga, Jon Anakabe, Jose Gamez-Perez and Luis Cabedo
Polymers 2022, 14(12), 2337; https://doi.org/10.3390/polym14122337 - 9 Jun 2022
Cited by 7 | Viewed by 3248
Abstract
Moving toward a more sustainable production model based on a circular economy, biopolymers are considered as one of the most promising alternatives to reduce the dependence on oil-based plastics. Polyhydroxybutyrate-co-valerate (PHBV), a bacterial biopolyester from the polyhydroxialkanoates (PHAs) family, seems to be an [...] Read more.
Moving toward a more sustainable production model based on a circular economy, biopolymers are considered as one of the most promising alternatives to reduce the dependence on oil-based plastics. Polyhydroxybutyrate-co-valerate (PHBV), a bacterial biopolyester from the polyhydroxialkanoates (PHAs) family, seems to be an attractive candidate to replace commodities in many applications such as rigid packaging, among others, due to its excellent overall physicochemical and mechanical properties. However, it presents a relatively poor thermal stability, low toughness and ductility, thus limiting its applicability with respect to other polymers such as polypropylene (PP). To improve the performance of PHBV, reactive blending with an elastomer seems to be a proper cost-effective strategy that would lead to increased ductility and toughness by rubber toughening mechanisms. Hence, the objective of this work was the development and characterization of toughness-improved blends of PHBV with thermoplastic polyurethane (TPU) using hexamethylene diisocyanate (HMDI) as a reactive extrusion agent. To better understand the role of the elastomer and the compatibilizer, the morphological, rheological, thermal, and mechanical behavior of the blends were investigated. To explore the in-service performance of the blends, mechanical and long-term creep characterization were conducted at three different temperatures (−20, 23, 50 °C). Furthermore, the biodegradability in composting conditions has also been tested. The results showed that HMDI proved its efficiency as a compatibilizer in this system, reducing the average particle size of the TPU disperse phase and enhancing the adhesion between the PHBV matrix and TPU elastomer. Although the sole incorporation of the TPU leads to slight improvements in toughness, the compatibilizer plays a key role in improving the overall performance of the blends, leading to a clear improvement in toughness and long-term behavior. Full article
(This article belongs to the Special Issue Polymers in Food Packaging Applications)
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14 pages, 3259 KiB  
Article
Assessment of Petroleum-Based Plastic and Bioplastics Degradation Using Anaerobic Digestion
by Benjamin Nachod, Emily Keller, Amro Hassanein and Stephanie Lansing
Sustainability 2021, 13(23), 13295; https://doi.org/10.3390/su132313295 - 1 Dec 2021
Cited by 21 | Viewed by 8428
Abstract
Bioplastics have emerged as a viable alternative to traditional petroleum-based plastic (PET). Three of the most common bioplastic polymers are polyhydroxybutyrate-valerate (PHBV), polylactide (PLA), and cellulose-based bioplastic (CBB). This study assessed biodegradation through anaerobic digestion (AD) of these three bioplastics and PET digested [...] Read more.
Bioplastics have emerged as a viable alternative to traditional petroleum-based plastic (PET). Three of the most common bioplastic polymers are polyhydroxybutyrate-valerate (PHBV), polylactide (PLA), and cellulose-based bioplastic (CBB). This study assessed biodegradation through anaerobic digestion (AD) of these three bioplastics and PET digested with food waste (FW) at mesophilic (35 °C) and thermophilic (55 °C) temperatures. The four plastic types were digested with FW in triplicate batch reactors. Additionally, two blank treatments (inoculum-only) and two PHBV treatments (with FW + inoculum and inoculum-only) were digested at 35 and 55 °C. The PHBV treatment without FW at 35 °C (PHBV-35) produced the most methane (CH4) normalized by the volatile solids (VS) of the bioplastics over the 104-day experimental period (271 mL CH4/g VS). Most bioplastics had more CH4 production than PET when normalized by digester volume or gram substrate added, with the PLA-FW-55 (5.80 m3 CH4/m3), PHBV-FW-55 (2.29 m3 CH4/m3), and PHBV-55 (4.05 m3 CH4/m3) having 848,275 and 561%, respectively, more CH4 production than the PET treatment. The scanning electron microscopy (SEM) showed full degradation of PHBV pellets after AD. The results show that when PHBV is used as bioplastic, it can be degraded with energy production through AD. Full article
(This article belongs to the Special Issue Innovation in Waste-to-Energy Technology)
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18 pages, 1449 KiB  
Review
Review on the Biological Degradation of Polymers in Various Environments
by Silvia Kliem, Marc Kreutzbruck and Christian Bonten
Materials 2020, 13(20), 4586; https://doi.org/10.3390/ma13204586 - 15 Oct 2020
Cited by 159 | Viewed by 10993
Abstract
Biodegradable plastics can make an important contribution to the struggle against increasing environmental pollution through plastics. However, biodegradability is a material property that is influenced by many factors. This review provides an overview of the main environmental conditions in which biodegradation takes place [...] Read more.
Biodegradable plastics can make an important contribution to the struggle against increasing environmental pollution through plastics. However, biodegradability is a material property that is influenced by many factors. This review provides an overview of the main environmental conditions in which biodegradation takes place and then presents the degradability of numerous polymers. Polylactide (PLA), which is already available on an industrial scale, and the polyhydroxyalkanoates polyhydroxybutyrate (PHB) and polyhydroxybutyrate-co-valerate (PHBV), which are among the few plastics that have been proven to degrade in seawater, will be discussed in detail, followed by a summary of the degradability of further petroleum-, cellulose-, starch-, protein- and CO2-based biopolymers and some naturally occurring polymers. Full article
(This article belongs to the Special Issue Biodegradation or Biodeterioration of Non-metallic Materials)
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9 pages, 9637 KiB  
Communication
A Brief Report on an Implantation of Small-Caliber Biodegradable Vascular Grafts in a Carotid Artery of the Sheep
by Larisa V. Antonova, Andrey V. Mironov, Arseniy E. Yuzhalin, Evgeniya O. Krivkina, Amin R. Shabaev, Maria A. Rezvova, Vadim O. Tkachenko, Mariam Yu. Khanova, Tatiana Yu. Sergeeva, Sergei S. Krutitskiy and Leonid S. Barbarash
Pharmaceuticals 2020, 13(5), 101; https://doi.org/10.3390/ph13050101 - 21 May 2020
Cited by 17 | Viewed by 3830
Abstract
The development of novel biodegradable vascular grafts of a small diameter (<6 mm) is an unmet clinical need for patients requiring arterial replacement. Here we performed a pre-clinical study of new small-caliber biodegradable vascular grafts using a sheep model of carotid artery implantation. [...] Read more.
The development of novel biodegradable vascular grafts of a small diameter (<6 mm) is an unmet clinical need for patients requiring arterial replacement. Here we performed a pre-clinical study of new small-caliber biodegradable vascular grafts using a sheep model of carotid artery implantation. The 4 mm diameter vascular grafts were manufactured using a mix of polyhydroxybutyrate/valerate and polycaprolactone supplemented with growth factors VEGF, bFGF and SDF-1α (PHBV/PCL-GFmix) and additionally modified by a polymer hydrogel coating with incorporation of drugs heparin and iloprost (PHBV/PCL-GFmixHep/Ilo). Animals with carotid artery autograft implantation and those implanted with clinically used GORE-TEX® grafts were used as control groups. We observed that 24 h following surgery, animals with carotid artery autograft implantation showed 87.5% patency, while all the PHBV/PCL-GFmix and GORE-TEX® grafts displayed thrombosis. PHBV/PCL-GFmixHep/Ilo grafts demonstrated 62.5% patency 24 h following surgery and it had remained at 50% 1 year post-operation. All the PHBV/PCL grafts completely degraded less than 1 year following surgery and were replaced by de novo vasculature without evidence of calcification. On the other hand, GORE-TEX® grafts displayed substantial amounts of calcium deposits throughout graft tissues. Thus, here we report a potential clinical usefulness of PHBV/PCL grafts upon their additional modification by growth factors and drugs to promote endothelialization and reduce thrombogenicity. Full article
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15 pages, 2593 KiB  
Article
Mechanical and Hydrothermal Aging Behaviour of Polyhydroxybutyrate-Co-Valerate (PHBV) Composites Reinforced by Natural Fibres
by Karolina Mazur and Stanisław Kuciel
Molecules 2019, 24(19), 3538; https://doi.org/10.3390/molecules24193538 - 30 Sep 2019
Cited by 38 | Viewed by 3781
Abstract
Biodegradable composites based on poly (3-hydroxybutyrate-co-3-hydroxyvalerate), reinforced with 7.5% or 15% by weight of wood fibers (WF) or basalt fibers (BF) were fabricated by injection molding. BF reinforced composites showed improvement in all properties, whereas WF composites showed an increase in Young’s modulus [...] Read more.
Biodegradable composites based on poly (3-hydroxybutyrate-co-3-hydroxyvalerate), reinforced with 7.5% or 15% by weight of wood fibers (WF) or basalt fibers (BF) were fabricated by injection molding. BF reinforced composites showed improvement in all properties, whereas WF composites showed an increase in Young’s modulus values, but a drop in strength and impact properties. When compared with the unmodified polymer, composites with 15% by weight of BF showed an increase of 74% in Young’s modulus and 41% in impact strength. Furthermore, the experimentally measured values of Young’s modulus were compared with values obtained in various theoretical micromechanical models. The Haplin-Kardas model was found to be in near approximation to the experimental data. The morphological aspect of the biocomposites was studied using scanning electron microscopy to obtain the distribution and interfacial adhesion of the fibers. Additionally, biodegradation tests of the biocomposites were performed in saline solution at 40 °C by studying the weight loss and mechanical properties. It was observed that the presence of fibers affects the rate of water absorption and the highest rate was seen for composites with 15% by weight of WF. This is dependent on the nature of the fiber. After both the first and second weeks mechanical properties decreased slightly about 10%. Full article
(This article belongs to the Special Issue Advances in Natural Fiber Composites and Their Interfacial Adhesion)
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