Polymer/Ceramic Composite Membranes and Their Application in Pervaporation Process

Pervaporation(PV),as an environmental friendly and energy-saving separation technology,has been received increasing attention in recent years.This article reviews the preparation and application of macroporous ceramic-supported polymer composite pervaporation membranes.The separation materials of polymer/ceramic composite membranes presented here include hydrophobic polydimethylsiloxane(PDMS) and hydrophilic poly(vinyl alcohol)(PVA),chitosan(CS) and polyelectrolytes.The effects of ceramic support treatment,polymer solution properties,interfacial adhesion and incorporating or blending modification on the membrane structure and PV performance are discussed.Two in-situ characterization methods developed for polymer/ceramic composite membranes are also covered in the discussion.The applications of these composite membranes in pervaporation process are summarized as well,which contain the bio-fuels recovery,gasoline desulfuration and PV coupled proc-ess using PDMS/ceramic composite membrane,and dehydration of alcohols and esters using ceramic-supported PVA or PVA-CS composite membrane.Finally,a brief conclusion remark on polymer/ceramic composite mem-branes is given and possible future research is outlined.

Selective laser sintering of polymer-coated Al_2O_3/ZrO_2/TiC ceramic powder

A type of polymer-coated Al2O3/ZrO2/TiC ceramic powder was prepared. The laser sintering mechanism of polymer-coated Al2O3/ZrO2/TiC powder was investigated by studying the dynamic laser sintering process. It is found that the mechanism is viscous flow when the sintering temperature is between 80 ℃ and 120 ℃, and it is melting/solidification when the temperature is above 120 ℃. The process parameters of selective laser sintering were optimized by using ortho-design method. The results show that the optimal parameters include laser power of 14 W, scanning velocity of 1 400 mm/s, preheating temperature of 50 ℃ and powder depth of 0.15 mm. A two-step post-treatment process is adopted to improve the mechanical properties of laser sintered part, which includes polymer debinding and high temperature sintering. After vacuum sintering for 2 h at 1 650 ℃, the bending strength and fracture toughness of Al2O3/ZrO2/TiC ceramic part reach 358 MPa and 6.9 MPa·m1/2, respectively.

Effect of E-44 Epoxy Resin and Pyrolysis Temperature on the Adhesion Strength of SiBCN Ceramic

An adhesive of the SiBCN ceramic was synthesized through the polymer derived ceramics(PDC)route.Meanwhile with higher adhesion strength and simpler process condition,the polyborosilazane(PSNB)was modified by E-44 epoxy resin.The E-44 epoxy resin was used to promote the oxidation process of SiBCN,in other words,to produce more amount of SiO2-B2O3 glasses.The phase composition,elemental analysis,chemical bonds and microstructure were investigated by using X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),and scanning electron microscope(SEM)measurements.The E-44 modified adhesives were cured at 120℃in air for 2 h,and were pyrolyzed at 1200,1400,and 1500℃for 2 h in air,respectively.The highest adhesion strength of the modified adhesive was up to 5.33,12.23,and 12.50 MPa after being heat treated at 1200,1400,and 1500℃,respectively.Finally,we proposed an adhesion model and revealed the adhesion mechanism of SiBCN ceramic.

Fabrication and Life Prediction of SSiC Ceramic Joint Joined with Silicon Resin YR3370

Joints between sintered silicon carbide （SSiC） were produced using a polysiloxane silicon resin YR3370 （GE Toshiba Silicones） as joining material. Samples were heat treated in a 99.99% nitrogen flux at temperatures ranging from 1 100 ℃ to 1 300 ℃. Three point bending strength of the joint reached the maximum of 179 MPa as joined at 1 200℃. The joining layer is continuous, homogeneous and densified and has a thickness of 2 μm -5μm. The joining mechanism is that the amorphous silicon oxycarbide （SixOyCz） ceramic pyrolyzed from silicon resin YR3370 acts as an inorganic adhesive to SSiC substrate, which means the formation of the continuous Si-C bond structure between SixOyCz structure and SSiC substrate. Life prediction of the ceramic joint can be realized through the measurement of the critical time of the joint after the cyclic loading test.

Structural characteristics and properties of polyurethane modified TDE-85/MeTHPA epoxy resin with interpenetrating polymer networks

Diglycidyl-4,5-epoxycyclohexane-1,2-dicarboxylate(TDE-85)/methyl tetrahydrophthalic anhydride (MeTHPA) epoxy resin was modified with polyurethane(PU) and the interpenetrating polymer networks(IPNs) of PU-modified TDE-85/MeTHPA resin were prepared. The structural characteristics and properties of PU-modified TDE-85/MeTHPA resin were investigated by Fourier transform infrared(FTIR) spectrum,emission scanning electron microscopy(SEM) and thermogravimetry(TG). The results indicate that epoxy polymer network (Ⅰ) and polyurethane polymer network (Ⅱ) of the modified resin can be obtained and the networks (Ⅰ) and (Ⅱ) interpenetrate and tangle highly each other at the phase interface. The micro morphology presents heterogeneous structure. The integrative properties of PU-modified TDE-85/MeTHPA epoxy resin are improved obviously. The PU-modified TDE-85/ MeTHPA resin's tensile strength reaches 69.39 MPa,the impact strength reaches 23.56 kJ/m,the temperature for the system to lose 1% mass (t1%) is 300 ℃,and that for the system to lose 50% mass (t50%) is 378 ℃. Compared with those of TDE-85/MeTHPA resin,the tensile strength,impact strength,t1% and t50% of the PU-modified resin increases by 48%,115%,30 ℃,11 ℃,respectively. The PU-modified TDE-85/MeTHPA resin has the structure characteristics and properties of interpenetrating polymer networks.

Synthesis and Characterization of Polyurethane and Epoxy Resin Interpenetrating Polymer Network

A series of Polyurethane (PU)/bisphenol A based Epoxy Resin(EP) Interpenetrating Polymer Networks(IPN) were synthesized and characterized by SEM, DSC, TGA and DMTA. It was found that IPN shows the best compatibility and damping properties when the ratio of PU/EP is 80 to 20. The results show that chain-extender and higher molecular weight of PPG are able to improve the properties of compatibility, damping and thermal properties.

A novel chain-extended urea containing hyperbranched polymer used as toughening modifier for epoxy resin

A new kind of reactive toughening accelerator for epoxy resin, amine-teminated hyperbranched polymer (H2O-NMe2) was synthesized and characterized by FT-IR spectroscopy. Dynamic mechanical analysis (DMA) was used to study the glass transition temperature (Tg), loss factor (tanδ) and activation energy (Ea) by using multiplexing frequency. The results show that the Ea at glassy relaxation process of modified system is about 70-80 kJ/mol higher than that of unmodified system, and the high modulus and good thermal properties are still maintained.

SYNTHESIS, CHARACTERIZATION, METAL-UPTAKE BEHAVIOR OF BIS(BENZIMIDAZOLE) RESIN SUPPORTED ON EPOXIDE POLYMER

The new chelate resins, abbreviated as PNBMZs and PBBMZs based on epoxide polymer, were synthesized by polycondensation of N,N-diglycidyl-4-glycidyloxyaniline or 1,4-bis（2,3-epoxypropyl）benzene with the primary amine group of 1,3-bis（benzimidazol-2yl）propylamine （BBPAH）. The ion exchangers contain 2.71-3.23 mmol of the ligand contents per gram of the resin. Batch extraction capacities were determined for the metal chloride salts in buffer solutions in the pH range from -1 to 6.0. The chelate resins were very selective for Cu^2＋, Zn^2＋, Cd^2＋ in the presence of other divalent transition metal ions. The maximum uptake capacities of PNBMZ （synthetic molar ratio = 1：1.5） under non-competitive condition were found to be 0.94 mmol/g for Cu^2＋ at pH = 2, 1.3 mmol/g for Cd^2＋ at pH = 1 and 1.75 mmol/g for Zn^2＋ at pH = -1 respectively. While in the case of PBBMZ, it was 1.39 mmol/g for Cd〉 at pH = 1. The metal-uptake behaviors for both of them showed strong pH dependence, and their extraction capacities increase with decreasing pH. The uptake of Cu^2＋ by the resin PNBMZs at pH = 1 was found to be rather fast with t1/2 = 18 min. Metal-uptake experiments under competitive conditions also confirm that the chelate resins have a high selectivity for Cu^2＋, Zn^2＋, Cd^2＋ and the contrary pH dependence.

SYNTHESES AND ADSORPTION PROPERTIES OF POLYMER RESINS CONTAINING BENZIDINE AND ITS DERIVATIVES

Three chelating resins were prepared by reacting poly (beta-chloroethyl glycidyl ether) with benzidine, o-tolidine and o-dianisidine respectively, and their structures were confirmed by IR spectra and elementary analyses. The adsorption properties of the resins for Au(III), pd(II), Pt(IV), Hg(II), Cu(II), Pb(II) and Zn(II) were also investigated. The results show that the resin incorporating o-dianisidine exhibits high affinity for Au(III) within a broad range of hydrochloric acid, and selectively sorbs Au(III) in the coexistance of Cu(II), Zn(II) and Mg(II). Desorption of Au(III), Pd(II) and Pt(IV) sorbed proceeded quantitatively using 0.1 mol/l hydrochloric acid containing 2%-10% thiourea as desorbents.

PREPARATION OF MICROGEL-EPOXY RESIN TWO-PHASE POLYMERS BY IN SITU POLYMERIZATION~*

Microgel-epoxy resin two-phase polymers were prepared by in situ copolymerization of ethylenic monomers with unsaturated polyesters. The choice of monomers and the effect of monomer concentration on microgel particle size were discussed. Agglomeration of particles played a significant role in the early stage of polymerization. The microgel dispersion in epoxy resin was stable after the finish of polymerization. Upon curing the particles remained well dispersed.

The Influence of Ceramic Surface Treatments on the Microtensile Bond Strength of Resin Cements to Y-TZP Ceramic

The effects of surface conditioning methods on the microtensile bond strength of Y-TZP ceramic were studied based on airborne particle abrasion and resin cements.Eight square-shaped（φ12 mm×5 mm high） Y-TZP ceramic were studied blocks（LAVATM,3M ESPE,USA） and flat occlusal dentin blocks were fabricated,pre-treated（airborne abrasion with 125μm Al2O3 particles,tribochemical silica coating with 110 μm Al2O3 particles modified by silica oxide）,and bonded to each other using resin cements（Panavia F 2.0,RelyX Unicem）.Thereafter the trilayer specimens were cut into microbar specimens with a bonding area of approximately 1.0±0.1 mm2 and then microtensile bond strength tests were performed.The Y-TZP ceramic following airborne particle abrasion with 125μm Al2O3 and silicoating,the surface roughness of Y-TZP and its surface silica content were confirmed to increase.Overall,the Y-TZP ceramic surface treatment with a tribochemical silica coating showed the highest microtensile bond strength of the phosphate monomer-based resin cement to Y-TZP ceramic（mean MPa=18.11±0.27（Panavia F 2.0）,17.45±0.39（Rely X Unicem）.In cases in which a silica coating was applied,there was no significant difference in the bonding strength depending on resin cements（P0.05）.

Ablation Property of Ceramics/Carbon Fibers/Resin Novel Super-hybrid Composite

A novel super-hybrid composite (NSHC) is prepared with three-dimension reticulated SiC ceramic (3DRC), high performance carbon fibers and modified phenolic resin (BPR) in this paper. Ablation performance of super-hybrid composite is studied. The results show that the NSHC has less linear ablation rate compared with pure BPR and CF/BPR composite, for example, its linear ablation rate is 50% of CF/BPR at the same fiber content. Mass ablation rate of the NSHC is slightly lower than that of pure BPR and CF/BPR composite because of their difference in the density. Scanning electron microscopic analysis indicates that 3DRC can increase anti-erosion capacity of materials because its special reticulated structure can control the deformation of materials and strengthen the stability of integral structure.

Durability Testing of Composite Aerospace Materials Based on a New Polymer Carbon Fiber-Reinforced Epoxy Resin

In this study,the durability of a new polymer carbonfiber-reinforced epoxy resin used to produce composite material in the aerospacefield is investigated through analysis of the corrosion phenomena occurring at the microscopic scale,and the related infrared spectra and thermal properties.It is found that light and heat can con-tribute to the aging process.In particular,the longitudinal tensile strength displays a non-monotonic trend,i.e.,itfirst increases and then decreases over time.By contrast,the longitudinal compressive and inter-laminar shear strengths do not show significant changes.It is also shown that the inter-laminar shear strength of carbonfiber/epoxy resin composites with inter-laminar hybrid structure is better than that of pure carbonfiber materials.The related resistance to corrosion can be improved by more than 41%.

Effect of Multi-Hydroxyl Polymer-Treated MUF Resin on the Mechanical Properties of Particleboard Manufactured with Reed Straw

The poor bonding performance between aqueous adhesives represented by melamine-urea formaldehyde(MUF)resins and reed straw hinders their applications in the field of non-wood-based panels.Multi-hydroxyl polymers are highly reactive and are often used as crosslinkers.This study fabricated a resin with a strengthened crosslinked structure by combining a multi-hydroxyl polymer and MUF resin prepolymer.The reed particleboard was prepared by using this resin as an adhesive and reed stalk as the matrix.The results show that neighboring molecules combined to form C–O–C bonds that strengthened the cross-linked structure of the resin.In addition,the viscosity of the resin was increased,and a continuous adhesive layer on the surface of reed particles was formed,which slowed the penetration of reed particles.The adhesive layer significantly improved the mechanical properties of the reed particleboard.The maximum modulus of rupture(MOR),modulus of elasticity(MOE),and internal bonding strength(IB)of the reed particleboard were 33.53,4126,and 0.79 MPa,respectively.The IB of the board was 3.3 times higher than that of the reed particleboard prepared with a conventional MUF resin.Reed straw is a non-wood biomass material that has the advantage of sustainable development and may replace woodbased materials to produce particleboard.This resin-prepared reed particleboard is expected to be used in areas such as custom furniture and engineering materials.

Epoxy Methacrylate Resin as Binder Polymer for Black Negative-Tone Photoresists

Epoxy acrylate (EA) resin, which originates from epoxides, has long been served as a photocurable coating and adhesive material owing to its double bonds. Specifically, alkaline-developable EA resins can be used as a binder polymer in negative-tone photoresists. In this work, we synthesized a series of acidic polyester-type epoxy methacrylate resins, characterized the intermediates and products, and tested their performance as a binder polymer for the photolithographic micro-patterning of the pixel-defining layer on organic light-emitting diodes in comparison to a widely used commercial binder polymer. Copolymer-type binder polymer BP-2-2 was produced excellent patterning with no residue due to its high compatibility with the black mill base.

Evaluation of Sawdust and Rice Husks as Fillers for Phenolic Resin Based Wood-Polymer Composites

We produced Wood-Polymer Composites (WPCs) with phenolic resin (PR) filled with saw dust (SD) and rice husks (RH) in a PR:fillerratio of 60:40 wt.%. RH and SD were grinded and sieved into particles μm. The aim of this research work was to evaluate sawdust and rice husks as fillers for sustainable phenolic resin based WPCs. Therefore, we investigated the thermal stability of PR/RH and PR/SD WPCs then we studied and compared the tensile, flexural properties of PR/SD and PR/RH WPCs samples, as well as their dimensional stability after water absorption test. Furthermore, through ultraviolet light exposure, we evaluated the effects of photo-oxidation on the water stability and mechanical properties of PR/RH and PR/SD WPCs samples compared to unexposed ones. PR filled with SD presented better mechanical properties compared to PR/RH WPCs samples. However, PR/RH WPCs showed good mechanical properties, and better thermal resistance and better water repulsion capabilities compared to PR/SD WPCs samples. Although, long time UV exposure ended up lowering considerably the mechanical properties and water resistance of PR/SD and PR/RH WPCs, both RH and SD offer great added value as fillers for PR based WPCs;SD having better interactions with PR matrix compared to RH.

Fabrication and Characterization of Diatomite-supported Activated Carbon Functional Ceramic

Using porous diatomite ceramic as carrier and phenolic resin as carbon precursor, the activated carbon functional ceramic with the activated carbon fixed into porous ceramic was prepared by the impregnation load phenolic resin, carbonization and activation isolated air. The influences of impregnation, curing, carbonization, activation etc. on the material property were discussed. The iodine value, SEM, elemental analyzer, BET and spectrum analysis chart were used to characterize the microstructures and performance of material at different conditions. The results showed that the excellent comprehensive property of activated carbon functional ceramic was gained when it adsorbed phenolic resin in 4 h under vacuum condition at curing temperature of 150 ℃ for 0.5 h and carbonization temperature of 600 ℃ for 1.0 h, and then put into 25wt% KOH for 4.0 h at activation temperature of 700 ℃ for 1.5 h. The iodine value is 176.9 mg/g, the specific surface area can reach 86.3 m2/g and the yield of carbonization is 50.48%.

Ceramification of Composites of MgO-Al_(2)O_(3)-SiO_(2)/Boron Phenolic Resin with Different Calcine Time

The ceramifiable polymer composite of MgO-Al_(2)O_(3)-SiO_(2)/boron phenolic resin(MAS/BPF)with 40wt%of inorganic fillers was calcined at 1200℃for different time to promote ceramification of ceramifiable composite and improve heat resistance.The effects of different calcine time on the macroscopical morphology,mass loss,phase evolution,microstructure and chemical bond evolution of MAS/BPF composites were characterized by XRD,XPS,and SEM analyses.The experimental results reveal that the increase of calcine time result in the fewer holes,relatively denser and smoother top layer of MAS/BPF composites and protect the interior from deeper decomposition.The final residues of composites are amorphous carbon and C-O-Si-Al-Mg ceramic.And MAS/BPF composites show excellent mass stability,low shrinkage and self-supporting features after 2 h holding compared with BPF composites without 40wt%of inorganic fillers.

Fluxing Agents on Ceramification of Composites of MgO-Al2O3-SiO2/Boron Phenolic Resin

Fluxing agents of zinc borate, antimony oxide, galss frit A and glass frit B, with different melting or softening point temperatures, were added into MgO-Al_2O_3-SiO_2/boron phenol formaldehyde resin（MAS/BPF） composites to lower the formation temperature of eutectic liquid phase and promote the ceramification of ceramifiable composites. The effects of fluxing agents on the thermogravimetric properties, phase evolution, and microstructure evolution of MAS/BPF composites were characterized by TG-DSC, XRD and SEM analyses. The results reveal that the addition of a fluxing agent highly reduces the decomposition rate of MAS/BPF composites. Fluxing agents lower the formation temperatures of liquid phases of ceramifiable MAS/BPF composites obviously, and then promote the ceramification and densification process. The final residues of composites are ceramic surrounded by large amount of glass phases.