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Produced water (PW), a waste byproduct of oil and gas extraction, is a complex mixture containing numerous organic solubles and elemental species; these constituents range from polycyclic aromatic hydrocarbons to naturally occurring radioactive materials. Identification of these compounds is critical in developing reuse and disposal protocols to minimize environmental contamination and health risks. In this study, versatile extraction methodologies were investigated for the untargeted analysis of PW. Thin-film solid-phase microextraction with hydrophilic-lipophilic balance particles was utilized for the extraction of organic solubles from eight PW samples from the Permian Basin and Eagle Ford formation in Texas. Gas chromatography-mass spectrometry analysis found a total of 266 different organic constituents including 1,4-dioxane, atrazine, pyridine, and PAHs. The elemental composition of PW was evaluated using dispersive solid-phase extraction followed by inductively coupled plasma-mass spectrometry, utilizing a new coordinating sorbent, poly(pyrrole-1-carboxylic acid). This confirmed the presence of 29 elements including rare earth elements, as well as hazardous metals such as Cr, Cd, Pb, and U. Utilizing chemometric analysis, both approaches facilitated the discrimination of each PW sample based on their geochemical origin with a prediction accuracy above 90% using partial least-squares-discriminant analysis, paving the way for PW origin tracing in the environment.

The ultimate goal of this paper is to develop novel ceramic-polymer-based biocomposite orthopedic scaffolds with the help of additive manufacturing. Specifically, we incorporate a bioceramic known as amorphous magnesium phosphate (AMP) into polylactic acid (PLA) with the help of the melt-blending technique. Magnesium phosphate (MgP) was chosen as the bioactive component as previous studies have confirmed its favorable biomaterial properties, especially in orthopedics. Special care was taken to develop constant diameter AMP-PLA composite filaments, which would serve as feedstock for a fused filament fabrication (FFF)-based three-dimensional (3D) printer. Before the filaments were used for FFF, a thorough set of characterization protocols comprising of phase analysis, microstructure evaluations, thermal analysis, rheological analysis, and

Pyrrole was N-functionalized with solid carbon dioxide followed by chemical polymerization to create a new air-stable, granular, and water-insoluble sorbent, poly(pyrrole-1-carboxylic acid) (PPy-CO2). PPy-CO2 exhibited enhanced affinity for the sorption of metal ions compared to unfunctionalized PPy due to the incorporation of carboxylate functional groups directly onto the polymer backbone. As a freestanding sorbent material, immobilization to an additional solid support is not needed. Sorption, and therefore preconcentration, occurs simultaneously to achieve efficient removal and recovery of metal ions by a pH-dependent sorption-desorption mechanism. PPy-CO2 was evaluated on the analytical scale for the solid-phase extraction of a range of metal ions and found to efficiently preconcentrate rare earth elements (REEs), Th, and heavy metals (Cr, Fe, Cd, and Pb), which allowed quantitation by inductively coupled plasma mass spectrometry (ICP-MS). The impact of sorption parameters, such as solution pH, amount of sorbent, and sorption time, and the effect of desorption flow rate for recovery were investigated and optimized using ultrasound-assisted dispersive solid-phase extraction (UAD-SPE) with ICP-MS analysis. Maximum efficiency for sorption and recovery of most metal ions was achieved at a solution pH of 6.0, 10 mg of sorbent, a sorption time of 5 min, and desorption conditions of 1 mL of 2 M nitric acid applied at a flow rate of 0.25 mL min-1. Detection limits for REEs and Th ranged from 0.2-3.4 ng L-1 for REEs and Th and 0.9-5.7 ng L-1 for heavy metals. Linear ranges from 0.1-1000 μg L-1 for REEs and 0.1-500 μg L-1 for heavy metals and Th were also observed. PPy-CO2 successfully preconcentrated and facilitated the determination of the targeted metal ions in water matrices of varying complexity, including tap water, well water, river water, and produced water samples. These results indicate the potential application of PPy-CO2 for larger-scale recovery and removal of valuable or hazardous metal ions.

The cost and availability of 2,5-furandicarboxylic acid (FDCA), a monomer for poly(ethylene 2,5-furandicarboxylate) (PEF), limit the use of PEF as a biobased alternative to poly(ethylene terephthal...

Poly(ethylene terephthalate) (PET), known for its clarity, food safety, toughness, and barrier properties, is a preferred polymer for rigid packaging applications. PET is also one of the most recycled polymers worldwide. In light of climate change, significant efforts are underway to improve the carbon footprint of PET by synthesizing it from bio-based feedstocks. Often times, specific applications demand PET to be copolymerized with other monomers. This work focuses on copolymerization of PET with a bio-based co-monomer, 2,5-furandicarboxylic acid (FDCA) to produce the copolyester (PETF). We report the multifunction of FDCA to influence the esterification reaction kinetics and the depolymerization kinetics (via alkaline hydrolysis) of the copolyester PETF. NMR spectroscopy and titrimetric studies revealed that copolymerization of PET with different levels of FDCA improved the esterification reaction kinetics by enhancing the solubility of monomers. During the alkaline hydrolysis, the presence of FDCA units in the backbone almost doubled the PET conversion and monomer yield. Based on these findings, it is demonstrated that the FDCA facilitates the esterification, as well as depolymerization of PET, and potentially enables reduction of reaction temperatures or shortened reaction times to improve the carbon footprint of the PET synthesis and depolymerization process.

N-functionalization of pyrrole with carbon disulfide and subsequent chemical polymerization resulted in the development of a new sorbent material for the extraction of metals. The synthesized polymer, poly(pyrrole-N-carbodithioic acid) (PPy-CS2), is an air-stable, granular powder that is insoluble in water. PPy-CS2 combines pH-dependent chelation, extraction, and desorption sorbent properties that are exploited for the selective extraction and sensitive determination of heavy metals in water matrices using ultrasound-assisted dispersive micro solid-phase extraction and inductively coupled plasma mass spectrometry. Excellent removal and recovery of Cd(II), Co(II), Cu(II), Ni(II), Pb(II), and Zn(II) were achieved and compared with unfunctionalized polypyrrole, which demonstrated extraction resulted from chelation of the metal ions. The extraction efficiency of the PPy-CS2 sorbent as a function of pH, amount of sorbent, extraction time, and flow rate of the desorption solution were evaluated. Limits of detection ranged from 0.3 for cadmium to 11.2 ng/L for zinc with linear dynamic ranges from 0.1 to 500 μg/L and relative standard deviations from 2.2 to 6.3%. The sample preparation method was successfully applied for determination of the target metals in raw well water, treated well water, and river water. Validation was performed by analysis of a certified reference standard for trace metals in drinking water.

Poly(ethylene 2,5-furandicarboxylate) (PEF) has garnered considerable industrial and academic interest as a renewable alternative to traditional polyesters due to its superior barrier and thermal properties. While efforts for the industrial scale production of PEF from 2,5-furandicarboxylic acid (FDCA) and ethylene glycol (EG) are underway, most of the published literature on PEF follows the conventional terephthalic acid (TPA) based polyester synthesis protocol. In this study, we reveal for the first time that the solubility of FDCA is an order of magnitude higher in EG compared to that in TPA at the process temperatures. The enhanced solubility of FDCA in EG results in improved esterification kinetics especially at temperatures from 180–210 °C to yield complete end group conversion. We further demonstrate that it is advantageous to perform the direct esterification step of PEF synthesis in a lower temperature range than that in previous reports reducing the potential side reactions in addition to cost and energy savings at the industrial scale. This work can provide new insights into the sustainable synthesis of FDCA-based polyesters for bio-based packaging.

Of most solid materials available as potential solid electrolytes for lithium-ion batteries, the crystalline perovskite type lithium lanthanum titanate (Li0.5La0.5TiO3 or LLTO) has been shown to possess one of the highest room temperature bulk ionic conductivity. However, grain boundary contributions lower this value by two orders of magnitude. Herein, we present a composite of silica-based glass and perovskite which results in an amorphous composite having denser microstructure and better stability than the LLTO itself. Also, this composite possessed no grain boundary contributions and has an increased ionic conductivity than crystalline perovskite. An alternate fabrication route further improved the conductivity of the composite electrolyte.

Transparent oxyfluoride glass ceramics with a novel composition of Er3+, Yb3+:Sr1−xYxF2+x nano-crystals were processed. When excited under infrared light, an intense green upconverted luminescence was observed for the glass ceramic obtained from the precursor glass after a heat treatment of 4 h at 750 °C. X-ray diffraction and transmission electron microscopy analysis confirmed the precipitation of Sr1−xYxF2+x nano-crystals of sizes in the range of 9–45 nm in the heat treated samples. The position of Er3+, Yb3+ ions in the sample (either amorphous or crystalline phases) was studied at four different heat treatment temperatures of 600, 650, 700 and 750 °C. The measurements were based on analyzing the lifetimes of the 4S3/2 and 4I11/2 levels of erbium and the 2F5/2 level of ytterbium. Ytterbium and erbium ions started to incorporate into the crystalline phase when the heat treatment temperature was more than 650 °C and 600 °C, respectively. The sample that was heat treated at 750 °C for four hours showed the highest green upconversion intensity among the other heat treated samples. In this sample, majority of Er3+, Yb3+ ions were in the crystalline phase as the lifetime of 4S3/2 (Er3+) and 2F 5/2 (Yb3+) levels were increased to 500 μs and 2 ms, respectively, which are longer than their values in the precursor glass. High ion solubility of Er3+ and Yb3+ in the novel Sr1−xYxF2+x nano-crystals and their local environments in the nano-structure are believed to be the reasons for this high intense green upconversion.

The presence of highly modifiable chemical functional groups, abundance of functional groups, and their biological origin make proteins an important class of biomaterials from a fundamental science and applied engineering perspective. Hence, the utilization of proteins from the animal rendering industry (animal protein, AP) for high-value, nonfeed, and nonfertilizer applications is intensely pursued. Although this leads to the exploration of protein-derived plastics as a plausible alternative, the proposed methods are energy-intensive and not based on protein in its native form, which leads to high processing and production costs. Here, we propose, for the first time, novel pathways to develop engineered hybrid systems utilizing AP in its native form and epoxy resins with mechanical properties ranging from toughened thermosets to elastic epoxy-based systems. Furthermore, we demonstrate the capability to engineer the properties of epoxy–AP hybrids from high-strength hybrids to elastic films through controlling the interaction, hydrophilicity, as well as the extent of cross-linking and network density. Through the facile introduction of cochemicals, a sevenfold increase in the mechanical properties of the conventional epoxy–AP hybrid is achieved. Similarly, because of better compatibility afforded by the similar hydrophilicity, AP demonstrated higher cross-linking capability with a water-soluble epoxy (WEP) matrix, resulting in an elastic WEP–AP hybrid without any external aid.

Correction for ‘Role of enhanced solubility in esterification of 2,5-furandicarboxylic acid with ethylene glycol at reduced temperatures: energy efficient synthesis of poly(ethylene 2,5-furandicarboxylate)’ by Anup S. Joshi et al., React. Chem. Eng., 2018, 3, 447–453.

Calcium phosphates (CaPs) are major chemical constituents of mammalian bone. Their osteoconductivity in vitro and in vivo has encouraged their use in biomaterial applications such as implant materials and drug delivery. High aspect ratio nanoparticles are attractive for many biomedical applications; however, precise control of the phase and morphology is challenging. The impact of fuel-to-oxidant ratio, pH, and cation chemistry on morphology and phase was studied for CaP-based compositions by microwave-assisted solution combustion synthesis (MASCS) in a urea–nitrate (fuel–oxidant) system. An initial calcium to phosphate ratio of 1.5 was used. Highly crystalline hydroxyapatite (HA) and biphasic CaP nanoparticle compositions were produced as confirmed by x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. MASCS was capable of synthesizing high aspect ratio (∼5 to 20) single and biphasic CaP nanoparticles with diameters ranging from 250 to 500 nm and lengths between 2 and 10 μm.

Airborne particulate matter samples were collected during biosolids applications in the summer 2009. The biosolids were applied with the injection method. The major emphasis of the analysis was on providing in depth information such as size, shape, morphology, and chemical composition of different particles collected before, during, and after land application of biosolids. A significant correlation was observed between sampling stages and size distribution of particles. Particles with larger diameter (> 10 μm) during the application stage were observed to be very high. The particle shape analysis identified particles as polygons and spherical in shape as defined by the shape factor. There was a significant increase in agglomerates and floccules for the application stage. The elemental composition of particles obtained by energy dispersive spectroscopy spectra suggests that the particles collected contained elements such as C, O, Na, Mg, Al, Si, S, K, Ca, Fe, Cu, and Zn. It was observed that Cr, Pb, P, Cd, and Mn were present only in particles collected during the application stage and were not detected during the pre-application stage or the post-application stage. Presence of these elements during the application stage could be attributed to the biosolids application. © 2011 American Institute of Chemical Engineers Environ Prog, 32: 325-334, 2013

Halloysite nanotubes (HNT) reinforced polylactic acid (PLA) nanocomposite fibers were produced using an electrospinning approach for biomedical applications. The PLA/HNT nanocomposite fibers were characterized using x-ray diffraction (XRD) and scanning electron microscopy (SEM). The various factors such as type of solvent, solution concentration, HNT loading and feed rate, affecting the electrospinning process, and the morphology of the nanofibers were investigated, and the optimum values for these parameters are suggested. The results indicated that the addition of dimethylformamide (DMF) to chloroform facilitated the electrospinning process because of the improvement in electrical conductivity and viscosity of the solution. Nanometer-sized fibers were obtained by the addition of HNT to PLA. HNT loadings had a significant effect on the morphology of the nanofibers. Bead-free fibers were produced at feed rates between 1 and 4 mL/h.

Nanoscale Bi–Te particles with thermoelectric properties on copper substrate were investigated. The substrate was prepared by electroplating copper layer on a copper zinc alloy plate in a copper sulfate solution. Electrodeposition of the Bi–Te alloy particles was then performed in a nitrate bath. The electrolyte is composed of 0.05 M bismuth nitrate and 0.01 M tellurium dioxide dissolved in 2.0 M HNO 3 . Cyclic voltammetry and quartz microbalance tests associated with the electrodeposition process were conducted to show the mechanism and kinetics of the deposition. The morphology and compositional analysis of Bi–Te was obtained using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) respectively. The morphology analysis suggested that nanoscale Bi–Te particles were obtained and the EDS results indicated that the surface of the copper substrate contained Cu 2 O. The atomic ratio 1:1 for Bi:Te in the alloy, which is equivalent to the weight percentage of Bi:Te = 62%:38% was confirmed from the data obtained.

The structural complexity of vapor-grown carbon nanofibers means that they require a method that determines both their elastic properties and their corresponding morphology. A three-point bending test method was developed combining atomic force microscopy, transmission electron microscopy (TEM) and focused ion beam techniques to suspend individual nanofibers and measure their deflection coupled with accurate determinations of inner and outer diameters and morphology using high resolution TEM. This resulted in much improved accuracy and reproducibility of the measured values of the elastic modulus which ranged from 6 to 207 GPa. The data showed two distinct trends, with higher values of the modulus when the outer wall thickness of the nanofibers is larger than that of the inner wall, with the values decreasing with the overall wall thickness. These results suggest that the more ordered layers of the outer wall, closest to the inner wall, are mostly responsible for the nanofiber strength. For large nanofiber wall thicknesses of greater than 80 nm, the elastic modulus becomes independent of the thickness with a value of approximately 25 GPa. The results also demonstrate that this technique can be a standardized one for the detailed study of mechanical properties of nanofibers and their relationship to morphology.

The lack of a low cost, high volume method to produce carbon nanotubes has greatly limited their commercialization. Carbon nanofibers have a similar structure and properties as nanotubes and are a commercially viable alternative to them. In recent years many of the difficulties of commercial nanofiber production have been overcome through innovations in their manufacturing process. It is now possible to produce carbon nanofibers of different grades, such as thinner and thicker walled ones, and low heat treated and high heat treated ones. Most significantly, commercial quantities can now be produced of carbon nanofibers that have been surface functionalized with carboxylic acid groups, making them suitable for further functionalization and new classes of applications, such as biomedical sensors and drug delivery. Despite their cost advantages and availability more widespread use of carbon nanofibers has been hampered by uncertainties in their molecular structure and a lack of physical property measurements. However, recent theoretical and experimental studies have addressed these deficiencies showing that these fibers have a cone-helix structure under the usual manufacturing conditions. Additionally, small amounts of a segmented carbon nanotube structure, commonly called a bamboo structure, are also present. When the conical nanofibers were heat treated they were found to transform to a stacked cone structure. Advances in surface functionalization have allowed a variety of groups to be incorporated on them, significantly enhancing their properties and potential applications. Finally, the recent development of a new method to measure the elastic properties and morphology of single nanofibers has clearly demonstrated the high strength of these fibers. These nanofibers now represent a well understood and well characterized graphitic carbon nanomaterial that can be manufactured at low cost in large quantities, and have the potential to bring widespread use of nanotechnology to a variety of fields.

Vapor grown carbon nanofibers have been extensively manufactured and investigated in recent years. In this study commercially available vapor grown carbon nanofibers subjected to different processing and post processing conditions were studied employing high resolution TEM images. The analysis showed that the fibers consist primarily of conical nanofibers, but can contain a significant amount of bamboo nanofibers. Most conical nanofibers were found to consist of an ordered inner layer and a disordered outer layer, with the cone angle distribution of the inner layers indicating that these cannot have a stacked cone structure but are compatible with a cone-helix structure. Fibers that have been heat treated to temperatures above 1,500 °C undergo a structural transformation with the ordered inner layers changing from a cone-helix structure to a highly ordered multiwall stacked cone structure. The bamboo nanofibers were found to have a tapered multiwall nanotube structure for the wall and a multishell fullerene structure for the cap of each segment, surrounded by a disordered outer layer. When these fibers are heat treated the disordered outer layers transform to an ordered multiwall nanotube structure and merge with the wall of each segment. The end caps of each segment transform from a smooth multiwall fullerene structure to one consisting of disjointed graphene planes. A reaction-diffusion mechanism is proposed to explain the growth and structure of the bamboo nanofibers.

Bio-based polymer foams have been gaining immense attention in recent years due to their positive contribution towards reducing the global carbon footprint, lightweighting, and enhancing sustainability. Currently, polylactic acid (PLA) remains the most abundant commercially consumed biopolymer, but suffers from major drawbacks such as slow crystallization rate and poor melt processability. However, blending of PLA with a secondary polymer would enhance the crystallization rate and the thermal properties based on their compatibility. This study investigates the physical and compatibilized blends of PLA/poly (butylene succinate-co-adipate) (PBSA) processed via supercritical fluid-assisted (ScF) injection molding technology using nitrogen (N2) as a facile physical blowing agent. Furthermore, this study aims at understanding the effect of blending and ScF foaming of PLA/PBSA on crystallinity, melting, and viscoelastic behavior. Results show that compatibilization, upon addition of triphenyl phosphite (TPP), led to an increase in molecular weight and a shift in melting temperature. Additionally, the glass transition temperature (Tg) obtained from the tanδ curve was observed to be in agreement with the Tg value predicted by the Gordon–Taylor equation, further confirming the compatibility of PLA and PBSA. The compatibilization of ScF-foamed PLA–PBSA was found to have an increased crystallinity and storage modulus compared to their physically foamed counterparts.

Context: Solid lipid nanoparticles (SLNs) can efficiently and efficaciously incorporate anti-cancer agents. Objective: To prepare and characterise tamoxifen (TAM)-loaded SLNs. Materials and methods: Glyceryl monostearate, Tween-80, and trehalose were used in SLNs. SLNs were tested via dynamic light scattering (DLS), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). Results: Characterisation studies revealed SLNs of about 540 nm with a negative surface charge and confirmed the entrapment of TAM in the SLNs. The entrapment efficiency was estimated to be 60%. Discussion: The in vitro drug release profile demonstrated a gradual increase followed by a release plateau for several days. A drug concentration-dependent increase in cytotoxic activity was observed when the SLNs were evaluated in cell cultures. Conclusion: Biocompatible and stable lyophilised SLNs were successfully prepared and found to...

There is an increasing demand for an injectable cell coupled three-dimensional (3D) scaffold to be used as bone fracture augmentation material. To address this demand, a novel injectable osteogenic scaffold called PN-COL was developed using cells, a natural polymer (collagen type-I), and a synthetic polymer (polycaprolactone (PCL)). The injectable nanofibrous PN-COL is created by interspersing PCL nanofibers within pre-osteoblast cell embedded collagen type-I. This simple yet novel and powerful approach provides a great benefit as an injectable bone scaffold over other non-living bone fracture stabilization polymers, such as polymethylmethacrylate and calcium content resin-based materials. The advantages of injectability and the biomimicry of collagen was coupled with the structural support of PCL nanofibers, to create cell encapsulated injectable 3D bone scaffolds with intricate porous internal architecture and high osteoconductivity. The effects of PCL nanofiber inclusion within the cell encapsulated collagen matrix has been evaluated for scaffold size retention and osteocompatibility, as well as for MC3T3-E1 cells osteogenic activity. The structural analysis of novel bioactive material proved that the material is chemically stable enough in an aqueous solution for an extended period of time without using crosslinking reagents, but it is also viscous enough to be injected through a syringe needle. Data from long-term in vitro proliferation and differentiation data suggests that novel PN-COL scaffolds promote the osteoblast proliferation, phenotype expression, and formation of mineralized matrix. This study demonstrates for the first time the feasibility of creating a structurally competent, injectable, cell embedded bone tissue scaffold. Furthermore, the results demonstrate the advantages of mimicking the hierarchical architecture of native bone with nano- and micro-size formation through introducing PCL nanofibers within macron-size collagen fibers and in promoting osteoblast phenotype progression for bone regeneration.

For several decades, composites made of polylactic acid-calcium phosphates (PLA-CaP) and polylactic acid-co-glycolic acid-calcium phosphates (PLGA-CaP) have seen widespread uses in orthopedic applications. This paper reviews the fabrication aspects of these composites, following the ubiquitous materials science approach by studying "processing-structure-property" correlations. Various fabrication processes such as microencapsulation, phase separation, electrospinning, supercritical gas foaming, etc., are reviewed, with specific examples of their applications in fabricating these composites. The effect of the incorporation of CaP materials on the mechanical and biological performance of PLA/PLGA is addressed. In addition, this paper describes the state of the art on challenges and innovations concerning CaP dispersion, incorporation of biomolecules/stem cells and long-term degradation of the composites.

Bi-functional coatings of carbonated calcium deficient hydroxyapatite (CDHA) on Ti alloys were developed by using a biomimetic coating process. The bi-functionality was achieved by loading alendonate sodium (AS), an approved bisphosphonate drug used for the treatment of osteoporosis, into the inner layers of CDHA coatings. Three possible methods of loading AS into CDHA coatings were systematically studied and compared. The results indicated that the co-precipitation method had greater benefits and can modify the release profile of AS by incorporating AS in the inner layers of the coatings. As a preliminary study, the influences of applied AS dosage to CDHA coatings were evaluated using XRD and SEM. In vitro tests indicated that the AS content on CDHA coatings played a significant role, and optimum AS content in local area is beneficial for osteoblast cells proliferation. It is expected that the CDHA–AS coatings via the co-precipitation approach have potential for bone tissue engineering applications.

Cross-sections of laser fabricated nanosharp tips and microbumps on silicon and metal thin films are produced and examined in this work. These structures are formed with a Q-switched neodymium doped yttrium aluminum garnet nanosecond-pulse laser, emitting at its fourth harmonic of 266 nm, using a mask projection technique to generate circular laser spots, several microns in diameter. Cross-section of selected structures were produced using a focused ion beam and were characterized via electron microscopy. The diffraction patterns of the silicon samples indicate that the laser formed tip maintains the same single crystal structure as the original silicon film. Examinations of the laser formed structures in metal films confirm that the microbumps are hollow, while revealing that the vertical protrusions are solid.