Porous yttria‐Stabilized Zirconia Ceramics Fabricated by Nonaqueous‐Based Gelcasting Process with PMMA Microsphere as Pore‐Forming Agent

Porous yttria‐stabilized zirconia (YSZ) ceramics were fabricated using tert‐butyl alcohol (TBA)‐based gelcasting with monodisperse polymethylmethacrylate (PMMA) microspheres as both pore‐forming agent and lubricant agent. The TBA‐based slurry of 50 vol% solid loading with excellent rheological properties appropriate for casting was successfully prepared by using a commercial polymer dispersant DISPERBYK‐163 as both dispersant and stabilizer. The distribution of the spherical pores made from PMMA microspheres was very homogeneous. Their average diameter decreased from 16.9 to 15.7 μm when the sintering temperature was increased from 1350°C to 1550°C. The compressive strength increased from 14.57 to 142.29 MPa and the thermal conductivity changed from 0.17 to 0.65 W/m·K when the porosity decreased from 71.6% to 45.1%. The results show that this preparation technology can make all the main factors controllable, such as the porosity, the size and shape of pores, the distribution of pores, and the thickness and density of pore walls. This is significant for fabricating porous ceramics with both high compressive strength and low thermal conductivity.     

Preparation of calcium hexaluminate porous ceramics by gel-casting method with polymethyl methacrylate as pore-forming agent

Calcium hexaluminate (CA₆) porous ceramics were prepared by gel-casting method, with α-Al₂O₃ and CaCO₃ as raw materials and polymethyl methacrylate (PMMA) microspheres as pore-forming agent. The effects of the amount of pore-forming agent PMMA microspheres on the phase composition, bulk density, apparent porosity, flexural strength, microstructure, thermal shock stability and thermal conductivity of CA₆ porous ceramics were systematically studied. The pores of CA₆ porous ceramics are mainly formed by the burning loss of PMMA microspheres and the decomposition of organic matter. Adding an appropriate amount of PMMA microspheres as pore-forming agent has a positive effect on the thermal shock stability of CA₆ porous ceramics. When the amount of pore-forming agent is 15 wt%, the volume density of CA₆ porous ceramics is 1.33 g/cm³, the porosity is 63%, the flexural strength is 13.9 MPa, the thermal shock times can reach 9 times, and the thermal conductivity is 0.293 W/(m·K), which can meet the application in refractory, ceramics or high temperature cement industries.     

Effects of thermal treatment on the CO2 sorption of triblockcopolymers derived from polyimide and poly(methylmethacrylate)

ABA‐type triblock copolymers were synthesized using 4,4‐(hexafluoroisopropylidene) diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) and poly(methyl methacrylate) (PMMA). The films were characterized by determining the effects of different content ratios and thermal decomposition of PMMA block on CO₂ sorption properties. TGA results showed that a thermal labile block can be completely decomposed under a previously reported thermal condition. SEM results presented that the asperity was micro‐phase separation caused by the PMMA block content rate. Numerous pores with sizes of approximately 10 to 50 nm were detected on Block(28/72) and Block(10/90). The isotherms of all films fitted the dual‐mode sorption model, and CO₂ sorption decreased with increased PMMA content rate. Infinite‐dilution CO₂ solubility depended on the Langmuir's site of each polymer because S_H0/S₀ of PI and Block(PI/PMMA) varied from 0.84 to 0.92 CO₂ affinity was increased by thermal treatment as indicated by the higher b and S₀ values of thermally treated films than those of nontreated films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42208.     

Novel fabrication route for porous silicon carbide ceramics through the combination of in situ polymerization and reaction bonding techniques

For the first time, an in situ polymerization technique was applied to produce mullite‐bonded porous SiC ceramics via a reaction bonding technique. In this study, SiC microsized particles and alumina nanopowders were successfully coated by polyethylene (PE), which was synthesized from the particle surface in a slurry phase reactor with a Ziegler–Natta catalyst system. The thermal studies of the resulting samples were performed with differential scanning calorimetry and thermogravimetric analysis. The morphology analysis obtained by transmission electron microscopy and scanning electron microscopy (SEM) confirmed that PE was successfully grafted onto the particle surface. Furthermore, the obtained porous ceramics were characterized in terms of their morphologies, phase composition, open porosity, pore size distribution, and mechanical strength. SEM observations and mercury porosimtery analysis revealed that the quality of the dispersion of nanosized alumina powder into the microsized SiC particles was strongly enhanced when the particles were coated by polymers with in situ polymerization. This resulted in a higher strength and porosity of the formed ceramic porous materials with respect to the traditional process. In addition, the X‐ray diffraction results reveal that the amount of mullite as the binder increased significantly for the samples fabricated by this novel method. The effects of the sintering temperature, forming pressure, and polymer content on the physical and mechanical properties of the final porous ceramic were also evaluated in this study. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40425.     

Pore-forming agent induced microstructure evolution of freeze casted hydroxyapatite

There were interconnected small lamellar pores, big spherical pores and ceramic walls in the hydroxyapatite (HAP) ceramics fabricated by a freeze casting/pore-former method. As keeping the content of polymethyl methacrylate (PMMA) constant and decreasing the size of PMMA, the size of spherical pores and length of ceramic wall both decreased, and the compressive strength increased. As keeping the size of PMMA and decreasing the content of PMMA, the open porosity decreased and compressive strength increased. The shapes of pores caused by ice crystals were reticular, lamellar and treelike, in turn. The HAP ceramics with the spherical pores of 150-250 μm, open porosity of 62.13% and compressive strength of 7.01 MPa are prospective to have biomedical application.     

Low-temperature sintering of (Pb1−xCdx)(Zr0.965Ti0.035)O3 ferroelectric ceramics for multilayer device application

Low-temperature sintering behaviour and ferroelectric properties of lead zirconate titanate (PZT95/5) ferroelectric (FE) ceramics doped with CdO were investigated. The addition of CdO significantly promoted the densification and decreased the sintering temperature of PZT95/5 ceramic. When the addition of CdO content is 1?mol-%, PCZT95/5 ceramics with a relative high density of approximately 97.5% can be obtained by sintering at 1100°C and exhibits excellent electric properties with d₃₃ values of 65 pC/N, this d₃₃ value is close to that of PZT95/5 ceramic sintered at 1350°C. With an increase in the CdO content, the FE phase content decreases and the antiferroelectric (AFE) phase content increases gradually. When the CdO content is 2?mol-%, the most of FE phase of PCZT 95/5 ceramics changes to AFE phase, the polarisation value is quite small and the d₃₃ value drops to zero.     

Enhanced Thermoelectric Performance of CdO Ceramics Via Ba2+ Doping

Polycrystalline Cd_1?xBa_xO (0 ≤ x ≤ 0.08) ceramics were synthesized via conventional solid‐state reaction method, and the effect of Ba²⁺ doping on the microstructure as well as the thermoelectric transport properties of the samples were investigated. It was found that doping of Ba²⁺ can inhibit the grain growth of CdO, resulting in a considerable reduction in grain size. Moreover, with the increase in Ba²⁺ doping content, both the electrical conductivity and the thermal conductivity of Cd_1?xBa_xO decreased, whereas the Seebeck coefficient increased. A high ZT value of 0.47 was achieved for Cd_0.99Ba_0.01O at 1000 K, 38% higher than the undoped CdO, mostly due to reduction of the thermal conductivity.     

Thermal behavior and properties of polystyrene/poly(methyl methacrylate) blends

The thermal behavior and properties of immiscible blends of polystyrene (PS) and poly(methyl methacrylate) (PMMA) with and without PS‐b‐PMMA diblock copolymer at different melt blending times were investigated by use of a differential scanning calorimeter. The weight fraction of PS in the blends ranged from 0.1 to 0.9. From the measured glass transition temperature (T_g) and specific heat increment (ΔC_p) at the T_g, the PMMA appeared to dissolve more in the PS phase than did the PS in the PMMA phase. The addition of a PS‐b‐PMMA diblock copolymer in the PS/PMMA blends slightly promoted the solubility of the PMMA in the PS and increased the interfacial adhesion between PS and PMMA phases during processing. The thermogravimetric analysis (TGA) showed that the presence of the PS‐b‐PMMA diblock copolymer in the PS/PMMA blends afforded protection against thermal degradation and improved their thermal stability. Also, it was found that the PS was more stable against thermal degradation than that of the PMMA over the entire heating range. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 609–620, 2004     

Synthesis,characterization, optical,and dielectric properties of polyvinyl chloride/cadmium oxide nanocomposite films

Nano‐sized cadmium oxide (CdO) was synthesized using a sol–gel method and mixed with poly(vinyl chloride) (PVC). X‐ray diffraction and high‐resolution transmission electron microscopy measurements indicated that the average particle size of the CdO is about 70.18 nm. Scanning electron microscopy images revealed a good dispersion of CdO nanoparticles on the surface of the PVC films. The optical energy band gap (E_g) showed a decrease from 5.08 to 4.88 eV with increasing the CdO content. The refractive index dispersion of the nanocomposite films was found to obey the single oscillator model. The dispersion parameters were changed by CdO incorporation. According to the frequency and temperature dependence of the dielectric constant (ε′), the observed α_a‐relaxation peaks were assigned to the micro‐Brownian motion of the polymer main chains. The influence of CdO nanoparticles content on the ac conductivity and the activation energy of PVC nanocomposite films were discussed. It was found that both dielectric and optical properties were reinforced by the adding of CdO nanoparticles to the PVC matrix. Finally, the results of the present system are compared with those of similar materials. POLYM. COMPOS., 35:1842–1851, 2014. © 2014 Society of Plastics Engineers     

Preparation of three-dimensionally linked pore-like porous atomized ceramics with high oil and water absorption rates

Ceramic atomization cores are a new application of porous ceramics; however, the challenging regulation of the pore structures of porous ceramics has limited their application. To improve the low liquid absorption rates and low liquid storage capacity of porous ceramics in the field of atomization, this study used three substances, polymethyl methacrylate (PMMA), starch, and diatomaceous earth, to produce porous ceramics with a three-dimensional interconnected triple-porous structure by sacrificial templating. In the porous ceramics, large pores resulting from PMMA increase liquid storing capacity, medium pores resulting from the starch facilitate the transport of liquid, and small pores resulting from diatomaceous earth enhance capillary action, significantly increasing the rate of liquid absorption. By varying the PMMA contents and type of starch in the preform, water and oil storage capacities of up to 123% and 143%, respectively, can be achieved. We found that an optimized porous ceramic with dimensions of 15 mm × 15 mm × 15 mm absorbs water rapidly (reaching saturation in only 1.67 s), demonstrates good solid–liquid properties and shape stability, and is recyclable (requires drying before reuse). The proposed porous ceramics have promising atomization core and oil–water separation applications.     

Poly(methyl methacrylate)/SIO2 hybrid membranes: Effect of solvents on structural and thermal properties

In this paper, hybrid organic–inorganic membranes were prepared using three different solvents and characterized. The hybrid membranes were fabricated using sol–gel technique, which had polymethyl‐methacrylate (PMMA) and tetraethyl orthosilicate (TEOS) as materials, with 80/20 ratio. The thin films were then characterized using FTIR, SEM, EDX, and mapping techniques. From the preliminary characterization, hybrid membranes were found to have nano and ultra scale tight‐pores ranges, which was influenced by the solvent used. The SEM images clearly show that hybrid membranes have homogenous and smooth surface. FTIR spectroscopy uncovered all the signature peaks characteristic of silicate structures in the near‐surface regions. Fingerprints of Si? O? Si groups in cyclic and linear molecular substructures were also present. From DSC analysis, the T_g value of the PMMA moieties in hybrids membranes was in the order H‐15‐Toluene < Pure PMMA < H‐15‐THF < H‐15‐DMF. Furthermore, from TGA analysis it was found that the hybrid membranes have higher thermal stability compared with that of pure PMMA. EDX and mapping analysis showed that the composition and distribution of particles in the membranes were different and dependent on the solvents used. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Physical and mechanical properties of poly(methyl methacrylate)‐grafted natural rubber synthesized by methyl methacrylate photopolymerization initiated by N,N‐diethyldithiocarbamate functions previously created on natural rubber chains

Well‐defined poly(methyl methacrylate) (PMMA)‐grafted natural rubbers (NRs) were prepared to study the structure–property relationships. Syntheses were achieved by the photopolymerization of methyl methacrylate initiated by N,N‐diethyldithiocarbamate groups created beforehand in side positions on the NR chains. With this procedure, good control of the graft density and PMMA content could be obtained. Thermal, morphological, and mechanical properties of NR‐g‐PMMA copolymers were studied as a function of the NR/PMMA composition and graft density. NR‐g‐PMMAs containing 15–80% grafted PMMA showed characteristics of heterogeneous materials (characterized by two glass‐transition temperatures, those of PMMA and NR, in differential scanning calorimetry). Under these conditions, they developed the morphology of thermoplastic elastomers with PMMA nodules dispersed in the rubber matrix when the PMMA content was near 20%; conversely, they developed the morphology of softened thermoplastics with rubber nodules dispersed in PMMA when the PMMA content was near 80%. Graft copolymers containing about 20% PMMA remained essentially rubbery, but they were already different from pure NR. On the other hand, the thermal stability of NR wash improved after the introduction of PMMA grafts onto NR chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of PMMA composites activated with starch for immobilization of L‐asparaginase

Poly (methyl methacrylate) (PMMA)–starch composites were prepared by emulsion polymerization technique for L‐asparaginase (L‐ASNase) immobilization as highly activated support. The hydroxide groups on the prepared composites offer a very simple, mild and firm combination for enzyme immobilization. The pure PMMA and PMMA‐starch composites were characterized as structural, thermal and morphological. PMMA‐starch composites were found to have better thermal stability and more hydrophilic character than pure PMMA. L‐ASNase was immobilized onto PMMA‐starch composites contained the different ratio of starch (1, 3, 5, and 10 wt %). Immobilized L‐ASNase showed better performance as compared to the native enzyme in terms of thermal stability and pH. K_m value of immobilized enzyme decreased approximately eightfold compared with the native enzyme. In addition to, immobilized L‐ASNase was found to retain 60% of activity after 1‐month storage period at 4 °C. Therefore, PMMA‐starch composites can be provided more advantageous in terms of enzymatic affinity, thermal, pH and storage stability as L‐ASNase immobilization matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43421.     

Preparation and properties of polycarbonate nanocomposites using attapulgite grafted poly(methyl methacrylate) as a potential nanofiller

The Core‐shell hybrid particles with attapulgite (ATP) as the core and polymethylmethacrylate (PMMA) as the shell (ATP‐g‐PMMA) were prepared via reversible addition‐fragmentation chain transfer (RAFT) polymerization method. The diameter of ATP‐g‐PMMA was increased to 50–60 nm, and the surface hygroscopicity was decreased observably after surface grafting. Then, ATP‐g‐PMMA hybrid particles were filled into the polycarbonate (PC) by melt mixing to afford nanocomposites, and the mechanical properties, microstructures, thermal stability, and rheological behavior of nanocomposites were investigated by varying ATP‐g‐PMMA concentration in the range 1, 3, 5, and 7 wt % in PC. Fourier Transform infrared spectroscopy (FTIR) suggested that there is no esterification reaction between particles and matrix. Slight changes in tensile strength, and noticeable decrease of elongation and impact strength were observed with the increase in ATP‐g‐PMMA particles loading. The morphology evaluated by field‐emission scanning electron microscopy (FESEM) indicated that ATP‐g‐PMMA was dispersed with a diameter range of 80–100 nm, and phase separation was appeared with increasing ATP‐g‐PMMA loadings. Thermogravimetric analysis (TGA) results revealed the thermal stability of composites was strengthened. The disentanglement and interface slip induced by preferred orientation and directional arrangement of ATP‐g‐PMMA resulted in lower complex viscosity (η*) and higher loss factor (tan δ) compared with the pristine PC. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42262.     

Modification of porous suspension‐PVC particles by stabilizer‐free aqueous dispersion polymerization of absorbed monomers

The modification of porous PVC particles by an in‐situ stabilizer‐free polymerization/crosslinking of a monomer/crosslinker/peroxide solution absorbed within the PVC particles is presented. The modifying crosslinked polymers are polystyrene (PS) crosslinked with DVB (divinyl benzene), polymethyl methacrylate (PMMA) crosslinked with ethylene glycol dimethacrylate (EGDMA), and styrene‐MMA copolymer crosslinked with DVB. The modified PVC particles characterization includes polymerization yield, non‐extractables, ¹³C solid‐state CPMAS NMR, porosity measurements and also morphology and dynamic mechanical behavior (DMTA). The levels of nonextractable fractions found and ¹³C solid‐state CPMAS NMR results are indicative of low chemical interaction in the semi‐IPN PVC particles. Particle porosity levels and SEM observations indicate that styrene and MMA mainly polymerize within the PVC particles' bulk and just small amounts in the pores. MMA polymerization in the PVC pores is as crusts covering the PVC pore surfaces, whereas styrene polymerization in the PVC pores is by filling the pores. Dynamic mechanical studies show that tanδ and the storage modulus curves are influenced by the incorporation of PS and XPS but not by the incorporation of PMMA and XPMMA.     

Synthesis of macroporous β-tricalcium phosphate with controlled porous architectural

β-Tricalcium phosphate (TCP) macroporous ceramics were produced by a new manufacturing procedure. A polymeric scaffold constituted of polymethylmethacrylate balls (PMMA), welded together by a thermal forming treatment, is impregnated with a TCP aqueous suspension. After drying step, the thermal removal of the organic compound generates an interconnected macroporosity inside the piece. The coalescence of PMMA balls during the thermal forming treatment follows a sintering mechanism of viscous flow type. This behaviour allows to control the dimension of bridging between particles and thus, the interconnection between pores of sintered material. This new process allows to carry out materials with macropore dimensions which can vary between 100 μm at several millimetres and a perfectly controlled size of interconnection ranging between 0.3 and 0.6 times the macropore diameter. Total porosity volume evolves in an interval from 70 to 80%.     

The capillary and thermal performance of the porous silicon nitride ceramics with nearly spherical pore structure

The capillary and thermal performance of porous Si₃N₄ ceramics with nearly spherical pore structure has been investigated by altering the addition and diameter of pore-forming agent polymethyl methacrylate (PMMA) in this work. An exponential model is used to evaluate the liquid uptake capacity of porous Si₃N₄ ceramics. Porous Si₃N₄ ceramics fabricated by 5 μm PMMA with 40 wt.% addition possess the lowest capillary time constant and show the best capillary performance owing to the perfect balance between friction resistance and capillary force. The thermal conductivity of porous Si₃N₄ ceramics is significantly impacted by their porosity. Alexander model with an exponent of .96 is suitable for predicting the thermal conductivity of porous Si₃N₄ ceramics due to its R-squared up to .99. Moreover, with the addition and diameter of PMMA decrease, the flexural strength of porous Si₃N₄ ceramics increases. These results support the application of porous Si₃N₄ ceramics in the field of mass and heat transfer.     

Preparation and characteristics of polyacrylic ester‐based water‐free powder coatings in supercritical carbon dioxide

Powder coating for dry coating technique of paper as the promising method has attracted more and more attentions in recent years due to its advantages in reducing the dosage of water and saving energy compared with conventional coating. This study focused on the in situ polymerization of methyl methacrylate (PMMA) under a water‐free condition in supercritical carbon dioxide in the presence of inorganic kaolin. The effects of varying the concentrations of the monomer, initiator, and stabilizer on the molecular weight and morphology of the resultant PMMA were investigated and discussed. Then the powder coating was systematically evaluated and characterized by gel permeation chromatography, scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Meanwhile, the feasibility of manufacturing PMMA/kaolin powder coatings was explored, and the mechanism of polymerization and the thermal degradation kinetics of powder coating were studied. The experimental results showed that the properties of PMMA as a film former were suitable with the molecular weight and narrow molecular weight distribution close to that in conventional coating when the concentration of monomer was about 10 wt %, concentration of initiator ～1–1.5 wt % and stabilizer about 10 wt % with respect to monomer. Moreover, the interfacial bonds and dispersion situation of polyacrylic ester‐based water‐free powder coating particles were fairly well, the powder coating possesses good film‐forming property combined with outstanding thermal‐stability performance. The combination of these characteristics makes PMMA/kaolin powder coating an excellent candidate for dry coating technique of paper applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42439.     

Effect of aminobisphosphonated copolymer on the thermal stability and flammability of poly(methyl methacrylate)

Methyl methacrylate was copolymerized with propyl N,N‐tetramethylbis(phosphonate)‐bis(methylene)aminemethyl methacrylate (MAC₃NP₂). The thermal degradation and flammability of this modified poly(methyl methacrylate) (PMMA) were compared with those of pure PMMA using thermogravimetric analysis (TGA) and pyrolysis combustion flow calorimetry (PCFC). The morphology of char was investigated using scanning electron microscopy and the yield of phosphorus using energy‐dispersive X‐ray analysis. The gases evolved during degradation in TGA were analysed using Fourier transform infrared spectroscopy. The total heat release and heat release capacity of the reactively modified PMMA are reduced, as compared to pure PMMA. The modified PMMA presents a better thermal stability (above 290 °C) than pure PMMA and leads to an important char formation. A comparison among TGA, PCFC and the amount of phosphorus in the condensed phase gives useful information about the role of phosphorus in the flame retardancy of the copolymer. The result reveals the effect of phosphorus not only in the condensed phase but also in the vapour phase. Copyright © 2011 Society of Chemical Industry     

Poly(methyl methacrylate)/montmorillonite nanocomposites prepared with a novel reactive phosphorus–nitrogen‐containing monomer of N‐(2‐(5,5‐dimethyl‐1,3,2‐dioxaphosphinyl‐2‐ylamino)ethyl)‐ acrylamide and its thermal and flame retardant properties

A novel reactive phosphorus–nitrogen‐containing monomer, N‐(2‐(5,5‐dimethyl‐1,3,2‐dioxaphosphinyl‐2‐ylamino)ethyl)‐acrylamide (DPEAA), was synthesize and characterized. Flame retardant poly(methyl methacrylate)/organic‐modified montmorillonite (PMMA‐DPEAA/OMMT) nanocomposites were prepared by in situ polymerization by incorporating methyl methacrylate, DPEAA, and OMMT. The results from X‐ray diffraction and transmission electron microscopy (TEM) showed that exfoliated PMMA‐DPEAA/OMMT nanocomposites were formed. Thermal stability and flammability properties were investigated by thermogravimetric analysis, cone calorimeter, and limiting oxygen index (LOI) tests. The synergistic effect of DPEAA and montmorillonite improved thermal stability and reduced significantly the flammability [including peak heat release rates (PHRR), total heat release, average mass loss rate, etc.]. The PHRR of PMMA‐DPEAA/OMMT was reduced by about 40% compared with pure PMMA. The LOI value of PMMA‐DPEAA/OMMT reached 27.3%. The morphology and composition of residues generated after cone calorimeter tests were investigated by scanning electronic microscopy (SEM), TEM, and energy dispersive X‐ray (EDX). The SEM and TEM images showed that a compact, dense, and uniform intumescent char was formed for PMMA‐DPEAA/OMMT nanocomposites after combustion. The results of EDX confirmed that the carbon content of the char for PMMA‐DPEAA/OMMT nanocomposites increased obviously by the synergistic effect of DPEAA and montmorillonite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011