Properties of waterborne polyurethane films: effects of blend formulation with hydroxyl telechelic natural rubber and modified rubber seed oils

A series of new waterborne polyurethanes (WPUs) was successfully prepared by the prepolymer process from the bio-renewable sources hydroxytelechelic natural rubber (HTNR with MW 3000 g mol^?1) and hydroxylated rubber seed oil (HRSO), with DMPA fixed at 5.6 wt%. The effects of ratio of HTNR and HRSO (ranging from 1.00/0 to 0.10/0.90) and of hydroxyl value (OHV) of HRSO (200 or 270 mgKOH/g) on final properties were studied. It was found that the particle size of WPU increased significantly with both HRSO/HTNR ratio and OHV of HRSO. Chemical structure of the WPU films was confirmed by FT-IR. The water uptake, mechanical, dynamic mechanical properties and thermal stability of WPU film improved with both HRSO content and OHV of HRSO, while swelling in THF decreased. All these WPU films had similar Tg. This article reports novel green biobased WPU with promising applications as adhesive for shoe industries.

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Effect of MnO on the Phase Development, Microstructures, and Dielectric Properties of 0.95Na0.5K0.5NbO3–0.05LiTaO3 Ceramics

Lead-free piezoelectric ceramics in the system 0.95Na_0.5K_0.5NbO₃–0.05LiTaO₃ were modified with ≤1 mol% MnO. Maximum densities occurred at a sintering temperature of 1050°C. Characteristic changes in the relative intensity of X-ray diffraction peaks were consistent with Mn ions substituting on the perovskite lattice to produce a change from orthorhombic to a mixture of tetragonal and orthorhombic phases. Grain growth during secondary recrystallization was also affected, leading to increased grain sizes. The dielectric constant increased from ∼600 in unmodified ceramics to ∼1040 in ceramics prepared with 0.5 mol% MnO.     

Structural and electrical properties of Na0.47K0.47Li0.06NbO3 lead-free piezoelectric ceramics modified by AgSbO3

(1?x)Na_0.47K_0.47Li_0.06NbO₃ (NKLN)–xAgSbO₃ lead-free piezoelectric ceramics were prepared using a reaction sintering method. The effects of AgSbO₃ doping on the structural and electrical properties of NKLN ceramics sintered at 1000–1040 °C were studied. The dopant affected densification, phase content, sintering temperature, microstructure and electrical properties. Variations in the relative intensity of X-ray diffraction peaks were consistent with Ag⁺ and Sb⁵⁺ ions substituting on the perovskite lattice to produce a change in the proportions of co-existing tetragonal and orthorhombic phases. Grain growth during secondary re-crystallization was also affected. The temperature of the orthorhombic–tetragonal (O–T) phase transition and the Curie temperature (T_C) decreased as a result of AgSbO₃ modifications. The dielectric and piezoelectric properties are enhanced for the composition near the orthorhombic–tetragonal polymorphotropic phase boundary. The 0.92Na_0.47K_0.47Li_0.06NbO₃–0.08AgSbO₃ ceramics exhibited optimum electrical properties (d₃₃=252 pC/N, ε_r=1450, tan δ=0.02, and T_C=280 °C). These results reveal that (1?x)Na_0.47K_0.47Li_0.06NbO₃–xAgSbO₃ ceramics are promising materials for lead-free piezoelectric application.     

Reaction-sintering of lead-free piezoceramic compositions: (0.95 − x)Na0.5K0.5NbO3–0.05LiTaO3–xLiSbO3

Incorporation of LiSbO₃ into the lead-free piezoceramic composition 0.95Na_0.5K_0.5NbO₃–0.05LiTaO₃ produced a change from an orthorhombic to tetragonal crystal system in samples produced by reaction-sintering. The inferred limit of solid solution along the compositional join, (0.95 − x)Na_0.5K_0.5NbO₃–0.05LiTaO₃–xLiSbO₃, occurred at x ~ 0.06. Differential scanning calorimetry indicated broad peaks at temperatures associated with ferroelectric–paraelectric transitions. The transition temperatures decreased with increasing values of x, up to x = 0.06. Microstructures showed secondary grain growth; a slight decrease in grain-size with increasing LiSbO₃ modification was identified.     

Compositional analysis and electrical properties of Sb,Mn-doped barium strontium titanate PTCR ceramics with TiO<Subscript>2</Subscript> and SiO<Subscript>2</Subscript> sintering additives

The secondary phase compositions in Sb-doped (Ba, Sr)TiO₃ ceramics containing SiO₂ and excess TiO₂ sintering additives have been examined by XRD, BEI and EPMA techniques. It is shown that alongside the primary (Ba_0.797Sr_0.2Sb_0.003)TiO₃ phase, (Ba_1.95Sr_0.05)₂(Ti_1.2Si_1.8)O₈ and Sb-doped (Ba_0.99Sr_0.01)₆Ti₁₇O₄₀ phases form at the intergranular regions. Substitution of up to 0.04 mol% MnO₂ enhances the PTCR effect, giving a ratio ρ_max/ρ_min ∼ 7 × 10⁵ for the optimum 0.04% MnO₂ composition. At this level Mn cannot be detected in the microstructure by EPMA, however in insulating samples containing 0.08 mol% of MnO₂, it was detected in the (Ba_0.99Sr_0.01)₆Ti₁₇O₄₀ intergranular phase.     

Ceramic/natural rubber composites: influence types of rubber and ceramic materials on curing,mechanical, morphological,and dielectric properties

Influence of different types of rubber and ceramic material on cure characteristics, mechanical, morphological, and dielectric properties of natural rubber (NR) vulcanizate was studied. Two types of ferroelectric ceramic materials: barium titanate (BaTiO₃) and lead titanate (PbTiO₃) were prepared by solid-state reaction with calcinations at 1100 °C for 2 h. The ceramic powders were then characterized by X-ray diffraction (XRD), particle size analyzer, and SEM techniques. Ceramic/rubber composites were then prepared by melt mixing of rubber and ceramic powders. Two different types of NR (i.e., epoxidized NR [ENR] and unmodified NR) and two types of ceramic powders (i.e., BaTiO₃ and PbTiO₃) were exploited. It was found that incorporation of ceramic powders in rubber matrix and the presence of epoxirane rings in ENR molecules caused faster curing reaction, and higher delta torque but lower elongation at break. This is attributed to lower mobility of molecular chains and higher interaction between ENR molecules. Furthermore, SEM results revealed that the BaTiO₃ composites showed finer and better distribution of the particles in the rubber matrix than that of the PbTiO₃ composite. This caused superior mechanical properties of the BaTiO₃ composites. Furthermore, higher dielectric constant and loss tangent was observed in the ENR/BaTiO₃ composites.     

Effects of Nb-doping on the micro-structure and dielectric properties of (Bi0.5Na0.5)TiO3 ceramics

Bismuth sodium titanate [(Bi_0.5Na_0.5)TiO₃ or BNT] ceramics incorporated with 0, 1, 5, 10, 15 and 20 mol% niobium were prepared by conventional solid state reaction method. The green bodies were sintered at 1050 °C for 2 h to obtain dense ceramics. The effects of substitution of niobium ion for titanium ion in BNT ceramics on micro-structure and dielectric properties were investigated. X-ray diffraction analysis showed the presence of a secondary phase when more than 5 mol% niobium was added. Within the solubility limit, Nb doping caused the grain size of BNTNb to be smaller than the undoped sample. The investigation of the dielectric properties showed that the transition temperature (T_c) was found to shift towards lower temperature as the content of Nb increased. In this research, the donor-type behavior and induced charged defects had significant influence on the electrical properties of Nb-doped BNT ceramics.     

Effect of Calcination Conditions and Excess Alkali Carbonate on the Phase Formation and Particle Morphology of Na0.5K0.5NbO3 Powders

Sodium-potassium niobate [Na_0.5K_0.5NbO₃] powders were prepared following the conventional mixed oxide method. An orthorhombic XRD pattern, consistent with single-phase Na_0.5K_0.5NbO₃, was obtained after calcination at 900°C for 6 h. Introducing 5 mol% excess Na₂CO₃ and K₂CO₃ into the starting mixture allowed milder calcination conditions to be used, for example 800°C for 2 h. Primary particles in 5 mol% excess samples were cuboid, with maximum sizes of ∼2.5 μm. Equiaxed 0.3–0.4-μm particles were formed for non-excess powders, and also for powders prepared with 1 and 3 mol% excess alkali carbonates. The results suggest liquid formation during calcination of the excess 5-mol% starting powders.     

Properties of barium-strontium titanate PTCR ceramics sintered on different powder beds

Barium-strontium titanate (BST) ceramics, co-doped with Sb and Mn oxides, were sintered on different powder beds: Sb-doped BST; Al₂O₃; or Sb,Mn-codoped BST powder. Phase formation, microstructure and the electrical properties of the samples were analysed. The PTCR behavior depended significantly on the type of powder bed used. The BST ceramic pellet sintered on the Sb-BST powder displayed the largest PTCR effect, with a ρ_max/ρ_RT ratio of ∼10⁶. This was an order of magnitude greater than for samples sintered on the other two powders. Complex impedance analysis confirmed that this was due to a large increase in grain boundary resistance at 250 °C.