Thermal degradation behaviors and fire retardant properties of poly(1,3,4-oxadiazole)s (POD) and poly(m-phenylene isophthalamide) (PMIA) fibers

Thermal degradation behaviors and fire retardant properties of poly(1,3,4-oxadiazole)s (POD) and poly(m-phenylene isophthalamide) (PMIA) fibers were investigated. The thermal gravimetric analysis (TGA) demonstrated that POD exhibited higher onset thermal degradation temperature (T_onset) than PMIA, exceeding nearly 80 °C. The thermal degradation kinetics, evaluated by the modified Coats-Redfern method, displayed that the apparent activation energy (E_a) of POD and PMIA fibers was similar when the conversion rate (α) ranges from 0.2 to 0.5, while with the α from 0.6 to 0.8, the E_a of POD was significantly lower than that of PMIA. The fire retardant performance of POD and PMIA fibers were evaluated by cone calorimeter under heat fluxes of 35, 50 and 75 kW/m², during which the temperature of the fibers were monitored by a thermocouple. Surprisingly, POD fibers showed inferior fire retardant performance in comparison with PMIA, with lower time to ignition (TTI) and higher peak heat release rate (PHRR). The origin of the different fire retardant properties of both fibers was revealed by analyzing the residual chars and gaseous products during thermal pyrolysis. The morphology confirmed that stable and compact chars can be formed in PMIA. In addition, the Fourier Transform Infrared Spectroscopy (FTIR) characterization of the residual char revealed that POD can form carbonaceous chars at the heat flux of 50 kW/m², while the heat flux of PMIA was 75 kW/m². The pyrolysis products characterized by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) indicated that POD can be pyrolyzed completely at 600 °C, while the temperature of PMIA was 700 °C.     

Fabrication and properties of dope-dyed Poly(m-phenylene isophthalamide) fibers via wet spinning

Poly(m-phenylene isophthalamide) (PMIA) fibers play an irreplaceable role in the area of high-temperature resistance. It is usually difficult to dye PMIA fibers due to their rigid molecular structure and high crystallinity. In this study, the dope-dyed PMIA fibers with different amounts of pigment were fabricated by wet spinning. The properties of the pigment were analyzed, including size distribution and dispersive properties. The results showed that the pigment was easy to disperse in the fibers when the average diameter of the pigment was smaller than 500 nm. The color fastness of the colored PMIA fibers was tested, and their thermal properties and mechanical properties were also analyzed. The results of thermal gravity analysis (TGA) indicated that the colored PMIA fibers maintained good thermal performance. Compared to uncolored PMIA fibers, the colored PMIA fibers became lighter after exposing to simulated sunlight for 50 h. The breaking tenacity of fibers exceeded 2.0 cN/dtex, and the retentivity was above 80 % after being exposed to simulated sunlight for 50 h. These suggested the good mechanical performance of colored PMIA fibers. Dope-dyed PMIA fibers with good mechanical properties and thermal performance were successfully developed.     

The Preparation and Characterization of Ultrafine Fatty Acid Ester/Poly(<Emphasis Type="Italic">meta</Emphasis>-phenylene isophthalamide) Phase Change Fibers Designed for Thermo-regulating Protective Clothing

Poly(meta-phenylene isophthalamide, PMIA)-based phase change fibers (PCFs) with fatty acid ester (i.e. HPCMEs) as the functional ingredient were successfully fabricated by emulsion electrospinning. Subsequent characterizations by FE-SEM, TEM, DSC and TGA were performed to investigate their morphology, structure, thermal storage and decomposition behavior, respectively. Experimental results reveal that the fabricated PCFs are randomly arranged and show a good cylindrical structure with fiber diameters ranging from tens to hundreds of nanometers. Most of the HPCMEs are well encapsulated by PMIA sheaths and appear as isolated segments or elongated channels inside the fiber. Given their proper phase change span (30-40°C), considerable enthalpies, good shape stability and greatly enhanced thermal resistance, the prepared HPCMEs/PMIA PCFs are expected to have wide prospects in thermo-regulating protective clothing and other fields related to thermal energy storage.     

Electrospun SiO<Subscript>2</Subscript>/PMIA nanofiber membranes with higher ionic conductivity for high temperature resistance lithium-ion batteries

The nanofiber membrane prepared by electrospinning has been widely applied in lithium-ion batteries. A powerful strategy for designing, fabricating and evaluating Poly-m-phenylene isophthalamide (PMIA) nanofiber membrane with SiO₂ nanoparticles was developed by electrospinning in this paper. The morphology, crystallinity, thermal shrinkage, porosity and electrolyte uptake, and electrochemical performance of the SiO₂/PMIA nanofiber membranes were investigated. It was demonstrated that the nanofiber membrane with 6 wt% SiO₂ possessed notable properties, such as better thermal stability, higher porosity and electrolyte uptake, resulting in higher ionic conductivity (3.23×10^-3 S·cm^-1) when compared with pure PMIA nanofiber membrane. Significantly, the SiO2/PMIA nanofiber membrane based Li/LiCoO₂ cell exhibited more excellent cycling stability with capacity retention of 95 % after 50 cycles. The results indicated that the SiO₂-doped PMIA nanofiber membranes had a potential application as separator in high temperature resistance lithium-ion batteries.     

Fabrication of electrospun meta-aramid nanofibers in different solvent systems

Meta-aramid fibers were dissolved in four different solvent systems (DMAc, DMF, NMP, and DMSO) and two kinds of salts (LiCl and CaCl₂) were also introduced in this paper. Meta-aramid fibers had a limited solubility in above four solvents, however, fast dissolution could be obtained after adding a certain amount of salt (LiCl or CaCl₂). The concentration of salts was found to be an important role in affecting meltaging, dissolving time and viscosity of electrospun solution. Electrospun meta-aramid nanofibers mats were successfully prepared. A series of characterizations had been carried out by using SEM. The results shows the diameter of meta-aramid nanofibers ranging from 100 to 500 nm. The average diameter of the nanofibers increased with the concentration of meta-aramid fiber solution and the salt solution. A preferable morphology of meta-aramid nanofibers could be obtained under LiCl/DMAc system. While the electrospun nanofibers made in CaCl₂/DMAc solvent system had a better performance in thermal stability than that prepared in LiCl/DMAc system. Among the four kinds of prepared nanofibers, the nanofibersmat electrospun in LiCl/DMAc system with a concentration of meta-aramid solution at 11 wt% exhibit the best mechanical properties.     

Cellulose nanofiber-reinforced silk fibroin composite film with high transparency

We successfully prepared optically transparent silk fibroin-cellulose nanofiber (CN) composite films from solvent casting using a stable CN suspension in an aqueous silk fibroin solution. The transmittance of the silk fibroin composite films was observed by a UV-visible spectrophotometer. The secondary structural change of the silk fibroin caused by the incorporation of CNs was characterized using Fourier transform infrared spectroscopy. A tensile test was carried out to investigate the mechanical properties. The results showed that the composite film exhibited visible-light transmittance of 75 %, and its mechanical strength and Young’s modulus were increased by 44 % and 35 %, respectively, as compared to a neat silk fibroin film.     

Fly ash/polyurethane thin film for the adsorption of volatile organic compounds (VOCs) from air

Polyurethane (PU) films containing different amounts of fly ash particles (FAPs) were prepared by simple solution casting method. The morphological, thermal, and mechanical properties of the composite films were investigated by several characterization methods. Results show that sufficient amounts (up to 40 wt%) of FAPs can be incorporated throughout the film. The presence of FAPs within PU film not only acts as filler to increase the mechanical strength of the film but also increases its volatile organic compounds (VOCs) adsorption capacity. The VOCs adsorption capacity of FAPs/PU composite films were investigated on three different compounds (chloroform, toluene, and benzene). It showed consistent trend in the order of toluene > benzene > chloroform for all the samples. The VOCs adsorption capacity of PU film was found to be increased by two fold when 20 wt% of FA was incorporated through it. The present results suggest the potential use of FAPs as filler materials for PU films with improved VOCs adsorption from outdoor and indoor air.     

Crystal structure and thermal properties of poly(vinylidene fluoride)-carbon fiber composite films with various drawing temperatures and speeds

PVDF-CF composite films were prepared using a melt pressing method. The PVDF-CF composite films were cut into rectangular shapes with a gauge length and width of 10 and 5 mm, respectively. The films were drawn using a universal testing machine equipped with a hot chamber. The drawing temperatures and speeds were 50∼150 °C and 100∼000 %/min, respectively. The crystal structure and physical properties of the resulting PVDF-CF films were investigated by wide angle X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis and scanning electron microscopy. The crystal form of the initial films was the 〈alpha〉 phase (non polarity, lamellar structure) of PVDF. The maximum draw ratio was 4.2. The drawn PVDF-CF films prepared at 100 °C were mainly the 〈beta〉 phase (polarity, fibrillar structure) of PVDF. With increasing drawing speeds, the 〈alpha〉 phase became the dominant phase of PVDF in the PVDF-CF films. The thermal properties of the PVDF-CF films improved with increasing drawing temperature, and the dynamic mechanical properties improved with increasing drawing speed.     

Fabrication and characterization of porous cellulose acetate films by breath figure incorporated with capric acid as form-stable phase change materials for storing/retrieving thermal energy

Porous cellulose acetate (CA) films by breath figure (BF) incorporated with capric acid as form-stable phase change materials (PCMs) were fabricated and characterized for storing and retrieving thermal energy. Effects of different solvents, CA concentration and film thickness on morphology, microstructure and thermal energy storage property of formstable PCMs were investigated by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analyzer and differential scanning calorimetry (DSC), respectively. The results indicated that the prepared CA films were porous with DMF, acetone, and dichloromethane (DCM) as the solvents, and capric acid absorption capacity was as high as 86.9, 75.0 and 82.2 % with the specific surface area of 4.8, 2.8 and 1.8 m²/g. Moreover, porous CA film with 5 % CA concentration and 0.5 mm thickness prepared by using DMF as solvent had larger specific surface area and higher thermal energy storage properties. The fabricated form-stable PCMs could well maintain their PCM characteristics and demonstrated great temperature regulation ability and had potential applications in building energy conservation.     

Synthesis and thermal properties of polyhydroxyamide copolymer and its derivatives

We synthesized a polyhydroxyamide (PHA) copolymer via low-temperature solution polymerization of 3,3'-dihydroxybenzidine with terephthaloyl chloride (80.0 mol%) and isophthaloyl chloride (20.0 mol%) in N,Ndimethylacetamide with the aid of LiCl. We prepared the PHA copolymer derivatives containing the fluorine-based substituents and investigated their solubility, cyclization behavior, and thermal properties using a differential scanning calorimeter (DSC), a thermogravimetric analyzer (TGA), and the simultaneous thermogravimetric analyzer coupled with a mass spectrometer (STA-MS). The chemical structures of the PHA copolymer and its derivatives, as well as the polybenzoxazoles (PBOs) obtained through thermal cyclization of the copolymer and derivatives, were determined by a fourier transform infrared (FT-IR) spectroscopic analysis. The PHA copolymer could be dissolved in organic solvents only with the aid of LiCl, while its derivatives were readily soluble in DMA_c and NMP without LiCl at room temperature. The DSC and TGA results demonstrated that the PHA copolymer derivatives could be converted to PBOs at a lower temperature than the PHA copolymer.     

Carbon nanofiber/poly(vinylidene fluoride-hexafluoro propylene) composite films: The crystal structure and thermal properties with various drawing temperatures

Carbon nanofiber (CNF)/polyvinylidene fluoride-hexafluoro propylene (PVDF-HFP) composite film was prepared by solution casting and melt pressing. The resultant 2 % CNF/PVDF-HFP composite films were uniaxially drawn at 50 °C, 75 °C, and 100 °C, respectively. In the SEM images, the morphology of drawn CNF/PVDF-HFP composite film confirmed the orientation of the CNF and the polymer matrix. The WAXD results showed the coexistence crystal phase of PVDF-HFP. The drawn CNF/PVDF-HFP composite film demonstrates improved electrical properties. The DSC thermogram results indicated no change in the melting temperature but slightly increased crystallinity with increasing drawing temperature. Dynamic mechanical analysis and tensile test showed an improvement in the storage modulus and stress at a drawing temperature of 75 °C.     

Preparation and properties of crosslinkable waterborne polyurethanes containing aminoplast

In order to improve the water swelling, thermal/mechanical and adhesion properties of waterborne polyurethane (WBPU), a series of the crosslinkable WBPUs containing hydrophilic ionic component, dimethylol propionic acid (20 mole%), were prepared by in-situ polymerization using a cross-linker hexakis (methoxymethyl) melamine (HMMM). Effects of the HMMM content (2, 4, and 6 wt%) and curing temperature on these properties of the crosslinked WBPUs samples were investigated. All properties were found to increase with increasing HMMM content. It was found that the optimum curing temperature of the WBPU films and adhesives was near 120°C, which was not dependent on the HMMM content.     

Film preparation by melt- or compression-process using poly(vinyl chloride) powder swollen with dimethylformamide

A melt-process was used to prepare high molecular weight Poly(vinyl chloride) (PVC) films without the use of a conventional plasticizer and heat stabilizer. Rigid PVC powder was swollen with dimethylformamide containing 4∼10 vol% water to reduce its melting temperature. The swollen powder was pressed at a relatively low temperature of 75∼125 °C to form a film shape, and then washed and dried. The visible light transmittance, X-ray diffraction, density and the tensile properties of the resulting films were examined to estimate the success or failure of film formation. The films could be produced by not only the melt-process but also a compression-process using the rigid, highly swollen PVC powder. The resulting films had no voids, which are generally observed in PVC products formed by a solution process. The minimum temperature for these processes decreased with decreasing water content in the mixture: The minimum temperatures according to the water content in the mixture to produce faultless films through the melt-process were 4 %–105 °C, 6 %–115 °C, 8 and 10 %–125 °C, while those through the compression process were 4 %–95 °C, 6 and 8 %–105 °C, 10 %–115 °C.     

Influence of noncellulosic contents on nano scale refinement of waste jute fibers for reinforcement in polylactic acid films

In the present study, nanofibrils of cellulose are extracted from waste jute fibers using high energy planetary ball milling process in wet condition. The rate of refinement of untreated fibers having non-cellulosic contents was found slower than treated fibers due to strong holding of fiber bundles by non-cellulosic contents. At the end of three hours of wet milling, untreated fibers were refined to the size of 850 nm and treated fibers were refined to the size of 443 nm. In the subsequent stage, composite films of poly lactic acid (PLA) were prepared by solvent casting with 3 wt% loading of untreated jute nanofibrils, treated jute nanofibrils and microcrystalline cellulose. The influence of non-cellulosic contents on mechanical properties of PLA films are investigated based on results of tensile test, dynamic mechanical analysis and differential scanning calorimetry. The maximum improvement was observed in case of treated jute nanofibril/PLA composite film where initial modulus and tensile strength increased by 207.69 % and 168.67 %, respectively as compared to neat PLA film. These improvements are attributed to the increased interaction of treated jute nanofibrils with PLA matrix due to their higher precentage of cellulosic contents and mechanically activated surface.     

Nanocellulose reinforced PVA composite films: Effects of acid treatment and filler loading

Nanocellulose was prepared by acid hydrolysis of microcrystalline cellulose (MCC) at different hydrobromic acid (HBr) concentrations. Polyvinyl alcohol (PVA) composite films were prepared by the reinforcement of nanocellulose into a PVA matrix at different filler loading levels and subsequent film casting. Chemical characterization of nanocelluloses was performed for the analysis of crystallinity (X_c), degree of polymerization (DP), and molecular weight (M_w). The mechanical and thermal properties of the nanocellulose reinforced PVA films were also measured for tensile strength and thermogravimetric analysis (TGA). The acid hydrolysis decreased steadily the DP and M_w of MCC. The crystallinity of MCC with 1.5 M and 2.5 M HBr showed a significant increase due to the degradation of amorphous domains in cellulose. Higher crystalline cellulose showed the higher thermal stability than MCC. From X-ray diffraction (XRD) analysis, nanocellulose samples showed the higher peak intensity than MCC cases. Reduction of MCC particle by acid hydrolysis was clearly observed from scanning electron microscope (SEM) images. The tensile and thermal properties of PVA composite films were significantly improved with the increase of the nanocellulose loading.     

Dry-jet wet spinning of polyhydroxyamide fibers

A high molecular weight polyhydroxyamide (PHA) solution in N, N-dimethyl acetamide (DMAc) was prepared from 3,3′-dihydroxybenzidine and isophthalic chloride (IPC), which was used for spinning PHA fiber. Before spinning, the diffusion property of DMAc into various coagulants was examined. The fiber was well formed in coagulants such as water/ethanol with a composition of 5/5, ethanol, and ethanol/isopropanol with a composition of 7/3 and 5/5. However, the PHA fiber spun in the water/ethanol mixture contained voids. After the fiber spun in ethanol was annealed at over 350°C, the ultimate stress and initial modulus of the fiber increased from 75.5 MPa and 3.22 GPa to 369 MPa and 29.5 GPa, respectively. These properties of the PHA fiber spun by the dry spinning method were also enhanced, attaining 154 MPa and 5.56 Gpa, respectively.     

Preparation and characterization of hair keratin/gelatin blend films

Abstract: Keratin solution was extracted from human hairs and used as subject for preparation of keratin/gelatin blend films. This study was aimed to explore the suitable method using for keratin extraction and extend to study the blend film properties. The blend films were prepared by simple evaporation method. After homogeneously mixed between keratin and gelatin solution at different ratios, the solution were placed on the plates and left in an oven at 40 degrees C for 3 days. All of the films were then analyzed for their morphology, secondary structures and thermal properties by using SEM, FTIR and TGA, respectively. The result from SEM images showed that native keratin films have the highest rough surface compared to other films. In addition, the smooth surface of films gradually increased when the gelatin content increased. Keratin blending with gelatin showed structural changes, especially at the absorption bands of 3300-2900 cm(-1) as well as the amide I, II and III regions. Moreover, thermal properties of the keratin films were enhanced by blending with gelatin. This study suggested that gelatin help to improve some properties of keratin while still remain its strength.     

Preparation and characterization of cellulose nanofiber reinforced thermoplastic starch composites

In the present study, cellulose nanofibers composite films were manufactured based on thermoplastic starch. Nanofibers were extracted from rice straw employing a developed chemo-mechanical method. In the chemical step, almost all of non-cellulosic components were removed and a white pulp of cellulose microfibers was obtained. Then, a diluted suspension of fibers was ultrasonicated to destruct intermolecular hydrogen bonds achieving nanofibers networks. Afterward, bio-nanocomposites were prepared by film casting. In order to study the effect of nanofibers content on the composite properties, the mechanical and dynamic mechanical properties, morphology, humidity absorption, and transparency of films were investigated. The yield strength and Young modulus of nanocomposites were satisfactorily enhanced compared to the pure thermoplastic starch film. The glass transition temperature of films was shifted to higher temperatures by increasing nanofibers contents. The uniform dispersion of the nanofibers was investigated using SEM images. The humidity absorption resistance of films was significantly enhanced by using 10 wt% cellulose nanofibers. The transparency of the nanocomposites was reduced compared to the pure starch films.     

Crystal structure and thermal properties of poly(vinylidene fluoridehexafluoropropylene) films prepared by various processing conditions

Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP) films were prepared using either a melt pressing or solution casting methods. The resulting PVDF-HFP films were drawn uniaxially at various drawing temperatures and speeds. The mp-PVDF-HFP films were more transparent and had more drawability than the sc-PVDF-HFP films. The crystal form of the initial films was the alpha-phase (non polarity) of PVDF. The maximum draw ratio was 7.6. The mp-PVDF-HFP films were prepared at a drawing speed of 2500 %/min at 100 °C. With increasing drawing speed, the beta-phase (polarity) became the dominant phase of PVDF in mp-PVDF-HFP films. The thermal properties of the resulting PVDF-HFP films improved with increasing drawing temperature.     

Antibacterial blend films of cellulose and chitosan prepared from binary ionic liquid system

A new hybrid ionic liquids solvent, 1-allyl-3-methylimidazolium chloride (AMIMCl) and glycine hydrochloride (Gly·HCl) was utilized to dissolve chitosan and fabricate chitosan/cellulose (Cs/Ce) blend films with chitosan proportion varying from 2 to 35 wt.% through solution casting method. FTIR, XRD, TG, SEM and EA were used to evaluate the prepared composites. Besides, the mechanical property and antibacterial activity were also analyzed. The shifting of the characteristic peaks of -NH and C=O for chitosan, similar crystal pattern with low intensity diffraction peaks at 2θ of around 20°, superior thermal stability (increased T_onset) with chitosan ratio below 10 wt.% in the composites suggested that the interactions via hydrogen bonds formed between chitosan and cellulose. Besides, the elemental analysis showed that the actual N% contents from the chitosan in the blend films were roughly equivalent to the theoretical value though the inevitable residue of ionic liquids. Furthermore, the blends not only presented compact structure but also processed high bacterial reduction to E. coli and S. aureus at pH 6.3, which indicated that the Cs/Ce blend films prepared via the Gly·HCl/AMIMCl dissolution method were suitable for production of degradable antibacterial materials.