This study examines the feasibility of catalytically pretreated biochar derived from the dried exocarp or fruit peel of mangostene with Group I alkali metal hydroxide (KOH). The pretreated char was activated in the presence of carbon dioxide gas flow at high temperature to upgrade its physiochemical properties for the removal of copper, Cu(II) cations in single solute system. The effect of three independent variables, including temperature, agitation time and concentration, on sorption performance were carried out. Reaction kinetics parameters were determined by using linear regression analysis of the pseudo first, pseudo second, Elovich and intra-particle diffusion models. The regression co-efficient, R² values were best for the pseudo second order kinetic model for all the concentration ranges under investigation. This implied that Cu(II) cations were adsorbed mainly by chemical interactions with the surface active sites of the activated biochar. Langmuir, Freundlich and Temkin isotherm models were used to interpret the equilibrium data at different temperature. Thermodynamic studies revealed that the sorption process was spontaneous and endothermic. The surface area of the activated sample was 367.10 m²/g, whereas before base activation, it was only 1.22 m²/g. The results elucidated that the base pretreatment was efficient enough to yield porous carbon with an enlarged surface area, which can successfully eliminate Cu(II) cations from waste water.
The adsorption of tributyltin (TBT), onto three mesoporous silica adsorbents functionalized with calix[4]arene, p-tert-butylcalix[4]arene and p-sulfonatocalix[4]arene (MCM-TDI-C4, MCM-TDI-PC4 and MCM-TDI-C4S, respectively) has been compared. Batch adsorption experiments were carried out and the effect of contact time, initial TBT concentration, pH and temperature were studied. The Koble-Corrigan isotherm was the most suitable for data fitting. Based on a Langmuir isotherm model, the maximum adsorption capacities were 12.1212, 16.4204 and 7.5757 mg/g for MCM-TDI-C4, MCM-TDI-PC4 and MCM-TDI-C4S, respectively. The larger uptake and stronger affinity of MCM-TDI-PC4 than MCM-TDI-C4 and MCM-TDI-C4S probably results from van der Waals interactions and the pore size distribution of MCM-TDI-PC4. Gibbs free energies for the three adsorption processes of TBT presented a negative value, reflecting that TBT/surface interactions are thermodynamic favorable and spontaneous. The interaction processes were accompanied by an increase of entropy value for MCM-TDI-C4 and MCM-TDI-C4S (43.7192 and 120.7609 J/mol K, respectively) and a decrease for MCM-TDI-PC4 (-37.4704 J/mol K). It is obviously observed that MCM-TDI-PC4 spontaneously adsorbs TBT driven mainly by enthalpy change, while MCM-TDI-C4 and MCM-TDI-C4S do so driven mainly by entropy changes.
A metal-free mesoporous carbon nitride (MCN) was investigated for the first time as an adsorbent for N-nitrosopyrrolidine (NPYR), which is one of the nitrosamine pollutants. Under the same condition, the adsorption capability of the MCN was found to be higher than that of the MCM-41. Since the adsorption isotherm was consistent with Langmuir and Freundlich model equations, it was suggested that the adsorption of NPYR molecules on the MCN occurred in the form of mono-molecular layer on the heterogeneous surface sites. It was proposed that MCN with suitable adsorption sites was beneficial for the adsorption of NPYR. The evidence on the interaction between the NPYR molecules and the MCN was supported by fluorescence spectroscopy. Two excitation wavelengths owing to the terminal N-C and N=C groups were used to monitor the interactions between the emission sites of the MCN and the NPYR molecules. It was confirmed that the intensity of the emission sites was quenched almost linearly with the concentration of NPYR. This result obviously suggested that the MCN would be applicable as a fluorescence sensor for detection of the NPYR molecules. From the Stern-Volmer plot, the quenching rate constant of terminal N-C groups was determined to be ca. two times higher than that of the N=C groups on MCN, suggesting that the terminal N-C groups on MCN would be the favoured sites interacted with the NPYR. Since initial concentration can be easily recovered, the interactions of NPYR on MCN were weak and might only involve electrostatic interactions.
Cellulose carbamate (CCs) was produced from kenaf core pulp (KCP) using microwave reactor-assisted method. The effects of urea concentration and reaction time on the formation of nitrogen content in CCs were investigated. The CCs' solubility in LiOH/urea system was determined and its membranes were characterized. As the urea content and reaction time increased, the nitrogen content form in CCs increased which enhanced the CCs' solubility. The formation of CCs was confirmed by Fourier transform infrared spectroscopy (FT-IR) and nitrogen content analysis. The CCs' morphology was examined using Scanning electron microscopy (SEM). The cellulose II and crystallinity index of the membranes were confirmed by X-ray diffraction (XRD). The pore size of the membrane displayed upward trend with respect to the urea content observed under Field emission scanning electron microscope (FESEM). This investigation provides a simple and efficient procedure of CCs determination which is useful in producing environmental friendly regenerated CCs.
The large surface area of highly porous titanium structures produced by additive manufacturing can be modified using biofunctionalizing surface treatments to improve the bone regeneration performance of these otherwise bioinert biomaterials. In this longitudinal study, we applied and compared three types of biofunctionalizing surface treatments, namely acid-alkali (AcAl), alkali-acid-heat treatment (AlAcH), and anodizing-heat treatment (AnH). The effects of treatments on apatite forming ability, cell attachment, cell proliferation, osteogenic gene expression, bone regeneration, biomechanical stability, and bone-biomaterial contact were evaluated using apatite forming ability test, cell culture assays, and animal experiments. It was found that AcAl and AnH work through completely different routes. While AcAl improved the apatite forming ability of as-manufactured (AsM) specimens, it did not have any positive effect on cell attachment, cell proliferation, and osteogenic gene expression. In contrast, AnH did not improve the apatite forming ability of AsM specimens but showed significantly better cell attachment, cell proliferation, and expression of osteogenic markers. The performance of AlAcH in terms of apatite forming ability and cell response was in between both extremes of AnH and AsM. AcAl resulted in significantly larger volumes of newly formed bone within the pores of the scaffold as compared to AnH. Interestingly, larger volumes of regenerated bone did not translate into improved biomechanical stability as AnH exhibited significantly better biomechanical stability as compared to AcAl suggesting that the beneficial effects of cell-nanotopography modulations somehow surpassed the benefits of improved apatite forming ability. In conclusion, the applied surface treatments have considerable effects on apatite forming ability, cell attachment, cell proliferation, and bone ingrowth of the studied biomaterials. The relationship between these properties and the bone-implant biomechanics is, however, not trivial.
Morphological surface modifications have been reported to enhance the performance of biomedical implants. However, current methods of introducing graded porosity involves postprocessing techniques that lead to formation of microcracks, delamination, loss of fatigue strength, and, overall, poor mechanical properties. To address these issues, we developed a microwave sintering procedure whereby pure titanium powder can be readily densified into implants with graded porosity in a single step. Using this approach, surface topography of implants can be closely controlled to have a distinctive combination of surface area, pore size, and surface roughness. In this study, the effect of various surface topographies on in vitro response of neonatal rat calvarial osteoblast in terms of attachment and proliferation is studied. Certain graded surfaces nearly double the chance of cell viability in early stages (∼one month) and are therefore expected to improve the rate of healing. On the other hand, while the osteoblast morphology significantly differs in each sample at different periods, there is no straightforward correlation between early proliferation and quantitative surface parameters such as average roughness or surface area. This indicates that the nature of cell-surface interactions likely depends on other factors, including spatial parameters.
This paper focuses on the micro- and nano-topological organization of a hydrogel, constituted by a mixture of bacterial cellulose and acrylic acid, and intended for biomedical applications. The presence of acrylic acid promotes the formation of two interpenetrated continuous phases: the primary "pores phase" (PP) containing only water and the secondary "polymeric network phase" (PNP) constituted by the polymeric network swollen by the water. Low field Nuclear Magnetic Resonance (LF NMR), rheology, Scanning Electron Microscopy (SEM) and release tests were used to determine the characteristics of the two phases. In particular, we found that this system is a strong hydrogel constituted by 81% (v/v) of PP phase the remaining part being occupied by the PNP phase. Pores diameters span in the range 10-100 μm, the majority of them (85%) falling in the range 30-90 μm. The high PP phase tortuosity indicates that big pores are not directly connected to each other, but their connection is realized by a series of interconnected small pores that rend the drug path tortuous. The PNP is characterized by a polymer volume fraction around 0.73 while mesh size is around 3 nm. The theoretical interpretation of the experimental data coming from the techniques panel adopted, yielded to the micro- and nano-organization of our hydrogel.
This study evaluated the potential of stimuli-responsive bacterial cellulose-g-poly(acrylic acid-co-acrylamide) hydrogels as oral controlled-release drug delivery carriers. Hydrogels were synthesized by graft copolymerization of the monomers onto bacterial cellulose (BC) fibers by using a microwave irradiation technique. The hydrogels were characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). FT-IR spectroscopy confirmed the grafting. XRD showed that the crystallinity of BC was reduced by grafting, whereas an increase in the thermal stability profile was observed in TGA. SEM showed that the hydrogels exhibited a highly porous morphology, which is suitable for drug loading. The hydrogels demonstrated a pH-responsive swelling behavior, with decreased swelling in acidic media, which increased with increase in pH of the media, reaching maximum swelling at pH 7. The release profile of the hydrogels was investigated in simulated gastric fluid (SGF) and simulated intestinal fluid (SIF). The hydrogels showed lesser release in SGF than in SIF, suggesting that hydrogels may be suitable drug carriers for oral controlled release of drug delivery in the lower gastrointestinal tract.
Porous Carbon Nanoparticles (PCNs) with well-developed microporosity were obtained from bio-waste oil palm leaves (OPL) using single step pyrolysis in nitrogen atmosphere at 500-600 °C in tube-furnace without any catalysis support. The key approach was using silica (SiO2) bodies of OPL as a template in the synthesis of microporous carbon nanoparticles with very small particle sizes of 35-85 nm and pore sizes between 1.9-2 nm.
Porous structured silicon or porous silicon (PS) powder was prepared by chemical etching of silicon powder in an etchant solution of HF: HNO₃: H₂O (1:3:5 v/v). An immersion time of 4 min was sufficient for depositing Cu metal from an aqueous solution of CuSO₄ in the presence of HF. Scanning electron microscopy (SEM) analysis revealed that the Cu particles aggregated upon an increase in metal content from 3.3 wt% to 9.8 wt%. H₂-temperature programmed reduction (H₂-TPR) profiles reveal that re-oxidation of the Cu particles occurs after deposition. Furthermore, the profiles denote the existence of various sizes of Cu metal on the PS. The Cu-PS powders show excellent catalytic reduction on the p-nitrophenol regardless of the Cu loadings.
Recently, as a supplement of cement, the utilization of pozzolanic materials in cement and concrete manufacturing has increased significantly. This study investigates the scope to use pozzolanic wastes (slag, palm oil fuel ash and rice husk ash) as an alkali activated binder (AAB) that can be used as an alternative to cement. To activate these materials, sodium hydroxide solution was used at 1.0, 2.5 and 5.0 molar concentration added into the mortar, separately. The required solution was used to maintain the flow of mortar at 110% ± 5%. The consistency and setting time of the AAB-paste were determined. Mortar was tested for its flow, compressive strength, porosity, water absorption and thermal resistance (heating at 700 °C) and investigated by scanning electron microscopy. The experimental results reveal that AAB-mortar exhibits less flow than that of ordinary Portland cement (OPC). Surprisingly, AAB-mortars (with 2.5 molar solution) achieved a compressive strength of 34.3 MPa at 28 days, while OPC shows that of 43.9 MPa under the same conditions. Although water absorption and porosity of the AAB-mortar are slightly high, it shows excellent thermal resistance compared to OPC. Therefore, based on the test results, it can be concluded that in the presence of a chemical activator, the aforementioned pozzolans can be used as an alternative material for cement.
Multi-walled carbon nanotubes (MWCNTs) were prepared via chemical vapor deposition (CVD) using a series of different catalysts, derived from FeCoNiAl, CoNiAl and FeNiAl layered double hydroxides (LDHs). Catalyst-active particles were obtained by calcination of LDHs at 800 °C for 5 h. Nitrogen and hexane were used as the carrier gas and carbon source respectively, for preparation of MWCNTs using CVD methods at 800 °C. MWCNTs were allowed to grow for 30 min on the catalyst spread on an alumina boat in a quartz tube. The materials were subsequently characterized through X-ray diffraction, Fourier transform infrared spectroscopy, surface area analysis, field emission scanning electron microscopy and transmission electron microscopy. It was determined that size and yield of MWCNTs varied depending on the type of LDH catalyst precursor that is used during synthesis. MWCNTs obtained using CoNiAl-LDH as the catalyst precursor showed smaller diameter and higher yield compared to FeCoNiAl and FeNiAl LDHs.
Powder-based inkjet 3D printing method is one of the most attractive solid free form techniques. It involves a sequential layering process through which 3D porous scaffolds can be directly produced from computer-generated models. 3D printed products' quality are controlled by the optimal build parameters. In this study, Calcium Sulfate based powders were used for porous scaffolds fabrication. The printed scaffolds of 0.8 mm pore size, with different layer thickness and printing orientation, were subjected to the depowdering step. The effects of four layer thicknesses and printing orientations, (parallel to X, Y and Z), on the physical and mechanical properties of printed scaffolds were investigated. It was observed that the compressive strength, toughness and Young's modulus of samples with 0.1125 and 0.125 mm layer thickness were more than others. Furthermore, the results of SEM and μCT analyses showed that samples with 0.1125 mm layer thickness printed in X direction have more dimensional accuracy and significantly close to CAD software based designs with predefined pore size, porosity and pore interconnectivity.
A novel porous three-dimensional bone scaffold was developed using a natural polymer (alginate/Alg) in combination with a naturally obtained biomineral (nano cockle shell powder/nCP) through lyophilization techniques. The scaffold was developed in varying composition mixture of Alg-nCP and characterized using various evaluation techniques as well as preliminary in vitro studies on MG63 human osteoblast cells. Morphological observations using SEM revealed variations in structures with the use of different Alg-nCP composition ratios. All the developed scaffolds showed a porous structure with pore sizes ideal for facilitating new bone growth; however, not all combination mixtures showed subsequent favorable characteristics to be used for biological applications. Scaffolds produced using the combination mixture of 40% Alg and 60% nCP produced significantly promising results in terms of mechanical strength, degradation rate, and increased cell proliferation rates making it potentially the optimum composition mixture of Alg-nCP with future application prospects.
This paper studies parameters which affect the pore size diameter of a silicon membrane. Electrochemical etching is performed in characterise the parameter involved in this process. The parameter has been studied is volume ratio of hydrofluoric acid (HF) and ethanol as an electrolyte aqueous for electrochemical etch. This electrolyte aqueous solution has been mixed between HF and ethanol with volume ratio 3:7, 5:5, 7:3 and 9:1. As a result, the higher volume of HF in this electrolyte gives the smallest pore size diameter compared to the lower volume of HF. These samples have been dipped into HF and ethanol electrolyte aqueous with supplied 25 mA/cm2 current density for 20, 30, 40, and 50 minutes. The samples will inspect under Scanning Electron Microscope (SEM) to execute the pore formations on silicon membrane surface.
Earlier studies in our laboratory demonstrated that collagen extracted from ovine tendon is biocompatible towards human dermal fibroblast. To be able to use this collagen as a scaffold in skin tissue engineering, a mechanically stronger scaffold is required that can withstand manipulation before transplantation. This study was conducted to improve the mechanical strength of this collagen sponge using chemical crosslinkers, and evaluate their effect on physical, chemical and biocompatible properties. Collagen sponge was crosslinked with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and glutaraldehyde (GA). Tensile test, FTIR study and mercury porosimetry were used to evaluate mechanical properties, chemical property and porosity, respectively. MTT assay was performed to evaluate the cytotoxic effect of crosslinked collagen sponge on human dermal fibroblasts. The FTIR study confirmed the successful crosslinking of collagen sponge. Crosslinking with EDC and GA significantly increased the mechanical strength of collagen sponge, with GA being more superior. Crosslinking of collagen sponge significantly reduced the porosity and the effect was predominant in GA-crosslinked collagen sponge. The GA-crosslinked collagen showed significantly lower, 60% cell viability towards human dermal fibroblasts compared to that of EDC-crosslinked collagen, 80% and non-crosslinked collagen, 100%. Although the mechanical strength was better when using GA but the more toxic effect on dermal fibroblast makes EDC a more suitable crosslinker for future skin tissue engineering.
The unsteady two-dimensional laminar g-Jitter mixed convective boundary layer flow of Cu-water and Al2O3-water nanofluids past a permeable stretching sheet in a Darcian porous is studied by using an implicit finite difference numerical method with quasi-linearization technique. It is assumed that the plate is subjected to velocity and thermal slip boundary conditions. We have considered temperature dependent viscosity. The governing boundary layer equations are converted into non-similar equations using suitable transformations, before being solved numerically. The transport equations have been shown to be controlled by a number of parameters including viscosity parameter, Darcy number, nanoparticle volume fraction, Prandtl number, velocity slip, thermal slip, suction/injection and mixed convection parameters. The dimensionless velocity and temperature profiles as well as friction factor and heat transfer rates are presented graphically and discussed. It is found that the velocity reduces with velocity slip parameter for both nanofluids for fluid with both constant and variable properties. It is further found that the skin friction decreases with both Darcy number and momentum slip parameter while it increases with viscosity variation parameter. The surface temperature increases as the dimensionless time increases for both nanofluids. Nusselt numbers increase with mixed convection parameter and Darcy numbers and decreases with the momentum slip. Excellent agreement is found between the numerical results of the present paper with published results.
This study investigates the effects of an arbitrary wall shear stress on unsteady magnetohydrodynamic (MHD) flow of a Newtonian fluid with conjugate effects of heat and mass transfer. The fluid is considered in a porous medium over a vertical plate with ramped temperature. The influence of thermal radiation in the energy equations is also considered. The coupled partial differential equations governing the flow are solved by using the Laplace transform technique. Exact solutions for velocity and temperature in case of both ramped and constant wall temperature as well as for concentration are obtained. It is found that velocity solutions are more general and can produce a huge number of exact solutions correlative to various fluid motions. Graphical results are provided for various embedded flow parameters and discussed in details.
β-Cyclodextrin-ionic liquid polymer (CD-ILP) was first synthesized by functionalized β-cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using a toluene diisocyanate (TDI) linker to form insoluble CD-ILP (βCD-BIMOTs-TDI). The βCD-BIMOTs-TDI polymer was characterized using various tools and the results obtained were compared with those derived from the native β-cyclodextrin polymer (βCD-TDI). The SEM result shows that the presence of ionic liquid (IL) increases the pore size, while the thermo gravimetric analysis (TGA) result shows that the presence of IL increases the stability of the polymer. Meanwhile, Brunauer-Emmett-Teller (BET) results show that βCD-BIMOTs-TDI polymer has 1.254 m(2)/g surface areas and the Barret-Joyner-Halenda (BJH) pore size distribution result reveals that the polymer exhibits macropores with a pore size of 77.66 nm. Preliminary sorption experiments were carried out and the βCD-BIMOTs-TDI polymer shows enhanced sorption capacity and high removal towards phenols and As(V).
This research looks at the effects of partial slip on heat and mass transfer of peristaltic transport. The magnetohydrodynamic (MHD) flow of viscous fluid in a porous asymmetric channel has been considered. The exact solutions for the stream function, longitudinal pressure gradient, longitudinal velocity, shear stress, temperature and concentration fields are derived by adopting long wavelength and small Reynolds number approximations. The results showed that peristaltic pumping and trapping are reduced with increasing velocity slip parameter. Furthermore, temperature increases with increasing thermal slip parameter. Moreover, the concentration profile decreases with increasing porosity parameter, Schmidt number and concentration slip parameter. Comparisons with published results are found to be in good agreement.