Preparation and properties of 3-aminopropyltriethoxysilane functionalized graphene/polyurethane nanocomposite coatings

Silicone-modified graphene was successfully synthesized by treating graphene oxide with 3-aminopropyltriethoxysilane (AMEO) and then reduced by hydrazine hydrate. Subsequently, the AMEO-functionalized graphene was incorporated into polyurethane (PU) matrix to prepare AMEO-functionalized graphene/PU nanocomposite coatings. The functionalized graphene could disperse homogenously by means of a covalent connection with PU. AMEO-functionalized graphene (AFG)-reinforced PU nanocomposite coatings showed more excellent mechanical and thermal properties than those of pure PU. A 227 % increase in tensile strength and a 71.7 % improvement of elongation at break were obtained by addition 0.2 wt% of AFG. Meanwhile, thermogravimetric analysis reveals that thermal degradation temperature was enhanced almost 50 °C higher than that of neat PU, and differential scanning calorimetry analysis demonstrates that glass transition temperature decreased by around 9 °C. The thermal conductivity of AFG/PU nanocomposite coatings also increased by 40 % at low AFG loadings of 0.2 wt%.     

Preparation and characterization of a nitrogen-doped mesoporous carbon aerogel and its polymer precursor

Nitrogen-containing carbon aerogel was prepared from resorcinol–melamine–formaldehyde (R–M–F) polymer gel precursor. The polymer gel was supercritically dried with CO₂, and the carbonization of the resulting polymer aerogel under nitrogen atmosphere at 900 °C yielded the carbon aerogel. The polymer and carbon aerogels were characterized with TG/DTA–MS, low-temperature nitrogen adsorption/desorption (??196 °C), FTIR, Raman, powder XRD and SEM–EDX techniques. The thermal decomposition of the polymer aerogel had two major steps. The first step was at 150 °C, where the unreacted monomers and the residual solvent were released, and the second one at 300 °C, where the species belonging to the polymer network decomposition could be detected. The pyrolytic conversion of the polymer aerogel was successful, as 0.89 at.% nitrogen was retained in the carbon matrix. The nitrogen-doped carbon aerogel was amorphous and possessed a hierarchical porous structure. It had a significant specific surface area (890 m² g^?1) and pore volume (4.7 cm³ g^?1). TG/DTA–MS measurement revealed that during storage in ambient conditions surface functional groups formed, which were released upon annealing.     

A new intumescent flame‐retardant: preparation,surface modification,and its application in polypropylene

Melamine salt of tripentaerythriol phosphate (MTP), as a new intumescent flame‐retardant, was prepared from tripentaerythritol (TPE), polyphosphoric acid, phosphoric pentoxide, and melamine, and then incorporated into polypropylene (PP) to obtain flame‐retarded PP‐MTP. FT‐IR analysis showed that MTP was in the form of cage structure. The flammability, combustion behavior, and thermal degradation and stability of flame‐retarded PP were characterized by using LOI, UL‐94 test, cone calorimetry, and TGA, respectively. By SEM, the char structure of PP‐MTP was analyzed. XRD diffraction tests showed that PP‐matrix of PP‐MTP presented better crystallized phases, when MTP was modified by methyl hydrogen siloxane. The relations of the dispersion of MTP in PP matrix to the compatibility between PP and MTP, and to the flame retardancy were discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Effects of Cold Plasma Treatment on the Performance of Polyurethane Laminated Glass

The delamination of polyurethane (PU) laminated glass usually occurs at the interface between PU and inorganic glass. To prevent interlaminar delamination of PU and inorganic glass, PU was treated with cold plasma. The transparency of PU improved after cold plasma treatment. The cold plasma-treated PU showed 2 to 6 % higher transmittance than untreated PU. The adhesive strength of PU laminated glass increased by at least 96 % after cold plasma treatment. The adhesive strength of untreated PU samples rapidly decreased with increased hygrothermal aging time, whereas treated PU maintained almost 93 % of the original adhesive value even after hygrothermal aging for 30 days. FTIR analysis shows that –CO–O–C–, –C=O, and –CO–N groups appeared on the surface of cold plasma-treated PU, which resulted in the formation of hydrogen bonds at the interface between PU and silicate glass. After cold plasma treatment, the contact angle of PU changed from 105° to 79°, and the surface roughness of PU membranes changed from an average value of 19.74 to 57.16 nm.     

Formation of functional nanofibrous electrospun polyurethane and murivenna oil with improved haemocompatibility for wound healing

Electrospinning is an emerging tool and promising method to fabricate polymer nanofibers. The aim of this work was to fabricate electrospun polyurethane mats reinforced with murivenna oil for wound dressings. The scanning electron microscopy (SEM) micrographs showed the fiber diameter of nanocomposites in the range of 740 ± 160 nm and found to be decreased compared to pure polyurethane. Surface of nanocomposites was analyzed by Fourier transform infrared spectroscopy (FTIR) insinuated the interactions between PU and murivenna oil by the formation of hydrogen bond and changes in the characteristics peaks. Contact angle of the PU incorporated murivenna oil showed a decrease in its value compared to pure PU indicating the increased wettability and hydrophilic nature. The thermal degradation and stability of fabricated composites was found be enhanced compared to pure PU. The surface morphology through atomic force microscopy (AFM) analysis showed a change in surface roughness due to presence of murivenna oil in the polymer matrix. In blood compatibility results, both activated partial thromboplastin time (APTT) and prothrombin time (PT) were delayed due to improved surface properties and the addition of murivenna oil in the PU matrix. Compared to pure PU, the hemolysis assay of the PU incorporated murivenna oil showed a significant decrease in the percentage of lysis of red blood cells indicating better blood compatibility. Following the results, it was confirmed that fabricated novel scaffolds having better physicochemical and enhanced blood compatibility properties may be utilized for wound dressing.     

Migration and surface modification in polypropylene (PP)/polyhedral oligomeric silsequioxane (POSS) nanocomposites

This paper reports on the migration of POSS‐based nanocomposites both by annealing the melt and by heating the solid blend in the microwave oven. The migration proceeds to all surfaces of the sample as verified by ATR‐FTIR spectra of the bottom and top surfaces. Concentrations of POSS on the surface, exceeding 50%, are obtained. Polarity of the matrix increases POSS migration. During annealing at 190°C, a sublimation of POSS from the upper surface occurs. In air, sublimation is decreased by oxidizing the organic side groups of POSS and the PP to non‐volatile moieties. No sublimation occurs below 100°C. The AFM and SEM‐EDAX verified the high POSS concentration on the surface and indicated very pronounced roughness of the surface of the sample. The static contact angle measurements reveal very high hydrophobicity as well as low surface free energy (SFE) of the surface of the sample, which is close to that of Teflon and of pristine POSS. The migration of POSS is due to its lower surface tension, the entropy considerations, its lower cohesive energy with the matrix chains as compared to the cohesion energy between the chains, and the density and temperature fluctuations of the matrix chains which upon relaxation repulse and propel POSS to the surfaces. Copyright © 2008 John Wiley & Sons, Ltd.     

Effect of surface chemical modification for aluminum hypophosphite with hexa‐(4‐aldehyde‐phenoxy)‐cyclotriphosphazene on the fire retardancy,water resistance,and thermal properties for polyamide 6

The surface chemical modified aluminum hypophosphite (AHP) defined as MAHP was successful prepared through P–H bonds on AHP surface reacted with the aldehyde groups in hexa‐(4‐aldehyde‐phenoxy)‐cyclotriphosphazene made in our lab. The wettability of the flame retardants was evaluated by water contact angle tests, and the water contact angle of the prepared MAHP dramatically increased from 0° for AHP to 145°, which indicated the surface modification made the superhydrophilic AHP into superior hydrophobic MAHP. The prepared MAHP and AHP, respectively, incorporated into polyamide 6 (PA6) matrix to prepare flame retardant PA6 composites and the fire retardancy and thermal degradation behavior of flame retardant PA6 composites were investigated by limiting oxygen index, vertical burning test (UL‐94), cone calorimeter, and thermogravimetric analysis tests. The morphologies and chemical compositions of the char residues for PA6 composites were investigated by scanning electron microscopy and X‐ray photoelectron spectroscopy, respectively. The water resistant properties of flame retardant PA6 composites were evaluated by putting the samples into distilled water at 70°C for 168 hr, and the mechanical properties for flame retardant PA6 composites were investigated by the tensile, flexural, and Izod impact strength tests. The results demonstrated that the PA6/MAHP composites successfully passed UL‐94 V‐0 flammability rating, and the limiting oxygen index value was 27.6% when the loading amount of MAHP was 21 wt%. However, there is no rating in vertical burning tests for PA6/AHP composite with the same amount of AHP, which indicated the surface modification of AHP enhanced the flame retardancy efficiency for PA6 composites. The morphological structures and analysis of X‐ray photoelectron spectroscopy of char residues revealed that the surface modification of AHP benefited to the formation of a sufficient, flame retardant elements rich, more compact and homogeneous char layer on the materials surface during combustion, which prevented the heat transmission and diffusion, limit the production of combustible gases, inhibit the emission of smoke and then led to the reduction of the heat release rate and smoke produce rate. The mechanical properties results revealed that the surface modification of AHP enhanced the mechanical properties, especially the Izod impact strength comparing with that of PA6/AHP composites with the same amount of flame retardant. After water resistance tests, the PA6/MAHP composites remained superior flame retardancy and presented continuous and compact char layer after cone calorimeter tests; however, the fire retardancy for PA6/AHP composite obviously decreased, and the char layer was discontinuous with big hole caused by the extraction of AHP by water during water resistance tests. Copyright © 2017 John Wiley & Sons, Ltd.     

Preparation and characterization of the bacterial cellulose/polyurethane nanocomposites

New nanocomposites based on bacterial cellulose nanofibers (BCN) and polyurethane (PU) prepolymer were prepared and characterized by SEM, FT-IR, XRD, and TG/DTG analyses. An improvement of the interface reaction between the BCN and the PU prepolymer was obtained by a solvent exchange process. FT-IR results showed the main urethane band at 2,270 cm^?1 to PU prepolymer; however, in nanocomposites new bands appear as disubstituted urea at 1,650 and 1,550 cm^?1. In addition, the observed decrease in the intensity of the hydroxyl band (3,500 cm^?1) suggests an interaction between BCN hydroxyls and NCO-free groups. The nanocomposites presented a non-crystalline character, significant thermal stability (up to 230 °C) and low water absorption when compared to pristine BCN.     

Synthesis and thermal studies of flexible polyurethane nanocomposite foams obtained using nanoclay modified with flame retardant compound

This work presents thermal studies of nanocomposites based on the flexible polyurethane (PU) matrix and filled using montmorillonite organically modified with organophosphorus flame retardant compound. Flexible PU nanocomposite foams were prepared in the reaction carried out between reactive alcoholic hydroxyl and isocyanate groups with the ratio of NCO to OH groups equal to 1.05. The amount of an organoclay ranging from 3 to 9 vol% was added to the polyol component of the resin before mixing with isocyanate. The apparent density of PU foams was ranging from 0.066 to 0.077 g cm^?1. Thermal properties of the flexible PU nanocomposite foams were investigated by thermogravimetry and dynamical mechanical analysis. Glass transition temperatures (T _g) were defined as maximum peak on tanδ curve. Thermal decomposition was observed at 310–320 °C (calculated from the onset of TG curve). Tensile strength of the PU foams was determined using mechanical test. The microstructure of the nanoparticles and the composites was investigated by X-ray diffraction. Finally, it was confirmed that the thermal and mechanical properties of flexible PU nanocomposite depend on the amount of nanoclay.     

Application of cooling curve analysis in solidification pattern and structure control of grey cast irons

In this article, the composites based on long glass fibre reinforced polypropylene/intumescent flame retardant (LGFPP/IFR) were prepared by melt blending. The influence of thermal oxidative ageing on the LGFPP/IFR composites with different thermal oxidative ageing time at 140 °C was studied by means of oven heating. The thermal stability and flammability of the composites were respectively investigated by thermal gravimetric analysis (TG), limiting oxygen index (LOI), UL-94 test, cone calorimeter test (CCT), scanning electronic microscopy (SEM), mechanical properties test and energy-dispersive X-ray analysis (EDAX). A trend of increase first and then decrease in LOI values was shown in 0–50 days ageing, with the same trend as thermal stability obtained from TG in nitrogen condition. The CCT results indicated that the LGFPP/IFR composites after ageing achieved a higher heat release rate, which means a higher fire risk. The mechanical properties showed a global decrease in just 10 days ageing. Morphologies obtained from SEM showed that both the rupture of PP matrix and fibre interface debonding led to the decrease in mechanical properties. The EDAX proved that IFR particles could emerge and gather on the surface of sample in ageing procedure, which had great effects on the thermal stability and flame retardancy of the composites.     

Preparation and characterization of microencapsulated ammonium polyphosphate with polyurethane shell by in situ polymerization and its flame retardance in polyurethane

Microencapsulated ammonium polyphosphate (APP) with polyurethane (MCAPP) was prepared by in situ polymerization of pentaerythtritol (PER) and toluene‐2,4‐diisocyanate (TDI) in the presence of added APP. MCAPP was then incorporated into polyurethane (PU) to obtain flame retarded PU/MCAPP. Fourier transform infrared (FT‐IR) and X‐ray photoelectron spectroscopy (XPS) showed that APP was encapsulated by a layer of PU. It found that the optimal reaction time was 8 hr and microencapsulation led to an improvement in water leaching from scanning electron microscopy (SEM) and determination of water resistance. Thermal degradation of flame retarded PU was also investigated by thermogravimetric analysis (TGA). UL‐94 test and SEM were performed before and after water treatment at 75°C for seven days, and the results showed that PU loading of 30% MCAPP can maintain the V‐0 level, due to the shield effect of microencapsulation. Copyright © 2008 John Wiley & Sons, Ltd.     

Co-microencapsulate of ammonium polyphosphate and pentaerythritol in intumescent flame-retardant coatings

Co-microencapsulated ammonium polyphosphate (APP) and pentaerythritol (PER) [M (A&P)] is prepared using melamine–formaldehyde resin by in situ polymerization method and characterized using energy dispersive spectrometer and Fourier transform infrared spectra. Thermal stability and fire resistance behavior have been analyzed and compared. The co-microencapsulation of APP and PER leads to a great improvement of its thermal stability investigated by thermogravimetric analysis. The temperature of maximum mass loss rate of M (A&P) is 30 °C higher than that of APP/PER mixture. The flame-retardant effect of M (A&P) in coating composite is evaluated by carbonization volume, flame spread rate, and cone calorimeter. Results show that the flame-retardant properties of M (A&P) in coating composite is much better than that of APP/PER mixture coating composite.     

Melamine,silica, and ionic liquid as a novel flame retardant for rigid polyurethane foams with enhanced flame retardancy and mechanical properties

Rigid polyurethane (PU) foams were successfully filled with different weight ratios of melamine (1 wt%, 5 wt%, 10 wt%), silica (0.1 wt%) and ionic liquid, 1-Ethyl-3-methylimidazolium chloride, [EMIM]Cl (0.3 wt%). The aim of this study was to improve the flame retardancy of PU foams and to develop the synergistic effect between melamine, silica and ionic liquid on the flame-retardant PU foams. The influence of different loadings of the fillers was examined. The results showed that in comparison with unfilled foam, all modified compositions are characterized by higher density (41–46 kg m⁻³), greater compression strength (134–148 kPa), and comparable thermal conductivity (0.023–0.026 W m⁻¹ K⁻¹). Moreover, the reaction to fire of the PU composites has been investigated by the cone calorimeter test. The results showed that the fire resistance of PU foams containing as little as 1 wt% of melamine is significantly improved. For example, the results from the cone calorimeter test showed that the incorporation of the melamine, silica and ionic liquid significantly reduced the peak of heat release rate (pHRR) by ca. 84% compared with that of unmodified PU foam. SEM results showed that incorporated fillers can form an intumescent char layer during combustion which improves the reaction to fire of the composite foams.     

Melamine modified carbon felts anode with enhanced electrogenesis capacity toward microbial fuel cells

Surface electropositivity and low internal resistance are important factors to improve the anode performance in microbial fuel cells(MFCs). Nitrogen doping is an effective way for the modification of traditional carbon materials. In this work, heat treatment and melamine were used to modify carbon felts to enhance electrogenesis capacity of MFCs. The modified carbon felts were characterized using X-ray photoelectron spectroscopy(XPS), scanning electron microscope(SEM), atomic force microscopy(AFM)and malvern zeta potentiometer. Results show that the maximum power densities under heat treatment increase from 276.1 to 423.4 m W/m~2(700 °C) and 461.5 m W/m~2(1200 °C) and further increase to472.5 m W/m~2(700 °C) and 515.4 m W/m~2(1200 °C) with the co-carbonization modification of melamine.The heat treatment reduces the material resistivity, improves the zeta potential which is beneficial to microbial adsorption and electron transfer. The addition of melamine leads to the higher content of surface pyridinic and quaternary nitrogen and higher zeta potential. It is related to higher MFCs performance. Generally, the melamine modification at high temperature increases the feasibility of carbon felt as MFCs' s anode materials.     

Effect of boron containing materials on flammability and thermal degradation of polyamide‐6 composites containing melamine cyanurate

Three different boron containing materials, zinc borate (ZnB), borophosphate (BPO₄), and boron and silicon containing oligomer (BSi), were used to improve the flame retardancy of melamine cyanurate (MC) in a polyamide‐6 (PA‐6) matrix. The combustion and thermal degradation characteristics were investigated using limiting oxygen index (LOI), UL‐94 standard, thermogravimetric analysis‐Fourier transform infrared spectroscopy (TGA‐FTIR), differential scanning calorimeter (DSC), and scanning electron microscopy (SEM). All the three boron compounds showed no synergistic effect with MC, and only BPO₄ at high loadings showed comparable LOI values by increasing the dripping rate. For ZnB and BSi glassy film and char formation decreases the dripping rate and sublimation of melamine and give rise to low LOI. According to TGA‐FTIR results, addition of boron compounds does not alter the gaseous product distribution of both MC and PA‐6. The addition of boron compounds affects flame retardancy through physical means. It was noted from the TGA data that boron compounds reduced the decomposition temperature of both MC and PA‐6, also affecting the flame retardancy negatively by premature degradation of MC at low temperatures. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation and Flame Retardancy of Polyurethane/POSS Nanocomposites

Polyurethane/polyhedral oligomeric sisesquioxane (PU/POSS) nanocomposites were syn-thesized via polymerization utilizing the compatibility between POSS nanoparticles and 4,4'-diphenyl methylene diisocyanate. Scanning electron microscope images and Fouriertransform infrared spectra revealed that POSS nanoparticles were dispersed in PU matrix.Thermal gravimetric analysis was employed to investigate the thermal decomposition be-havior of PU/POSS nanocomposites at elevated temperatures. Then fire performance wasevaluated by limiting oxygen index, underwriters laboratories 94 testing and char residue morphology. These results showed that the addition of POSS promoted the formation of char residues which were covered on the surface of polymer composites, leading to the im-provement of thermal stability and flame retardancy.     

Determination of Melamine Based on the Formation of an Insoluble Copper-Melamine Complex and Flame Atomic Absorption Spectrometry

A copper-melamine complex was optimally synthesized by heating excess copper(II), as 50 m mol L^?1 copper(II) chloride in 50% (v/v) methanol, and melamine at 80°C. The amount of residual copper(II) in solution after removal of the copper-melamine complex was then measured by flame atomic absorption spectrometry. The concentration of depleted copper was proportional to the concentration of melamine, with a linear calibration curve (melamine concentration against copper absorbance) between 0.5 and 2.5 m mol L^?1 (R² = 0.9943) and with a limit of detection of 0.50 m mol L^?1. Although external standard calibration provided poor recoveries in fortified fish flesh (40% to 74% for 5 to 10 mg melamine/g), the method of standard addition provided acceptable values (90% to 93%), with a relative standard deviation of 3% to 10%. The results obtained with the standard addition method were in broad agreement with those obtained by high performance liquid chromatography.     

Solvent-Free Synthesis of ZnO Nanoparticles by a Simple Thermal Decomposition Method

This paper reports on a novel processing route for producing ZnO nanoparticles by solid-state thermal decomposition of zinc(II) acetate nanostructures obtained by the sublimation of zinc(II) acetate powder. The sublimation process of the Zn(OAc)₂ powder was carried out in the temperature 150 °C for 2 h. In addition, nanoparticles of ZnO were obtained by solid-state thermal decomposition of the synthesized Zn(OAc)₂ nanostructures. The synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy, and energy dispersive X-ray spectroscopy. The sublimation process of the Zn(OAc)₂ powder was carried out within the range of 150–180 °C. The XRD studies indicated the production of pure hexagonal ZnO nanoparticles after thermal decomposition.     

Pharmaceutical approaches involving carvedilol characterization,compatibility with different excipients and kinetic studies

This study was performed to investigate the physical–chemical characteristics of carvedilol (CRV), complemented by compatibility studies with a great variety of pharmaceutical excipients. Thermogravimetry and differential scanning calorimetry, supported by diffuse reflectance infrared fourier transform spectroscopy (DRIFT), X-ray powder diffraction, and scanning electron microscopy (SEM) were selected as the solid-state techniques for the intended analyses. In addition, non-isothermal methods were employed to investigate kinetic data of CRV decomposition process under nitrogen and air atmospheres. CRV is characterized by an endothermic sharp event (T _peak = 389.81 K and ΔH _fusion of ?176.28 J g^?1) and a thermal decomposition behavior in two stages, totalizing 98 % of mass loss. The CRV pattern diffraction presents prominent peaks at 2θ: 5.92°, 14.90°, 18.62°, 24.47°, and 26.30°, and the DRIFT spectrum showed the main characteristics bands for CRV chemical functional groups. The SEM photomicrographs demonstrate that CRV is characterized by irregular blocky shaped crystals. Zero order kinetics was determined by Ozawa method in both nitrogen and air atmospheres. The compatibility results showed no evidence of any incompatibility among CRV and all the excipients analyzed.     

Flammability properties of PI fabric coated with montmorillonite

In this study, polyimide (PI) fabric was coated with montmorillonite (MMT) which performed as a kind of flame retardant. Thermogravimetric analysis showed that PI coated with MMT left as much as 69 % char after heating to 700 °C, about 15 % more than uncoated PI fabric. Cone calorimeter testing (heat flux: 60 kW m^?2) showed that coated fabric reduced the total heat release and showed resistance to degradation from direct flame. Post-burn residues of samples were examined with SEM and revealed that the weave structure and fiber shape in all coated fabrics were preserved. In addition, heat-insulting test showed that the temperature difference of coated PI could reach 400 °C after 10 min at 800 °C. These results demonstrate that MMT coating is relatively effective for improving flame-retardant behavior to PI fabric.