Novel high‐performance wave‐transparent aluminum phosphate/cyanate ester composites

Advanced wave‐transparent composites are the key materials for many cutting‐edge industries including aviation and aerospace, which should have outstanding heat resistance, low dielectric constant and loss as well as good mechanical properties. A novel kind of high‐performance wave‐transparent composites based on surface‐modified aluminum phosphate AlPO₄(KH‐550) and cyanate ester (CE) was first developed. The dielectric and dynamic mechanical properties of AlPO₄(KH‐550)/CE composites were investigated intensively. Results show that AlPO₄(KH‐550)/CE composites have decreased dielectric loss and higher storage moduli than pure CE resin; in addition, the composites with suitable AlPO₄(KH‐550) concentration remain the outstanding thermal property and low dielectric constant of pure CE resin. The reasons attributing to these results are discussed from the effects of AlPO₄(KH‐550) on the key aspects such as morphology, curing mechanism, and interfacial adhesion of composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Ablation properties of aluminum silicate ceramic fibers and calcium carbonate filled silicone rubber composites

The ablative performance of aluminum silicate ceramic fiber (ASF) and calcium carbonate (CaCO₃) filled silicone rubber composites prepared through a two‐roll mill was examined. The properties of the composites were investigated by thermogravimetry, thermal conductivity measurements, and oxyacetylene torch testing. After the material was burnt, the structure and composition of the char were analyzed by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy (SEM). The results of the ablation test showed that the ablation resistance improved greatly in an appropriate filler scope. Combined with SEM, it was proven that a firm, dense, and thermal insulation layer, which formed on the composites surface during the oxyacetylene torch test, was a critical factor in determining the ablation properties. Thermogravimetric analysis revealed that the thermal stability of the composites was enhanced by the incorporation of ASF and CaCO₃. The thermal conductivity measurements showed that the silicone rubber composites had a very low thermal conductivity ranging from 0.206 to 0.442 W m^?1 K^?1; this significantly prevented heat from transferring into the inner matrix at the beginning of the burning process. The proportion of 20/40 phr (ASF/CaCO₃) was optimum for improving the ablation resistance of the silicone rubber composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41619.     

Thermal stability and ablation properties study of aluminum silicate ceramic fiber and acicular wollastonite filled silicone rubber composite

The thermal stability and ablation properties of silicone rubber filled with silica (SiO₂), aluminum silicate ceramic fiber (ASF), and acicular wollastonite (AW) were studied in this article. The morphology, composition, and ablation properties of the composite were analyzed after oxyacetylene torch tests. There were three different ceramic layers found in the ablated composite. In the porous ceramic layer, the rubber was decomposed, producing trimers, tetramers, and SiO₂. ASF and part of AW still remained and formed a dense layer. The SiO₂/SiC filaments in the ceramic layer reduced the permeability of oxygen, improving the ablation properties of the composites. The resultant ceramic layer was the densest, which acted as effective oxygen and heat barriers, and the achieved line ablation rate of the silicone composite were optimum at the proportion of 20 phr/40 phr (ASF/AW). Thermogravimetric analysis (TGA) confirmed that thermal stability of the composites was enhanced by the incorporation of ASF and AW. The formation of the ceramic layer was considered to be responsible for the enhancement of thermal stability and ablation properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39700.     

Enhanced mechanical and microwave-absorption properties of SiCf/AlPO4 composite with PIP–SiC interphase and the MWCNTs filler

A single-layer radar-absorbing structure in the X-band (8.2 GHz to 12.4 GHz) was designed and fabricated by blending multi-walled carbon nanotubes (MWCNTs) with the binder matrix of SiC fiber/aluminum phosphate matrix (SiC_f/AlPO₄) composite. The SiC interphase was successfully prepared on SiC fibers by a precursor infiltration and pyrolysis (PIP) method. The morphology of as-received interphase was observed by SEM, and its structure was characterized by XRD and Raman spectrum. The effects of PIP–SiC interphase on the mechanical and dielectric properties of the composite were investigated. The influence of MWCNTs content on the dielectric and microwave-absorption properties of coated SiC_f/AlPO₄ composite was discussed. When the content of MWCNTs was between 1.5 wt% and 3.5 wt% and the composite thickness is in the range of 2.5–3.5 mm, the SiC_f/AlPO₄ composite achieved excellent absorbing wave property in X-band.     

Hydrothermal synthesis of AlPO4-5 type zeolitic materials by using aluminum dross as a raw material

The hydrothermal synthesis of AIPO₄-5, which is one of the large pore size aluminum phosphate condensates like zeolitic materials, was carried out by using aluminum dross as a raw material. Triethylamine (TEA) was used as a structure directing agent (SDA) for AIPO₄-5 synthesis. Various physical properties such as crystal structure, surface texture and specific surface area were investigated for the obtained reaction product.AlPO₄-5 can be synthesized from aluminum dross under hydrothermal conditions at 453–473 K for 3 h. AlPO₄ salt as a by-product, which is a non-porous material, is formed at the same time. The crystal of the obtained AlPO₄-5 is hexagonal as observed by SEM photographs. It is desirable to heat-treat the reaction product at the temperature around 823 K to remove TEA. The crystal structure of AlPO₄-5 changes to non-porous aluminum phosphate in case of a heat treatment exceeding 973 K. The specific surface areas of the reaction product before and after heat treatment at 823 K are 18 and 360 m²/g, respectively.     

Influence of copper oxide nanomaterials in a poly(ether sulfone) membrane for improved humic acid and oil–water separation

In this study, self‐synthesized copper(I) oxide (Cu₂O) nanoparticles were incorporated in poly(ether sulfone) (PES) mixed‐matrix membranes (MMMs) through the phase‐inversion method. A cubic arrangement and crystallite size of 28 nm was identified by transmission electron microscopy and X‐ray diffraction (XRD) for the as‐synthesized Cu₂O particles. The pristine PES membrane had a higher contact angle value of 88.50°, which was significantly reduced up to 50.10° for 1.5 wt % PES/Cu₂O MMMs. Moreover, XRD analysis of the Cu₂O‐incorporated PES membrane exhibited a new diffraction pattern at 36.46°. This ensured that the Cu₂O nanoparticles were distributed well in the PES matrix. Interestingly, the water permeability progressively improved up to 66.72 × 10^?9 m s^?1 kPa^?1 for 1.5 wt % PES/Cu₂O MMMs. Furthermore, the membrane performances were also evaluated with different feed solutions: (1) bovine serum albumin, (2) humic acid, and (3) oil–water. The enhanced rejection and lower flux reduction percentage were observed for hybrid membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43873.     

Preparation,phase assemblage and microwave dielectric properties of AlPO4-BPO4-SiO2 ternaries

Microwave dielectric ceramics with low dielectric permittivities (?r<6), high quality values and temperature sable resonator frequencies are strongly desired with the development of millimeter wave communication. In this paper, a compositional design for low-k materials was proposed from the point view of crystal chemistry. AlPO₄-BPO₄-SiO₂ glass-ceramics were prepared by traditional solid state and sol-gel processes, respectively. The sintering behaviors, phase assemblages, microstructures and microwave dielectric properties of AlPO₄-BPO₄-SiO₂ ternaries have been studied. The solid solubility, glass forming ability and crystallization of the AlPO₄–BPO₄–SiO₂ ternaries can be understood by considering the structural flexibility via the degree of ionicity i of the bonds in the ternaries. All compositions demonstrate low dielectric permittivity less than five and negative temperature coefficient of resonant frequency. Maximum Q × f value could be obtained for the 0.45AlPO₄–0.45BPO₄–0.10SiO₂ composition prepared by sol-gel process after sintering at 1175 °C/2 h: ?_r～4.16, Q × f～59,519.     

Oxidation Resistance of AlPO4 Bonded Ceramic Coating Formed on Titanium Alloy for High‐Temperature Applications

AlPO₄ based coatings were prepared on Ti‐6Al‐2Zr‐1Mo‐1V titanium alloy using aluminum phosphate as a binder and Al₂O₃/Cr₂O₃ based mixing particles as the fillers. The microstructure, phase and chemical composition of the coatings were analyzed by SEM, XRD and EDS techniques. The high temperature infrared emissivity values of coated and uncoated titanium samples were tested. The results show that the coating had a higher infrared emissivity value (>0.8) than titanium substrate (0.15–0.3) in the wide wavelength range of 5–20 mm, which is attributed to the uniform dispersion of high emissivity Al₂O₃ and Cr₂O₃ particles in the AlPO₄ binder matrix. The coated titanium samples exhibited excellent oxidation resistance performance with significantly decreased oxidation rates at 600 and 800°C. The mass gain of the coated sample kept at a low and stable constant of 0.15 mg/cm², significantly lower than that of titanium substrate (0.54 mg/cm²) when oxidized at 600°C up to 100 h.     

Control of aluminum phosphate coating on mullite fibers by surface modification with polyethylenimine

Aluminum phosphate (AlPO₄) is a promising oxidation-resistant and weak interface for ceramic-matrix composites. In this research, AlPO₄ coating was deposited on mullite fibers by an improved liquid-phase method based on electrostatic attraction. A cationic polyelectrolyte, polyethylenimine (PEI), was used for surface modification of mullite fibers. The formation process, phase evolution and microstructure of the coating were studied. The zeta potential of AlPO₄ particles, PEI-adsorbed AlPO₄ particles, and PEI-adsorbed mullite particles was characterized to find the proper pH value for improving electrostatic attraction. The obtained AlPO₄ coating was porous and continuous, whose thickness could be controlled by multiple coating cycles. The relatively low calcination temperature (600 or 1000 °C) was a useful heat treatment method to develop bonding between coating and fiber as well as reduce the fiber strength degradation. The phase transformations of AlPO₄ have little volume change, and cristobalite AlPO₄ is thermal compatible with mullite. Therefore, the coating structure was preserved after calcining at 1200 °C. The technique is also applicable for other fibers contained mullite phase to fabricate high-performance AlPO₄ coated mullite/mullite composites.     

Novel aluminum phosphate/cyanate ester composites: Thermodegradation behaviors and kinetic analyses

Thermodegradation behaviors of novel aluminum phosphate/cyanate ester (AlPO₄(KH550)/CE) composites were studied in detail. Results show that thermodegradation behaviors and kinetic parameters of AlPO₄(KH550)/CE composites are greatly dependent on the AlPO₄(KH550) loading. The addition of AlPO₄(KH550) into CE resin changes the thermodegradation mechanism (mainly at the temperature lower than 450°C) and degradation process from two steps to three steps. Comparing with CE resin, AlPO₄(KH550)/CE composites have lower initial degradation temperature and greatly higher char yield. Besides, for each thermodegradation step, the more the AlPO₄ content, the smaller the activation energy value is. All reasons leading to these outcomes are investigated intensively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,characterization, and performance evaluation of PES/EDA‐functionalized TiO2 mixed matrix membranes for CO2/CH4 separation

Poor adhesion between hydrophobic polymers and hydrophilic inorganic fillers is a challenge that encumbers a high separation performance of mixed matrix membrane (MMM). In this study, Titanium(IV) oxide (TiO₂) nanoparticles were functionalized using ethylenediamine (EDA) before embedment in poly(ether sulfone) (PES) polymer matrix. MMMs were synthesized through dry phase inversion technique. Membranes morphology and nanoparticles dispersion was drastically enhanced posterior amine modification indicating an improved adhesion between the polymer and filler particles. Membranes thermal stability was likewise improved as higher degradation temperatures were perceived for PES/EDA–TiO₂ MMMs. Gas separation evaluation for pure carbon dioxide (CO₂) and methane (CH₄) gases revealed a remarkably enhanced separation performance upon amine‐grafting of TiO₂ as EDA‐TiO₂ MMMs exhibited a higher separation performance as compared to MMMs with pristine TiO₂. The highest ideal separation factor achieved was 41.52 with CO₂ permeability of 10.11 Barrer at an optimum loading of 5% wt of EDA‐TiO₂ which is threefold higher as compared to neat PES membrane and approximately twofold higher than MMMs with pristine TiO₂, respectively, at the same filler loading. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45346.     

Enhanced fracture toughness of epoxy resins with novel amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) triblock copolymers

Amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) (PES‐CTBN‐PES) triblock copolymers with controlled molecular weights of 15,000 (15K) or 20,000 (20K) g/mol were synthesized from amine‐terminated PES oligomer and commercial CTBN rubber (CTBN 1300x13). The copolymers were utilized to modify a diglycidyl ether of bisphenol A epoxy resin by varying the loading from 5 to 40 wt %. The epoxy resins were cured with 4,4′‐diaminodiphenylsulfone and subjected to tests for thermal properties, plane strain fracture toughness (K_IC), flexural properties, and solvent resistance measurements. The fracture surfaces were analyzed with SEM to elucidate the toughening mechanism. The properties of copolymer‐toughened epoxy resins were compared to those of samples modified by PES/CTBN blends, PES oligomer, or CTBN. The PES‐CTBN‐PES copolymer (20K) showed a K_IC of 2.33 MPa m^0.5 at 40 wt % loading while maintaining good flexural properties and chemical resistance. However, the epoxy resin modified with a CTBN/8K PES blend (2:1) exhibited lower K_IC (1.82 MPa m^0.5), lower flexural properties, and poorer thermal properties and solvent resistance compared to the 20K PES‐CTBN‐PES copolymer‐toughened samples. The high fracture toughness with the PES‐CTBN‐PES copolymer is believed to be due to the ductile fracture of the continuous PES‐rich phases, as well as the cavitation of the rubber‐rich phases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1556–1565, 2002; DOI 10.1002/app.10390     

Enhanced microwave absorbance of oxidized SiCf/AlPO4 composites via the formation of a carbon layer on the SiC fibre surface

A single-layer radar-absorbing structure active in the X-band (8.2?GHz to 12.4?GHz) was demonstrated by blending SiC fibres with an AlPO₄ matrix material. The as-prepared SiC_f/AlPO₄ composites were oxidized at 1273?K for several hours to investigate the effects of oxidation on the dielectric and wave-absorbing properties. Scanning and transmission electron microscopy were used to characterize the morphology and microstructure of the composites. The AlPO₄-SiO₂ solid solution during oxidation promoted the formation of a complete carbon layer on the SiC fibre surface. The real and imaginary parts of the SiC_f/AlPO₄ composites increased from 4.2–4.4 to 5.9–7.1 and from 0.08–0.2 to 3.9–5.2, respectively, with increasing oxidation time from 0 to 10?h, respectively. When the thickness of the composites increased from 2.9?mm to 3.3?mm, the wave-absorbing property noticeably improved due to the formation of a carbon layer on the SiC fibre surface after oxidation.     

Electrochemical performances of lithium ion battery using alkoxides of group 13 as electrolyte solvent

Tris(methoxy polyethylenglycol) borate ester (B-PEG) and aluminum tris(polyethylenglycoxide) (Al-PEG) were used as electrolyte solvent for lithium ion battery, and the electrochemical property of these electrolytes were investigated. These electrolytes, especially B-PEG, showed poor electrochemical stability, leading to insufficient discharge capacity and rapid degradation with cycling. These observations would be ascribed to the decomposition of electrolyte, causing formation of unstable passive layer on the surface of electrode in lithium ion battery at high voltage. However, significant improvement was observed by the addition of aluminum phosphate (AlPO₄) powder into electrolyte solvent. AC impedance technique revealed that the increase of interfacial resistance of electrode/electrolyte during cycling was suppressed by adding AlPO₄, and this suppression could enhance the cell capabilities. We infer that dissolved AlPO₄ components formed electrochemically stable layer on the surface of electrode.     

Mechanical properties of reinforced porcelain slabs with mullite whiskers introduced by aluminum silicate fiber

Mullite whiskers (3Al₂O₃·2SiO₂) reinforced porcelain slabs with high bending strength and fracture toughness were successfully prepared by calcining a kaolin-potash feldspar-albite mixture with aluminum silicate fibers (ASF, Al₂O₃·SiO₂). Effects of ASF content on the properties of porcelain slabs were investigated. Bending strength and fracture toughness of the samples reach the peak values, 39% and 19% higher than that of the blank samples when the amount of ASF is 5 wt%. The elongated and needle-like mullite whiskers are obtained in the substrates with ASF fiber addition, differing from the rod-shaped mullite whiskers in the blank ones. During the sintering process, ASF provides growth environment and ingredient for elongated mullite whiskers. The in-situ generated elongated mullite whiskers link the porcelain slabs substrate as a bridge and consume more energy before the fracture occurred. Therefore, mullite whiskers induced by ASF can offer reliable opportunity for preparation of porcelain slabs with good mechanical properties.     

Optical Properties and van der Waals–London Dispersion Interactions in Berlinite Aluminum Phosphate from Vacuum Ultraviolet Spectroscopy

The interband optical properties of single‐crystal berlinite AlPO₄ have been investigated in the vacuum ultraviolet (VUV) range using VUV spectroscopy and spectroscopic ellipsometry. The complex optical properties were directly determined from 0.8 to 45 eV. Band gap energies, index of refraction and complex dielectric functions, oscillator index sum rule, and energy loss functions were calculated through Kramers–Kronig transformation. Direct and indirect band gap energies of AlPO₄ over the absorption coefficient range of 33–11 000 cm^?1 are 8.06 and 7.89 eV, respectively. The index of refraction at 2 eV, n_vis, is 1.51. The interband transition features at 10.4, 11.4, 14.2, 16.2, 17.3, 21, 22.5, 24.5, and 31 eV were indexed and correlated with the electronic structure of AlPO₄. Strong similarities were observed between AlPO₄ and its structural isomorph SiO₂ in the exciton and interband transitions, resulting from the similarity of their constituent tetrahedra and the strong electron localization therein. The London dispersion spectrum for AlPO₄ was calculated, and the Hamaker coefficients for AlPO₄ with various interlayers were calculated using the Lifshitz method. These results elucidate the role of phosphate complex anions on the electronic structure and van der Waals forces in important organic and inorganic systems.     

Synthesis and Characterization of Sulfonated Cardo Poly(Arylene Ether Sulfone)s for Fuel Cell Proton Exchange Membrane Application

Sulfonated cardo poly(arylene ether sulfone)s ( SPPA ‐ PES ) with various degrees of sulfonation (DS) were prepared by post‐sulfonation of synthesized phenolphthalein anilide ( PPA ; N‐phenyl‐3,3′‐bis(4‐hydroxyphenyl)‐1‐isobenzopyrolidone) poly(arylene ether sulfone)s ( PPA ‐ PES ) by using concentrated sulfuric acid. PPA ‐ PES copolymers were synthesized by direct polycondensation of PPA with bis‐(4‐fluorophenyl)‐sulfone and 4,4′‐sulfonyldiphenol. The DS was varied with different mole ratios of PPA (24, 30, 40, 50 mol.%) in the polymer. The structure of the resulting SPPA ‐ PES copolymers and the different contents of the sulfonated unit were studied by Fourier transform infrared (FT‐IR) spectroscopy, ¹H NMR spectroscopy, and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymer with water. The ion exchange capacity (IEC) and proton conductivity of SPPA ‐ PES were evaluated according to the increase of DS. The water uptake (WU) of the resulting SPPA ‐ PES membranes was in the range of 20–72%, compared with 28% for Nafion 211®. The SPPA ‐ PES membranes showed proton conductivities of 23–82 mS cm^–1, compared with 194 mS cm^–1 for Nafion 211®, under 100% relative humidity (RH) at 80 °C.     

Degradation of Nextel™ 610‐based oxide‐oxide ceramic composites by aluminum oxychloride decomposition products

Nextel? 610 alumina fibers and alumina‐YAG (yttrium‐aluminum garnet) matrices were used to make oxide‐oxide ceramic matrix composites (CMCs) with and without monazite (LaPO₄) fiber‐matrix interfaces. Twelve sequential aluminum oxychloride (AlOCl) infiltrations with 1 hour heat treatments at 1100°C and a final 1 hour heat treatment at 1200°C were used for matrix densification. This matrix processing sequence severely degraded CMC mechanical properties. CMC tensile strengths and interlaminar tensile (ILT) strengths were less than 10 MPa and 1 MPa, respectively. Axial fracture of Nextel? 610 fibers was observed after ILT testing, highlighting the extreme degradation of fiber strength. Extensive characterization was done to attempt to determine the responsible degradation mechanisms. Changes in Nextel? 610 fiber microstructure after CMC processing were characterized by optical microscopy, SEM, and extensively by TEM. In AlOCl degraded fibers, grain boundaries near the fiber surface were wetted with a glass that contained Y₂O₃/SiO₂ or Y₂O₃/La₂O₃/P₂O₅/SiO₂, and near‐surface pores were partially filled with Al₂O₃. This glass must also contain some Al₂O₃ and initially some chlorine. AlOCl decomposition products were predicted using the FactSage^® Thermochemical code, and were characterized by mass spectrometry. Effects of AlOCl precursors on monazite coated and uncoated Nextel? 610 fibers tow and filament strength were evaluated. A mechanism for the severe degradation of the oxide‐oxide CMCs and Nextel? 610 fibers that involves subcritical crack growth promoted by release of chlorine containing species during breakdown of intergranular glasses in an anhydrous environment is proposed.     

The flame retardant effect of aluminum phosphinate in combination with zinc borate,borophosphate, and nanoclay in polyamide‐6

The effect of zinc borate (ZnB), borophosphate (BPO₄), and organoclay were studied to improve the flame retardancy of polyamide‐6 composites containing organic phosphinates. The flame retardancy of polyamide‐6 composites was investigated using limiting oxygen index (LOI), Underwriters Laboratories (UL‐94) standard, thermogravimetric analysis, Fourier transform infrared spectroscopy, and mass loss calorimeter. The addition of 15 wt% aluminum phosphinate (AlPi) increased the LOI value from 22.5 to 29.5, and V0 rating was obtained from UL‐94 test. The addition of organoclay, ZnB, and borophosphate does not change the predominant gas phase mechanism of AlPi during LOI and UL‐94 tests. The addition of organoclay increased the condensed phase mechanism of AlPi physically by the protective effect of layered silicate, whereas the addition of ZnB increased the condensed phase mechanism of AlPi chemically by the formation of boron aluminum phosphate species deducted from mass loss calorimeter studies. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of clay on properties of polyimide‐clay nanocomposites

Effect of clay on mechanical, thermal, moisture absorption, and dielectric properties of polyimide‐clay nanocomposites was investigated. Nanocomposites of polyimide (ODA‐BSAA) hybridized with two modified clay (PK‐802 and PK‐805) were synthesized for comparison. The silicate layers in the polymer matrix were intercalated/exfoliated as confirmed by wide‐angle X‐ray diffraction and transmission electron microscopy. Thermal stability, moisture absorption, and storage modulus for these nanocomposites are improved as hybridized clay increases. Reduced dielectric constants due to the hybridization of layered silicates are observed at frequencies of 1 kHz–1 MHz and temperatures of 35–150°C. The tetrahedrally substituted smectite (PK‐805) resulted in higher mechanical strength and dielectric constants than those of octahedrally substituted smectite (PK‐802), which could be attributed to their stronger ionic bonding between clay layer and polymer matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 318–324, 2007