Current commercialized vascular membranes to treat coronary heart disease (CHD) such as Dacron and expanded polytetrafluoroethylene (ePTFE) have been associated with biodegradable and thrombogenic issues that limit tissue integration. In this study, biodegradable vascular membranes were fabricated in a structure of electrospun nanofibers composed of polyurethane (PU), chitosan (CS) and elastin (0.5%, 1.0%, and 1.5%). The physicochemical properties of the membranes were analyzed, followed by the conduction of several test analyses. The blending of CS and elastin has increased the fiber diameter, pore size and porosity percentage with the appearance of identical chemical groups. The wettability of PU membranes was enhanced up to 39.6%, demonstrating higher degradation following the incorporation of both natural polymers. The PU/CS/elastin electrospun membranes exhibited a controlled release of CS (Higuchi and first-order mechanisms) and elastin (Higuchi and Korsmeyer-Peppas mechanisms). Delayed blood clotting time was observed through both activated partial thromboplastin time (APTT) and partial thromboplastin time (PT) analyses where significantly delay of 26.8% APTT was recorded on the PU membranes blended with CS and elastin, in comparison with the PU membranes, supporting the membrane's antithrombogenic properties. Besides, these membranes produced a minimum of 2.6 ± 0.1 low hemolytic percentage, projecting its hemocompatibility to be used as vascular membrane.
Rapid prototyping (RP) of microfluidic channels in liquid photopolymers using standard lithography (SL) involves multiple deposition steps and curing by ultraviolet (UV) light for the construction of a microstructure layer. In this work, the conflicting effect of oxygen diffusion and UV curing of liquid polyurethane methacrylate (PUMA) is investigated in microfabrication and utilized to reduce the deposition steps and to obtain a monolithic product. The conventional fabrication process is altered to control for the best use of the oxygen presence in polymerization. A novel and modified lithography technique is introduced in which a single step of PUMA coating and two steps of UV exposure are used to create a microchannel. The first exposure is maskless and incorporates oxygen diffusion into PUMA for inhibition of the polymerization of a thin layer from the top surface while the UV rays penetrate the photopolymer. The second exposure is for transferring the patterns of the microfluidic channels from the contact photomask onto the uncured material. The UV curing of PUMA as the main substrate in the presence of oxygen is characterized analytically and experimentally. A few typical elastomeric microstructures are manufactured. It is demonstrated that the obtained heights of the fabricated structures in PUMA are associated with the oxygen concentration and the UV dose. The proposed technique is promising for the RP of molds and microfluidic channels in terms of shorter processing time, fewer fabrication steps and creation of microstructure layers with higher integrity.
The development of bio-polyol from vegetable oil and its derivatives is gaining much interest from polyurethane industries and academia. In view of this, the availability of methyl oleate derived from palm oil, which is aimed at biodiesel production, provides an excellent feedstock to produce bio-polyol for polyurethane applications. In this recent study, response surface methodology (RSM) with a combination of central composite rotatable design (CCRD) was used to optimise the reaction parameters in order to obtain a maximised hydroxyl value (OHV). Three reaction parameters were selected, namely the mole ratio of epoxidised methyl oleate (EMO) to glycerol (1:5-1:10), the amount of catalyst loading (0.15-0.55%) and reaction temperature (90-150 °C) on a response variable as the hydroxyl value (OHV). The analysis of variance (ANOVA) indicated that the quadratic model was significant at 98% confidence level with (p-value > 0.0001) with an insignificant lack of fit and the regression coefficient (R2) was 0.9897. The optimum reaction conditions established by the predicted model were: 1:10 mole ratio of EMO to glycerol, 0.18% of catalyst and 120 °C reaction temperature, giving a hydroxyl value (OHV) of 306.190 mg KOH/g for the experimental value and 301.248 mg KOH/g for the predicted value. This result proves that the RSM model is capable of forecasting the relevant response. FTIR analysis was employed to monitor the changes of functional group for each synthesis and the confirmation of this finding was analysed by NMR analysis. The viscosity and average molecular weight (MW) were 513.48 mPa and 491 Da, respectively.
Novel bio-based polyurethane (PU) nanocomposites composed of cellulose nanofiller extracted from the rachis of date palm tree and polycaprolactone (PCL) diol based PU were prepared by casting/evaporation. Two types of nanofiber were used: cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs). The mechanical and thermal properties of the nanocomposite films were studied by DMA, DSC, and tensile tests and the morphology was investigated by SEM. Bionanocomposites presented good mechanical properties in comparison to neat PU. While comparing both nanofillers, the improvement in mechanical and thermal properties was more pronounced for the nanocomposites based on CNF which could be explained, not only by the higher aspect ratio of CNF, but also by their better dispersion in the PU matrix. Calculation of the solubility parameters of the nanofiller surface polymers and of the PU segments portend a better interfacial adhesion for CNF based nanocomposites compared to CNC.
New and emerging demand for polyurethane (PU) continues to rise over the years. The harmful isocyanate binding agents and their integrated PU products are at the height of environmental concerns, in particular PU (macro and micro) pollution and their degradation problems. Non-isocyanate poly(hydroxy urethane)s (NIPUs) are sustainable and green alternatives to conventional PUs. Since the introduction of NIPU in 1957, the market value of NIPU and its hybridized materials has increased exponentially in 2019 and is expected to continue to rise in the coming years. The secondary hydroxyl groups of these NIPU's urethane moiety have revolutionized them by allowing for adequate pre/post functionalization. This minireview highlights different strategies and advances in pre/post-functionalization used in biobased NIPU. We have performed a comprehensive evaluation of the development of new ideas in this field to achieve more efficient synthetic biobased hybridized NIPU processes through selective and kinetic understanding.
In this work, the physicochemical and blood compatibility properties of prepared PU/Bio oil nanocomposites were investigated. Scanning electron microscope (SEM) studies revealed the reduction of mean fiber diameter (709 ± 211 nm) compared to the pristine PU (969 nm ± 217 nm). Fourier transform infrared spectroscopy (FTIR) analysis exposed the characteristic peaks of pristine PU. Composite peak intensities were decreased insinuating the interaction of the bio oilTM with the PU. Contact angle analysis portrayed the hydrophobic nature of the fabricated patch compared to pristine PU. Thermal gravimetric analysis (TGA) depicted the better thermal stability of the novel nanocomposite patch and its different thermal behavior in contrast with the pristine PU. Atomic force microscopy (AFM) analysis revealed the increase in the surface roughness of the composite patch. Activated partial thromboplastin time (APTT) and prothrombin time (PT) signified the novel nanocomposite patch ability in reducing the thrombogenicity and promoting the anticoagulant nature. Finally the hemolytic percentage of the fabricated composite was in the acceptable range revealing its safety and compatibility with the red blood cells. To reinstate, the fabricated patch renders promising physicochemical and blood compatible nature making it a new putative candidate for wound healing application.
The feasibility of using dried attached-growth biomass from the polyurethane (PU) foam cubes as a solid carbon source to enhance the denitrification process in the intermittently aerated moving bed sequencing batch reactor (IA-MBSBR) during the treatment of low COD/N containing wastewater was investigated. By packing the IA-MBSBR with 8% (v/v) of 8-mL PU foam cubes saturated with dried attached-growth biomass, total nitrogen removal efficiency of 80% could be achieved for 10 consecutive cycles of operation when the intermittent aeration strategy of consecutive 1 h of aeration followed by 2 h of non-aeration period during the REACT period of the IA-MBSBR was adopted. Negligible release of ammonium nitrogen (NH4(+)-N) and slow-release of COD from the dried biomass would ensure that the use of this solid carbon source would not further burden the treatment system. The slow-releasing COD was found to have no effect in promoting the assimilation process and would also allow the carbon source to be used for many cycles of operation. The 'carbon-spent' PU foam cubes could be reused by merely drying at 60 °C at the end of the operational mode. Thus, the dried attached-growth biomass formed on the PU foam cubes could be exploited as an alternative solid carbon source for the enhancement of denitrification process in the IA-MBSBR.
Palm and soya oils were converted to monoglycerides via transesterification of triglycerides with glycerol by one step process to produce renewable polyols. Thermoplastic polyurethanes (TPPUs) were prepared from the reaction of the monoglycerides which act as polyol with 4,4'-methylenediphenyldiisocyanate (MDI) whereas, thermosetting polyurethanes (TSPUs) were prepared from the reaction of glycerol, MDI and monoglycerides in one pot. Characterization of the polyurethanes was carried out by FT-IR, (1)H NMR, and iodine value and sol-gel fraction. The TSPUs showed good thermal properties compared to TPPUs as well as TSPUs exhibits good properties in pencil hardness and adhesion, however poorer in flexural and impact strength compared to TPPUs. The higher percentage of cross linked fraction, the higher degree of cross linking occurred, which is due to the higher number of double bond presents in the TSPUs. These were reflected in iodine value test as the highest iodine value of the soya-based thermosetting polyurethanes confirmed the highest degree of cross linking. Polyurethanes based on soya oil showed better properties compared to palm oil. This study is a breakthrough development of polyurethane resins using palm and soya oils as one of the raw materials.
A study was carried out to produce polyurethane (PU) as a wood laminating adhesive from liquefied kenaf core (LKC) polyols by reacting it with toluene-2,4-diisocyanate (TDI) and 1,4-butanediol (BDO). The LKC polyurethane (LKCPU) adhesive has a molecular weight (MW) of 2666, viscosity of 5370 mPa s, and solids content of 86.9%. The average shear strength of the rubberwood (RW) bonded with LKCPU adhesive was 2.9 MPa. Most of the sheared specimens experienced a total adhesive failure. The formation of air bubbles through the liberation of carbon dioxide was observed to reduce the adhesive penetration and bonding strength which was obviously seen on the sheared specimens. The percentage of catalyst used can be varied based on the usage and working time needed. Nonetheless, the physical properties of LKCPU produced in this work had shown good potential as edge-bonding adhesive.
BACKGROUND: The clinical success of relining depends on the ability of reline resin to bond to denture base. Surface preparations may influence reline bond strength of urethane-based dimethacrylate denture base resin.
AIM: To investigate the effect of bur preparation on the surface roughness (R a ) of eclipse denture base resin and its shear bond strength (SBS) to an intra-oral self-curing reline material. The mode of reline bonding failure was also examined.
MATERIALS AND METHODS: Twenty-four cylindrical Eclipse™ specimens were prepared and separated into three groups of eight specimens each. Two groups were subjected to mechanical preparation using standard and fine tungsten carbide (TC) burs and the third group (control) was left unprepared. The R a of all specimens was measured using a contact stylus profilometer. Subsequently, relining was done on the prepared surface and SBS testing was carried out a day later using a universal testing machine.
RESULTS: One-way ANOVA revealed significant differences (P<0.05) in R a and SBS values for all the groups. Post-hoc Tukey's HSD test showed significant differences (P<0.05) between all the groups in the R a values. For SBS also there were significant differences (P<0.05), except between standard bur and control.
CONCLUSIONS: 1) There was a statistically significant difference in the R a of Eclipse™ specimens prepared using different carbide burs (P<0.05). 2) There was a statistically significant difference in the relined SBS (P<0.05) when prepared using different burs, but the difference between the standard bur and the control group was not statistically significant.
The performance of moving bed sequencing batch reactors (MBSBRs) added with 8 % (v/v) of polyurethane (PU) foam cubes as carrier media in nitrogen removal was investigated in treating low COD/N wastewater. The results indicate that MBSBR with 8-mL cubes achieved the highest total nitrogen (TN) removal efficiency of 37% during the aeration period, followed by 31%, 24% and 19 % for MBSBRs with 27-, 64- and 125-mL cubes, respectively. The increased TN removal in MBSBRs was mainly due to simultaneous nitrification and denitrification (SND) process which was verified by batch studies. The relatively lower TN removal in MBSBR with larger PU foam cubes was attributed to the observation that larger PU foam cubes were not fully attached by biomass. Higher concentrations of 8-mL PU foam cubes in batch reactors yielded higher TN removal.
Moving bed sequencing batch reactors (MBSBRs) packed with 8% (v/v) of 8-, 27- and 64-mL polyurethane (PU) foam cubes, respectively, were investigated for simultaneous 4-chlorophenol (4-CP) and nitrogen removal at increasing 4-CP concentration. When the 4-CP concentration exceeded 300 mg L(-1), the MBSBR with 27-mL foam cubes was observed to outperform the other MBSBRs in removing 4-CP and nitrogen. The reasons were: (1) there were more biomass in inner layer of the 27-mL cubes, compared to that of the 8-mL cubes, which was more shielded from the inhibitory effect of 4-CP and (2) the 27-mL cubes were more mobile than the 64-mL cubes. Although increasing 4-CP concentration to 600 mg L(-1) resulted in incomplete removal of 4-CP in the MBSBRs, results of the batch reactor with 27-mL foam cubes showed that complete 4-CP removal within the REACT period could be achieved by increasing the packing volume to 20%.
PURPOSE: The impact strength and the flexural properties of denture base materials are of importance in predicting their clinical performance upon sudden loading. This study compares the impact and transverse strengths and the flexural modulus of three denture base polymers.
MATERIALS AND METHODS: The investigation included a relatively new microwave-polymerized polyurethane-based denture material processed by an injection-molding technique, a conventional microwave-polymerized denture material, and a heat-polymerized compression-molded poly(methyl methacrylate) (PMMA) denture material. Impact strength was determined using a Charpy-type impact tester. The transverse strength and the flexural modulus were assessed with a three-point bending test. The results were subjected to statistical analysis using a one-way analysis of variance and the Scheffé test for comparison.
RESULTS: The impact strength of the microwave-polymerized injection-molded polymer was 6.3 kl/m2, while its flexural strength was 66.2 MPa. These values were lower than those shown by the two compression-molded PMMA-based polymers. The differences were statistically significant. The flexural modulus of the new denture material was 2,832 MPa, which was higher than the conventional heat-polymerized polymer but was comparable to the other microwave-polymerized PMMA-based polymer. The difference in the flexural modulus was statistically significant.
CONCLUSION: In terms of the impact and flexural strengths, the new microwave-polymerized, injection-molded, polyurethane-based polymer offered no advantage over the existing heat- and microwave-polymerized PMMA-based denture base polymers. However, it has a rigidity comparable to that of the microwave-polymerized PMMA polymer.
In this study, a small vascular graft based on polyurethane (PU) blended with chitosan (Ch) nanoparticles was fabricated using electrospinning technique. Initially, the chitosan nanoparticles were synthesized using ionic gelation method. UV-Vis spectrophotometer confirmed the presence of synthesized Ch nanoparticles by exhibiting absorption peak at 288 nm and the Fourier-transform infrared spectroscopy (FTIR) analysis confirmed the existence of the chitosan. Further, the synthesized Ch nanoparticles showed size diameter in the range of 134 ± 58 nm as measured using ImageJ. In the electrospun PU/chitosan graft, the fiber diameter and pore size diameter was found to be reduced compared to the pure PU owing to incorporation of chitosan into PU matrix. The FTIR spectrum revealed the presence of chitosan in the prepared nanocomposite membrane by the formation of the hydrogen bond and peak shift of CH and NH stretching. Moreover, the contact angle measurements revealed that the prepared graft showed decreased contact angle indicating hydrophilic nature compared to the pristine PU. The cytocompatibility studies revealed the non-toxic behavior of the fabricated graft. Hence, the prepared graft exhibiting significant physiochemical and non-toxic properties may be a plausible candidate for cardiovascular graft applications.
Essential oils play an important role in reducing the pain and inflammation caused by bone fracture.In this study, a scaffold was electrospun based on polyurethane (PU), grape seed oil, honey and propolis for bone tissue-engineering applications. The fiber diameter of the electrospun PU/grape seed oil scaffold and PU/grape seed oil/honey/propolis scaffold were observed to be reduced compared to the pristine PU control. FTIR analysis revealed the existence of grape seed oil, honey and propolis in PU identified by CH band peak shift and also hydrogen bond formation. The contact angle of PU/grape seed oil scaffold was found to increase owing to hydrophobic nature and the contact angle for the PU/grape seed/honey oil/propolis scaffold were decreased because of hydrophilic nature. Further, the prepared PU/grape seed oil and PU/grape seed oil/honey/propolis scaffold showed enhanced thermal stability and reduction in surface roughness than the control as revealed in thermogravimetric analysis (TGA) and atomic force microscopy (AFM) analysis. Further, the developed nanocomposite scaffold displayed delayed blood clotting time than the pristine PU in the activated prothrombin time (APTT) and partial thromboplastin time (PT) assay. The hemolytic assay and cytocompatibility studies revealed that the electrospun PU/grape seed oil and PU/grape seed oil/honey/propolis scaffold possess non-toxic behaviour to red blood cells (RBC) and human fibroblast cells (HDF) cells indicating better blood compatibility and cell viability rates. Hence, the newly developed electrospun nanofibrous composite scaffold with desirable characteristics might be used as an alternative candidate for bone tissue engineering applications.