Bio-based Hybrid Research Articles

Toward a bio-based hybrid inhibition of gas hydrate and corrosion for flow assurance

The development of a hybrid inhibition of corrosion and gas hydrate formation in offshore oil and gas fields is the main object of this study. Sunflower oil was used as an inexpensive and environmentally friendly resource for synthesizing a dual function inhibitor to prevail incompatibility difficulty between anti-hydrate and anti-corrosion reagents. The results of hydrate inhibition experiments revealed that phosphorylated waterborne polyurea/urethane (Ph-WPUU) can significantly reduce the average onset temperature and delay the induction time of hydrate nucleation compared to pure water. Besides, the constant value of torque at the 100 and 60% water-cuts with decane phase and foam-like methane-propane hydrate formed in the presence of Ph-WPUU occurred. This may indicate mitigation of hydrate particles agglomeration. On the other hand, the Ph-WPUU showed corrosion inhibition efficiency around 96% at 700 ppm concentration. Moreover, the quantum chemical study revealed that the presence of the triglyceride group of sunflower oil in the Ph-WPUU structure plays an effective role as an active site to interact with the carbon steel surface. These results indicate that the application of Ph-WPUU provides a bio-based strategy to develop and design single polymer molecules that exhibit both hydrate and corrosion inhibition, and this approach refers to the terms of green chemistry.

Development of a Renewable Hybrid Resin System by Blending Isocyanate with Novolac Phenolic Resins

Abstract The objective of this study was to develop a performance-competitive bio-based hybrid resin system composed of methylene diphenyl diisocyanate (MDI) resin and novolac phenol-formaldehyde (PF) resin for engineered wood panel manufacturing. A novolac PF resin and a bio-oil–modified PF resin were blended with MDI at weight ratios of PF to MDI of 85:15, 75:25, 50:50, and 25:75, respectively. The obtained hybrid resins were examined with Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA), and evaluated as plywood binders. The results indicated that the gel times and viscosities of hybrid resins were closely related to the weight ratio of PF resin to MDI. At a ratio lower than 75:25, the viscosities of hybrid resins were appropriate for plywood application. FTIR results showed some reactions between the novolac PF resin and MDI. TGA results showed that reacting novolac PF resin with MDI resin possibly increased the thermal stabilities of hybrid resins in the temperature range of 150°C to 300°C. Panel performance tests showed that blending novolac PF resin with MDI increased both the dry and the wet bonding strength of panels at the optimal ratio of 50:50. Replacing phenol with bio-oil of the hybrid resin had the trend of reducing the hybrid resin gel time and increasing panel dry and wet bonding strength.

Studies on the effects of different multiwalled carbon nanotube functionalization techniques on the properties of bio-based hybrid non-isocyanate polyurethane.

A novel synthesis method for multiwalled carbon nanotube (MWCNT) modified bio-based hybrid non-isocyanate polyurethane (HNIPU) is proposed in this paper. Modification methods for several properties of MWCNTs–HNIPU were systematically studied. MWCNTs were grafted with carboxyl and amino groups using a condensation reflux device. Au nanoparticles were synthesized on the surface of the MWCNTs via a reduction reaction and Fe3O4 particles were decorated on the MWCNTs using a hydrothermal method. FTIR, TEM, XRD, XPS and Raman techniques were employed to confirm the compositions and structures. Then, five different types of MWCNT were utilized for blending with non-isocyanate polyurethane (NIPU) via solution methods. After curing with epoxy resin E-51, the cross-linked composites were applied as coatings. A series of tests demonstrated that HNIPU composited with MWCNTs–COOH–Au had the highest Tg value, the best thermal, thermodynamic and mechanical properties, and excellent pencil hardness, adhesion, flexibility and impact strength, while HNIPU composited with MWCNTs–COOH–NH2 had the best water absorption and swelling properties. These results showed that the properties of hybrid non-isocyanate polyurethane can be adjusted via different MWCNT surface modification approaches or the addition of nanoparticles, so this kind of polyurethane has a vast development space for coating applications.

Facile synthesis of Ag NPs@ MIL-100(Fe)/ guar gum hybrid hydrogel as a versatile photocatalyst for wastewater remediation: Photocatalytic degradation, water/oil separation and bacterial inactivation

3D Hydrogel is one of the most popular adsorbents for water remediation due to its excellent concentration/ adsorption capacity. However, it remains a challenge to use the hydrogel alone for treating complex wastewater. In this work, we designed and fabricated a versatile bio-based hybrid hydrogel consisting of Ag NPs@ MIL-100(Fe) photocatalysts and guar gum (GG) via facile blending and self-crosslinking. The hybrid hydrogel integrated with multifunctions of dye adsorption and degradation, oil/water separation and antibacterial properties, thus enabling its applications in complex wastewater remediation process. The presence of Ag nanoparticles (Ag NPs) not only enhanced the photocatalytic activity of MIL-100(Fe), but also imparted the antibacterial activity of Ag NPs@MIL-100(Fe)/ GG hydrogel. Particularly, the bio-based GG hydrogel scaffold showed excellent injectable, remodeling, and self-healing properties, which enabled an effective oil/water separation ability (silicone oil, cyclohexane and canola oil) and facilitated the recyclability/sustainability of the nano-photocatalyst powders. This novel multifunctional 3D hybrid hydrogel provides new opportunities for wastewater remediation purpose.

Novel hybrid composite based on bio-PET with basalt/carbon fibre

The aim of this work was to evaluate the possibility of manufacturing hybrid composites based on one of the latest generations of bio derivative polyethylene terephthalate with equal amounts of basalt and carbon fibres. This combination of two types of fibres gives the opportunity to obtain synergistic strength and performance properties. Samples obtained by injection moulding were characterized by morphological, mechanical (tensile, flexural, impact) and processing (softening temperature, thermal expansion and shrinkage) properties. Light-weight and bio-based hybrid composites based on bio-PET matrix with already 10 wt% basalt fibres and 10 wt% carbon fibres are characterized by more than 90 % increase in tensile strength and they have almost four times increase in the modulus of elasticity at a wide range of temperatures. Due to the good mechanical properties of hybrid composites, they can be successfully used in various industry sectors, mainly for consumer goods, household appliances and in automotive industry. Products made of bio-based sources pose a significantly lower threat to the environment than those from petrochemical sources.

Development of a novel bio-based hybrid resin system for hygienic coating

A new water based organic-inorganic nano hybrid resin was synthesised through sol-gel technique by using alkoxysilane modified acrylic resin, silane monomer and chitosan as functional components. The uniqueness of this process is the incorporation of chitosan via in situ hydrolysis-condensation reaction of silane modified acrylic resin and methyl triethoxy silane in aqueous basic medium. The formation of nano silica and their bonding with chitosan in acrylic matrix has been confirmed by spectroscopic and SEM analysis. The coating based on such hybrid polymer exhibited excellent antibacterial activity, hydrophobicity and formaldehyde absorption ability. Such innovative bio-based resin has potential for application in hygienic interior decorative coating.

An Easy Synthesis for Preparing Bio-Based Hybrid Adsorbent Useful for Fast Adsorption of Polar Pollutants.

For the first time, γ-Al2O3 and Bio-Based Substances (BBS) hybrids (A-BBS) were prepared through a simple electrostatic interaction occurring between alumina, used as a support, and BBS (Bio-Based Substance from composted biowastes) carrying positive and negative charges, respectively. We evaluated the optimal amount of BBS to be immobilized on the support and the stability of the resulting A-BBS in order to use this novel hybrid material as an adsorbent for the removal of polar pollutants. Characterization was carried out by X-Ray Diffraction (XRD) for evaluating the crystal structure of the support, Fourier transform infrared spectroscopy (FT-IR) to evidence the presence of BBS on the hybrid material, thermogravimetric analysis (TGA) to measure the thermal stability of the hybrid materials and quantify the BBS amount immobilized on the support, N2 adsorption at 77 K for the evaluation of the surface area and porosity of the systems, Zeta potential measurements to evaluate the effect of BBS immobilization on the surface charge of the particles and choose the substrates possibly interacting with them. Firstly, we tested the adsorption capability of three samples differently coated with BBS toward cationic species considering various adsorbate/adsorbent ratio. Crystal Violet (CV) was chosen as model pollutant to compare the performance of the hybrid materials with those of other materials described in the literature. The adsorption data were modeled by Langmuir and Freundlich adsorption isotherms. Then, we studied the adsorption capability of the developed material towards molecules with different structures; for this purpose, two contaminants of emerging concerns (carbamazepine and atenolol) were tested. The results indicate that A-BBS could be applied in wastewater treatment for the removal of a significant amount of polar species. In addition, a comparison with literature data concerning CV adsorption was carried out in order to evaluate the environmental impact of synthetic routes used to prepare different adsorbents.

Fully Bio-Based Hybrid Composites Made of Wood, Fungal Mycelium and Cellulose Nanofibrils

Novel hybrid panel composites based on wood, fungal mycelium, and cellulose nanofibrils (CNF) were developed and investigated in the present study. In one set of experiments, mycelium was grown on softwood particles to produce mycelium-modified wood which was then hybridized with various levels of CNF as binder. The other set of experiments were conducted on unmodified wood particles mixed with CNF and pure mycelium tissue. It was found that the composites made of mycelium-modified wood and CNF resulted in enhanced physical and mechanical properties compared to the ones made by physically mixing wood, mycelium, and CNF. Scanning electron microscopy (SEM) images showed that mycelium modification covered wood particles with a network of fungal hyphae whereas CNF formed a uniform mycelial film over wood particles. Mycelium modification had a significant effect on reducing water absorption and thickness swelling of the hybrid composites and CNF increased the modulus of rupture and modulus of elasticity, optimally at 2.5% addition. We also present results and analysis pertaining to the development of unique lightweight composite systems with physical and mechanical properties optimized at 5% CNF addition with potential to be used in packaging and furniture applications.

Hybrid Cellulose-Silica Materials from Renewable Secondary Raw Resources: An Eco-friendly Method.

Hybrid organic–inorganic materials based on cellulose matrix and silica particles are obtained from wastes of the local paper recycling mill and sugarcane mill as renewable secondary raw materials. The performance comparison of these hybrid materials made from secondary raw materials against the materials made from pure, raw sources is discussed. The Fourier transform infrared spectra show that cellulose features prevail even at 43 wt% silica nanoparticles in the hybrid materials. Such a high content of silica originated from sugarcane bagasse ash and hollow glass microspheres contributes to the high thermal stability of the final composites, as seen by thermogravimetric analysis with very low water absorption. This one‐step approach of biobased hybrid materials represents an excellent way to produce high‐performance materials with high content of inorganic nanoparticles for a wide variety of applications like energy efficient building material completely cement‐free.

Cellulose-Silica Nanocomposites of High Reinforcing Content with Fungi Decay Resistance by One-Pot Synthesis.

Hybrid bionanocomposites based on cellulose matrix, with silica nanoparticles as reinforcers, were prepared by one-pot synthesis of cellulose surface modified by solvent exchange method to keep the biopolymer net void for hosting inorganic nanoparticles. Neither expensive inorganic-particle precursors nor crosslinker agents or catalysts were used for effective dispersion of reinforcer concentration up to 50 wt %. Scanning electron microscopy of the nanocomposites shows homogeneous dispersion of reinforcers in the surface modified cellulose matrix. The FTIR spectra demonstrated the cellulose features even at 50 weight percent content of silica nanoparticles. Such a high content of silica provides high thermal stability to composites, as seen by TGA-DSC. The fungi decay resistance to Trametes versicolor was measured by standard test showing good resistance even with no addition of antifungal agents. This one-pot synthesis of biobased hybrid materials represents an excellent way for industrial production of high performance materials, with a high content of inorganic nanoparticles, for a wide variety of applications.

Facile and Controlled Fabrication of Cu–Al Layered Double Hydroxide Nanosheets/Laccase Hybrid Films: A Route to Efficient Biocatalytic Removal of Congo Red from Aqueous Solutions

The development of biobased hybrid materials that can efficiently remove environmentally contaminants has broad practical applications for areas. In this work, a novel biomaterial–inorganic hybrid film was fabricated with Cu–Al layered double hydroxide (LDH) nanosheets as host and laccase as guest by using exfoliation/self-assembly monolayer technology. It included two processes: first, a nitric acid intercalation Cu–Al–NO3– LDHs was prepared with Cu–Al–CO32– LDHs through the ion-exchange method, and then Cu–Al–NO3– LDHs was exfoliated into a single-layer nanodispersion system with abundant Cu2+ ions on the surface of the positively charged layered double hydroxides to assemble the (LDHs/laccase)n hybrid multilayer film. The resulting (LDHs/laccase)n hybrid film was characterized by X-ray diffraction, scanning electron microscope, high-resolution transmission electron microscopy, scanning probe microscope, and UV–visible absorption spectroscopy, which all supported the formation of the layer-by-layer sand...

Hybrid biocomposites

Composites are primarily made using matrix and reinforcement as major components but may also contain several other fillers or additives. A majority of the composites are made using synthetic fibers and polymers. However, in the last few decades, focus has been on developing biocomposites using renewable resources. Conventionally, biocomposites are developed using natural fibers such as jute, Kenaf, or Ramie as reinforcement and synthetic resins such as polyethylene, polypropylene and epoxy as matrix. Typically, biocomposites contain either the reinforcement or matrix which makes the composites partially degradable. Such partially degradable composites provide good properties, but the presence of a nonbiodegradable component, particularly as a matrix limits their biodegradability. Alternatively, composites that contain both the matrix and reinforcement from renewable resources which make the composites completely degradable have also been developed. However, these completely biodegradablebiocomposites do not have the desired mechanical properties and stability at high humidities or in aqueous environments which restricts their application. In addition, natural fibers and resins used in biocomposites have inherent limitations and also not easily processable. To overcome limitation of using a single reinforcement or matrix derived from bioresources, hybrid composites that contain more than one reinforcement or matrix are developed. Such hybrid composites are manufactured by either intimately mixing two or more fibers or other reinforcing materials or by placing different layers of the reinforcement and molding them into composites using one or more resins. Conventionally, hybrid composites refer to metallic and ceramic based reinforcement, matrix and fillers. Although hybrid biocomposites are gaining significant attention, the presence of multiple reinforcements and/or matrix makes it difficult to process and also to predict the properties of such composites. Hence, understanding the properties and potential of using multiple reinforcements and/or matrix materials from renewable resources to develop biobased hybrid composites is highly desirable. This article discusses hybrid composites that contain a major proportion of renewable materials. Hybrid composites not only provide better properties but could also lead to substantial cost reduction due to the incorporation of inexpensive raw materials. These composites show potential for use in aeronautical, sporting goods, wind power turbine blades, helmets and civil construction such as pedestrian bridges and many other applications. This review provides an overview of the biobased materials used to develop hybrid composites, their processability and their potential applications. POLYM. COMPOS., 39:E30–E54, 2018. © 2017 Society of Plastics Engineers

Bio-Based Hybrid Polymers from Vinyl Ester Resin and Modified Palm Oil: Synthesis and Characterization

Abstract A series of bio-based hybrid thermosets composed of maleinated acrylated epoxidized palm oil (MAEPO) and vinyl ester resin (VE) were produced using free radical-induced crosslinking. The amount of petroleum-based resin which was replaced by bio-resin (MAEPO) was varied from 5 to 20 wt%. The structure of the polymer systems was investigated by scanning electron microscopy and dynamic mechanical analysis. The mechanical properties of the VE/MAEPO resins were studied using tensile, flexural and impact tests. The result obtained from structural analysis revealed that for the polymer hybrids with up to 20 wt% bio-resin content, there is good compatibility between MAEPO and VE as no phase separation was observed for these systems. The prepared eco-friendly bio-based thermosetting resins exhibit remarkable improvement in toughness parameters, such as ductility and impact strength, thereby showing potential for use in composites and nanocomposites applications.

Layer by layer deposition of polyethylenimine and bio-based polyphosphate on ammonium polyphosphate: A novel hybrid for simultaneously improving the flame retardancy and toughness of polylactic acid

In this study, a facile approach to fabricate a novel bio-based hybrid (BBH) with core/shell structure is presented by taking advantage of plant-derived resources. The BBH developed herein comprises of an inorganic core of ammonium polyphosphate (APP), covered with an organic shell that is constructed via layer-by-layer assembly of a novel bio-based polyelectrolyte (BPE) and polyethylenimine (PEI). BBH can simultaneously enhance the flame retardancy and toughness of polylactic acid (PLA) with very high efficiency. The flame retardant PLA composite can pass UL94 V0 rating at the BBH loading content of 10 wt%. The efficient flame retardant performance is due to its effectiveness in both gas and condensed phases. More importantly, the flame retardant PLA composite containing 10 wt% BBH exhibits ductile fracture with an elongation at break of 27.3%, which is much higher than that of neat PLA (8%). The debonding and plastic void deformation of the PLA matrix around the BBH are responsible for the enhanced toughness. This work provides important hints for devising highly efficient multifunctional flame retardant and broadening the application field of renewable resources.

Water-Soluble Cellulose Derivatives Are Sustainable Additives for Biomimetic Calcium Phosphate Mineralization

The effect of cellulose-based polyelectrolytes on biomimetic calcium phosphate mineralization is described. Three cellulose derivatives, a polyanion, a polycation, and a polyzwitterion were used as additives. Scanning electron microscopy, X-ray diffraction, IR and Raman spectroscopy show that, depending on the composition of the starting solution, hydroxyapatite or brushite precipitates form. Infrared and Raman spectroscopy also show that significant amounts of nitrate ions are incorporated in the precipitates. Energy dispersive X-ray spectroscopy shows that the Ca/P ratio varies throughout the samples and resembles that of other bioinspired calcium phosphate hybrid materials. Elemental analysis shows that the carbon (i.e., polymer) contents reach 10% in some samples, clearly illustrating the formation of a true hybrid material. Overall, the data indicate that a higher polymer concentration in the reaction mixture favors the formation of polymer-enriched materials, while lower polymer concentrations or high precursor concentrations favor the formation of products that are closely related to the control samples precipitated in the absence of polymer. The results thus highlight the potential of (water-soluble) cellulose derivatives for the synthesis and design of bioinspired and bio-based hybrid materials.

Tensile and flexural properties of polylactic acid-based hybrid green composites reinforced by kenaf, bamboo and coir fibers

Bio-based hybrid green composites in unidirectional configuration were prepared by using kenaf, bamboo and coir fibers to reinforce polylactic acid (PLA) polymer matrix. Three types of hybrid green composites: kenaf-coir/PLA, bamboo-coir/PLA and kenaf-bamboo-coir/PLA composites were investigated by tensile and flexural tests. Scanning electron microscopy and optical microscopy were used to observe their microstructural failures. Tensile strength of kenaf-bamboo-coir/PLA composites achieved 187MPa, approximately 20 and 78% higher than bamboo-coir/PLA and kenaf-coir/PLA, respectively. Young’s moduli of the three composites were low, ranging from 6.0 to 7.5GPa. High flexural strength was obtained in both kenaf-bamboo-coir/PLA (199MPa) and bamboo-coir/PLA (206MPa) composites, approximately 16 and 20% higher than that of kenaf-coir/PLA, respectively. However, kenaf-coir/PLA composites showed the highest flexural modulus, approximately 70% higher than other combinations. Higher strain energy per unit volume required to break (toughness) was characteristic of kenaf-bamboo-coir/PLA composites. It was found that the combination of high strength and stiffness of bamboo and kenaf fibers and high ductility of coir fiber improved tensile and flexural strengths compared to those of single fiber green composites.

Dispensing of hydrogel ink onto electrospun biodegradable paper for biomedical applications

In this contribution we present the development of a biobased hybrid material made from a mechanically stable, paper-like fleece combined with a hydrogel, which mimics the extracellular matrix (ECM) of soft tissue. We used methacryl-modified gelatin as described earlier for the formulation of dispensable hydrogel precursor-solutions (bioinks). By variation of the degree of modification we provided viscous liquid inks and physically gelling inks. After deposition, such bioinks could be chemically crosslinkend by UVB irradiation to form non-soluble hydrogels. We produced cell-free hydrogels as well as hydrogels loaded with human fibroblasts from skin biopsies. Freeform fabrication of thin hydrogel-coatings or of three-dimensional (3D) hydrogel constructs was achieved by application of digital 3D printing (bioprinting). For stabilization of the hydrogels we used fleece substrates produced from the biodegradable polymer poly (L-lactide) (PLA) and the modified biopolymer gelatin by electrospinning. The presence of the biomolecule component in the fleece added a more hydrophilic character to the PLA non-wovens, which was crucial for stable bonding of hydrogel and fleece.

Preparation and characterization of bio-based hybrid film containing chitosan and silver nanowires

A bio-based hybrid film containing chitosan (CS) and silver nanowires (AgNWs) has been prepared by a simple casting technique. X-ray diffraction (XRD), Fourier infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and UV–visible spectroscopy were employed to characterize the structure of bio-based film. The bio-based hybrid film showed unique performance compared with bare chitosan film. The incorporated nano-silver could improve the strength properly. The results revealed that AgNWs in CS film, improved its tensile strength more than 62% and Young modulus 55% compared with pure chitosan film. On the other hand tensile strength was increased 36.7% with AgNPs. Importantly, the film also exhibited conductivity and antibacterial properties, which may expand its future application.

Structural, mechanical and thermal properties of bio-based hybrid composites from waste coir residues: Fibers and shell particles

Polypropylene hybrid composites were produced by using coir fibers and coir shell particles at a total weight content of 20%. The effect of hybridization and coupling agent on the morphological, structural, thermal and mechanical properties was investigated. The morphological and structural results show that the coupling agent increased filler/matrix interfacial adhesion. Thermogravimetric analysis indicates that thermal degradation of shell particles (285/465 °C) is lower than coir fibers (331/474 °C). The combination of coir fibers and particles has a positive effect on the Young's modulus with hybrid composites showing intermediate values between non-hybrid composites (improvement between 35 and 50%). The modeling of the mechanical behavior of the manufactured composites was done by physical models (Voigt, Reuss, and Tsai–Pagano models).

Extent of genotypic variation for maize cell wall bioconversion traits across environments and among hybrid combinations

AbstractThe utilization of maize stover as a substrate for bioenergy production demands the development of dual-purpose hybrid varieties combining both, optimal grain yield and improved biomass processing amenability. In this study, our objectives were to assess how contrasting environments influence the expression of cell wall composition and bioconversion traits relevant to cellulosic fuel production, and to study how these traits are inherited in hybrid combinations. To this end, a panel of maize double haploid (DH) lines and their corresponding test-cross (TC) offspring were tested under different locations (primarily in the Netherlands) and characterized for a variety of cell wall compositional and bioconversion features relevant to cellulosic fuel production. Overall, the DH and TC sets displayed extensive genotypic diversity in cell wall composition, polymeric ultrastructure and bioconversion characteristics. Heritability for the different traits was generally high (h2 > ~0.60); essentially implying that systematic differences between genotypes remained constant across divergent environmental conditions. Moreover, correlations between the performance of DH lines and related TC hybrids were significant and favorable for most investigated traits. Strong associations (r > ~0.50) were especially prominent for cell wall lignin content, degree of substitution of cell wall glucuronoarabinoxylans and cell wall convertibility following pretreatment and enzymatic hydrolysis. In conclusion, complex cell wall bioconversion traits constitute accessible and reliable selection criteria for incorporation in modern breeding programs seeking to advance bio-based maize hybrid varieties. The high heritability and environmental stability of these traits guarantee high selection efficacy during the development of superior DH/inbred material; and their predominantly additive nature prescribe that preliminary selection at the inbred level will guarantee similar correlated genetic gains in hybrid breeding.