Enhanced dielectric and mechanical properties of polylactic acid/polycaprolactone blends by introducing double-layer carbon nanofillers

To overcome the issues of poor toughness and low dielectric constant associated with PLA, which limit its application in the electronics industry, we introduced an insulating polydopamine (PDA) layer on the surface of core-shell nickel-coated carbon nanotube (Ni-CNT) and nickel-coated graphene (Ni-GRA). Through a double-layer structural design approach, we successfully prepared polylactic acid (PLA)/polycaprolactone (PCL) blends that exhibit high dielectric constant (ε’) and low dielectric loss (tanδ). This innovative design led to impressive impact strengths of 29.41 kJ/m² for PLA/PCL/4Ni-GRAs and 22.54 kJ/m² for PLA/PCL/4Ni-CNTs. PDA enhanced the interfacial interactions between the filler and matrix, which improved the dispersion of Ni-CNTs and Ni-GRAs and contributed to the mechanical properties of the PLA/PCL blends. Simultaneously, PLA/PCL/4Ni-CNTs and PLA/PCL/4Ni-GRAs exhibited commendable integrated dielectric properties. The PDA@fillers form microcapacitors with the polymer matrix and the conductive Ni layer enhances ε’ and reduces the conductivity difference between fillers. Furthermore, the insulating PDA layer contributed to improved dispersion, inhibition of charge carrier migration, and reduction in tanδ. At 1000 Hz, the ε′ of PLA/PCL/4Ni-CNTs and PLA/PCL/4Ni-GRAs increased to 88.3 and 124.6, respectively, and the tanδ values remained below 1, indicating minimal dielectric loss. This provides a promising direction for eco-friendly materials with enhanced dielectric and mechanical properties.     

Relaxation behavior and activation energy of relaxation for polyimide and polyimide–graphene nanocomposite

The relaxation behavior of polyimide and its nanocomposite containing 10 wt % of graphene was studied by using the dynamic mechanical spectrometer. Dynamic mechanical analysis of polyimide and its composite was performed as a function of temperature and frequency in the temperature range of 25–480 °C and frequency range between 0.05 and 100 Hz. The effect of increasing frequency of testing from 0.05 to 100 Hz is a significant shift from the glass transition temperature, T_g, to higher temperature from 360 °C at 0.05 Hz to 420 °C at 100 Hz. The tan δ peak height for both α and β transitions decreased with increasing test frequency from 0.24 at 0.05 Hz to 0.08 at 100 Hz, due to increasing restriction to chain motion. At any given testing frequency, the T_g for the composite was shown to be higher than that for the matrix by about 5–10 °C. The Arrhenius equation was used to calculate the activation energy for both α and β transitions. The activation for α and β transitions for the composite and polyimide matrix were determined to be 688 and 537 kJ/mol and 313 and 309 kJ/mol, respectively, indicating that a significant increase in the energy barrier to chain relaxation occurred as a result of reinforcement of polyimide with low weight fraction of graphene. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43684.     

Relationship between structure and dynamic mechanical properties of thermoplastic polyurethane elastomer containing bi-soft segment

In this work, we investigated the microphase separation, mechanical, and dynamic mechanical properties of thermoplastic polyurethane elastomers (TPUs) with one-soft segment (polypropylene glycol, PPG, or hydroxyl-terminated polybutadiene, HTPB) or bi-soft segment (PPG and HTPB) using FTIR, XRD, SAXS and amplitude modulated-frequency modulated viscoelastic mode of AFM (AM-FM mode AFM) methods. The results showed that the microphase separation process of hard and soft segments (HS and SS) in TPU containing PPG and HTPB soft segments (PPG-HTPB-PU) was restricted by randomly alternated bi-soft segments, which results in formation of a low content of irregular-shaped hard domain (HD). In addition, the microphase separation of PPG-HTPB-PU induced a triple-phased structure of HD, HTPB rich phase and mesophase. The mesophase of PPG-HTPB-PU was formed of HS, PPG and HTPB segments which were excluded out of HD and HPTB rich domains during microphase separation process. The damping temperature range (at tan δ greater than 0.3) of PPG-HTPB-PU was from −14.6 to 32.1°C (46.5°C) which was more broad than that of TPU containing HTPB soft segment (HTPB-PU). The broad damping temperature range of PPG-HTPB-PU is mainly attributed to the enhanced energy consumption caused by the frictional motions of mixed segments of mesophase.     

Effect of crosslinking on mechanical and viscoelastic properties of semiinterpenetrating polymer networks composed of poly(vinyl chloride) and isocyanate crosslinked networks

Semiinterpenetrating polymer networks (SIPNs) of PVC/isocyanate/poly‐triol were prepared by premixing small (150 μm dia.) porous (30% voids) unplasticized PVC particles, 10% by weight of isocyanate, and a triol at different OH/NCO mol ratios. Three types of isocyanates (methylene bis‐phenyl diisocyanate (MDI), oligomeric MDI isocyanates (PAPI), and toluene diisocyanate (TDI) prepolymer/polytriol) were used. Two‐roll milling was followed by hot‐press curing. The tensile, flexural, and impact strengths increased when small amounts of crosslinked isocyanate networks were created in PVC. The isocyanate/polyol hydroxyl stoichiometry was varied, and the effects of crosslinking on the tensile, impact, and flexural strengths of PVC/isocyanate/triol SIPNs were examined. The strength increments were greater when the OH/NCO mole ratio went from 0 to 0.25, than when it went from 0.25 to 1.0. In many cases, increasing OH/NCO mol ratio from 0.5 to 1.0 decreased tensile, impact, and flexural strengths. Both PAPI and MDI (30% NCO content) gave bigger improvements in the these mechanical strengths than the TDI (only 9.7% NCO). These SIPN blends exhibited lower tan δ peak temperatures and a single distinct loss modulus, E″, peak values at lower temperatures than those of PVC that had been exposed to the same processing temperatures. Substantial amounts of isocyanate networks exist in SIPN phases according to DMTA studies. The OH/NCO ratio did not generally correlate with the decreases in the glass transition temperatures in these three sets of blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1402–1411, 2000     

A dynamic mechanical analysis method for predicting the curing behavior of phenol-formaldehyde resin adhesive

In this work, filter paper was proven to be suitable as the substrate for the preparation of dynamic mechanical analysis (DMA) testing specimens to predict the curing behavior of phenol-formaldehyde (PF) resin adhesives for its stability during the curing temperature span. With this method, the curing behavior of PF resin was monitored by DMA in tensile-torsion mode. With the strain curves, the onset of curing temperature of PF resin could be determined clearly. The curing degree of PF resin could be calculated by the integral area in strain curves. The method to combine storage modulus (G′), tan δ, and strain curves together could explain the curing behavior of PF resin more comprehensively than the commonly used method using only G′ and tan δ curves. The DMA test results of PF resin with different viscosity and with accelerator implied the reliability of this novelty method.     

Curing characteristics and kinetics of EPDM and EOC compounds in co-vulcanization as blend

Possibility of co-vulcanization of ethylene octene copolymer (EOC) and ethylene propylene diene terpolymer (EPDM) molecules was studied by assessing the curing characteristic and crosslinking kinetics of EOC and EPDM compounds. Regarding curing, the curing characteristics, cure rate index, and the torque difference (M_H − M_L) of the EPDM compound are quite similar to those of the EOC compounds at the curing temperature of 180 °C, especially when the EOC octene comonomer content is 5.9 or 9.7 mol %. The kinetic parameters E _a and k were analyzed. The study showed that EOC with 9.7 mol % octene comonomer content is very suitable for blending with EPDM, as it has crosslinking kinetics similar to the EPDM. This observation confirms the possibility of chemical co-crosslinking at EPDM–EOC interfaces, especially at the curing temperature of 180 °C. Differential scanning calorimetry and dynamic mechanical analysis were also used to assess interfacial crosslinking. The lowest activation energy of vulcanization is found for the EPDM/EOC blend with 9.7 mol % octene comonomer contents. Furthermore, chemical co-crosslinking in combination with chain flexibility in the EPDM/EOC blend with 9.7 mol % octene comonomer contents give lower tan δ at room temperature than for the blends with octene comonomer contents of 5.9 and 16.9 mol %. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47613.     

Aging of the Binders GAP-N100 and HTPB-IPDI Investigated by Torsion-DMA

The aging of the binders GAP-N100 and HTPB-IPDI was investigated by DMA in torsion mode to find out the changes in the storage shear modulus G′(ω), loss shear modulus G″(ω) and in the glass transition temperature T_G. The forced sinusodial deformation method was used with measuring frequencies between 0.1 Hz and 56.2 Hz. A measurement temperature range between −100°C and +50°C was applied. The DMA instrument was a Rheometrics Dynamical Spectrometer, type RDS II/7700. Non-aged GAP-N100 shows a well defined steep glass transition between −40°C and −25°C, which is found with aged samples also but shifted to higher temperatures. The glass transition of the binder HTPB-IPDI lies between −70°C and −10°C, but HTPB-IPDI has not a well defined glass transition. With aging it looses its glass transition, which can be seen by a smoothing out of the transition step in the curve G′(ω)=f(T). The behaviour and the differences of these binders are explainable on a molecular basis. The systematic shift of the glass transition temperature of the non-aged and aged GAP-N100 as well as of the non-aged HTPB-IPDI is describable by the Williams-Landel-Ferry equation. This equation was used to extrapolate the values of the glass transition temperatures to shear rates possible during operational use of propellants.     

High-damping polyurethane/hollow glass microspheres sound insulation materials: Preparation and characterization

The high-damping property of polyurethane elastomers and the low density of the hollow glass microspheres (HGM) were used to prepare the sound insulation materials in the present work. The transmission loss (TL) was measured to evaluate the HGM content on the sound insulation properties. The experimental results showed that the addition of HGM improved the hardness and compression modulus of the HGM-filled polyurethane composites, and the loss factor (tan δ) of polyurethane composites were greater than 0.9. The average transmission loss (ATL, from 63 to 6300 Hz) reached 37.32 dB when the content of HGM was 10 wt%. The ATL of the HGM-filled polyurethane composites with 15 wt% HGM in the damping control region and the mass control region were 31.94 and 46.78 dB, respectively. The synergistic effect of the microphase separation, the interfacial effect and the rigidity of polyurethane composites resulted in the improvement on sound insulation property. The polyurethane composite has a great potential application for the field of sound insulation materials.     

Influence of matrix viscosity on the dynamic mechanical performance of magnetorheological elastomers

Anisotropic magnetorheological elastomers (MREs) with different natural rubber matrix viscosities and industrial waste nickel zinc ferrite were prepared in order to assess the dynamic and mechanical performance of the materials. The curing characteristics of the anisotropic MREs were determined using a moving disk rheometer (MDR 2000). The loss tangent (tan δ) was measured through a parallel-plate rheometer over a frequency range of 1─100 Hz (Hz) and a strain amplitude range of 0.1─6%. It was found that tan δ increased with increasing matrix viscosity over the range of frequency and strain amplitude explored. Furthermore, as the matrix viscosity increased, the height of the tan δ peak also increased and the glass transition temperature (T_g) valued shifted to a higher temperature. It was also found that tensile strength and elongation at break increased with increasing matrix viscosity. The SEM micrographs revealed that the columnar structures became longer and thicker with a decrease in matrix viscosity. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48492.     

Dynamic mechanical analysis of fibre‐reinforced plastic composites based on carboxyl terminated poly(ethylene glycol) adipate modified epoxy and E glass fibre

Fibre reinforced plastic (FRP) composites prepared from E glass woven fabrics as reinforcing agent and carboxyl terminated poly(ethylene glycol) adipate (CTPEGA) modified epoxy as a matrix, were subjected to dynamic mechanical thermal analysis at a fixed frequency of 5 Hz. The volume fraction of glass was about 0.45. The concentration of CTPEGA in the matrix was varied gradually from 0 to 40 phr (phr stands for parts per hundred parts of resin), to investigate the effect of CTPEGA concentration on the dynamic properties of the composites. It was found that the tan δ peak temperature and storage modulus gradually decrease with incorporation of CTPEGA. However, the tan δ peak value increases up to 20 phr of CTPEGA concentration and decreases thereafter. The same trend was obtained in the case of impact strength. © 2000 Society of Chemical Industry     

Thermochemical investigation of lithium borate glasses and crystals

Lithium borate (LB) glasses and crystals with x = Li/(Li + B) = mole fraction of Li₂O of 0.2–0.5 have been synthesized by the quenching method. The thermodynamics of these materials were analyzed by high-temperature oxide melt solution calorimetry. The formation enthalpies from oxides of glasses range from −33.6 to −67.3 kJ/mol and those of crystals range from −42.1 to −77.4 kJ/mol, where compositions are given on the basis of one mole of (Li₂O + B₂O₃). The formation enthalpies of both glasses and crystals become more negative with increasing Li₂O mole fraction up to 0.5. The enthalpies of formation of glasses can be fit over the entire composition range (0 < x < 1) by a quadratic polynomial). The vitrification enthalpies were derived for x = 0.2 to 0.5 and ranged from 8.5 to 17.6 kJ/mol. The main factors controlling energetics are the strongly exothermic acid–base reaction between the network former (B₂O₃) and the network modifier (Li₂O) and the formation of tetrahedrally coordinated boron in the glasses and crystals.     

Studies on the Complexation of 3d Transition Metal Ions with NR/PEO Block Copolymer in Aqueous Medium

Polyethylene oxide (PEO) was chemically linked to natural rubber (NR) segments to form a block copolymer (BC), which proved to be a suitable material for complexing with selected first row transition metal ions in aqueous solution through batch adsorption method under noncompetitive mode. Optimum conditions for sorption were found to be 20 mmol/L initial concentration, pH at 6, ambient temperature, and 24 h. The order of decreasing adsorption capacity obtained is Mn(II) > Co(II) > Zn(II) > Ni(II) > Cu(II) > Fe(III). Freundlich isotherm shows the best fit indicating that the adsorption is of heterogeneous in nature. The complexation follows pseudo second-order kinetics. Exothermic character of the complexation was confirmed by thermodynamic study. For all metal ions, the standard free energy change values are negative for the different temperatures studied, which confirms the spontaneous character of the process. At ambient temperature, the free energy change lies between −2.35 and − 7.83 kJ/mol for all complexes. Values of activation energy for all the metal ion complexation is within the range 11–25 kJ/mol, which indicates chemical interaction via activated physico–chemical adsorption. Variation in stability constant of the complexes also follows the same order as given above. POLYM. ENG. SCI., 60:661–672, 2020. © 2020 Society of Plastics Engineers     

Improvement of mechanical characteristics of glycidyl azide polymer binder system by addition of flexible polyether

Two kinds of flexible chain polymer, poly(ethylene oxide‐co‐tetrahydrofuran) (P(EO‐co‐THF)) and polyalkylene oxide (PAO), were chosen to improve the mechanical properties of the network of glycidyl azide polymer (GAP)–based elastomers. The mechanical properties of the GAP binder system at 25 and −40 °C can be improved effectively. The effects of P(EO‐co‐THF) and PAO on the network parameters, hydrogen bonding effect, and crystallization property were studied to determine the enhancement mechanism. Based on the results, it can be concluded that for copolyurethane elastomers prepared with PAO content less than 15 wt % and P(EO‐co‐THF), the mechanical properties were enhanced by the reduction of bulk side groups in GAP, which improved the chemical crosslinking density, hydrogen bonding effect in elastomers, and the motility of the molecular chains, while for elastomers prepared with more than 15 wt % PAO, the crystallization of the PAO segments played a major role in the improvement of mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43840.     

A case study of the effect of Ni substitution on the sintering behaviours of Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxygen transport membranes

ABSTRACT

The sintering behaviours of undoped and 8 mol% B-site Ni-doped Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) under various conditions are systematically investigated. Ni doping increases the lattice parameter of BSCF. The grain size of the undoped BSCF increases from 1.52 to 64.8 μm with increasing sintering temperature from 900 at 1150 °C, while the grain size of the Ni-doped counterpart increases from 3.06 to 34.1 μm as the sintering temperature increases from 1000 to 1200 °C. The grain growth kinetics is analysed using the expression Dⁿ = tK ₀exp(-Q/RT). The grain growth exponent n is found to be 3 for the undoped BSCF and 4.7 for the Ni-doped BSCF. The grain growth activation energy (Q) is 650.7±30 kJ/mol for the undoped BSCF and 803.4±37 kJ/mol for the Ni-doped BSCF. This indicates that the Ni dopant has a negative influence on the densification and grain growth of BSCF.     

Effect of plasticizer and curing system on freezing resistance of rubbers

At glass transition temperature, T_g the rubber compound becomes stiff and brittle and it loses all its rubbery characteristics. This article deals with the changes in T_g of rubber blends based on natural rubber and polybutadiene rubber of varying vinyl content having different types and content of plasticizers, different curing systems and its effect on physico‐mechanical properties to improve its freezing resistance. The plasticizers used were dioctylphthalate (DOP), tricrecylphosphate (TCP), dioctyladipate (DOA), and oil type plasticizers like parafinic oil (P#2) and aromatic oil (A#2). Among the plasticizers, when DOP and DOA content was high, an appreciable decrease of T_g was found compared to TCP. Moreover, there was a remarkable decrease of T_g using DOA plasticizer, which shows more effective on freezing resistance. However, there was not much change in T_g with oil‐type plasticizers with high oil content compared to TCP plasticizer. The effect of cross‐linking systems such as conventional sulfur vulcanization (CV), efficient sulfur vulcanization (EV), and dicumyl peroxide (DCP) and rubber blends with varying vinyl content in polybutadiene rubber were also carried out. It was found that T_g in different cross‐linking system decreased in this order: CV < EV < DCP. It reveals that DCP cross‐linking system affect more for improving freezing resistance. Physico‐mechanical properties such as tensile strength, tear strength, hardness were also measured. The ratio of initial slope (M₀) to steady‐state slope (M₁), M₀/M₁ in tensile curves of different blends were verified, which in turn related to the physico‐mechanical properties and freezing resistance of rubber compounds. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39795.     

Water sorption in amorphous poly(ethylene terephthalate)

The water sorption characteristics of poly(ethylene terephthalate) (PET) amorphous samples of 250 μm thickness have been studied at various temperatures in a saturated atmosphere. Concerning diffusivity, one can distinguish the following two domains characterized by distinct values of the activation energy: E_D ≈ 36 kJ mol⁻¹ at T > 100°C, and E_D ≈ 42 kJ mol⁻¹ at T < 60°C, with a relatively wide (60–100°C) intermediary domain linked to the glass transition of the polymer. The crystallization of this latter occurs in the time scale of diffusion above 80°C but doesn't change the Fickian character of sorption curves. The equilibrium concentration m_∞ is an increasing function of temperature, but the solubility coefficient S decreases sharply with this latter, with the apparent enthalpy of dissolution ΔH_s being of the order of −28 kJ mol⁻¹ at T < 80°C and −45 kJ mol⁻¹ at T > 80°C. Density measurements in the wet and dry states suggest that water is almost entirely dissolved in the amorphous matrix at T < 80°C but forms partially a separated phase at T > 80°C. Microvoiding can be attributed to crystallization-induced demixing. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1131–1137, 1999     

Electric conductivity of silicone elastomers vulcanized by the hydrosilation reaction

Electrical conductance and hardness of silicone elastomers, prepared by the vulcanization reaction of hydrosilyl groups with vinyl groups in the presence of platinum catalyst, were measured. It is shown that the electric conductivity of the elastomers decreases as hardness increases and as the temperature decreases. An empirical equation is derived expressing electric conductivity σ as a function of hardness H and absolute temperature T, log σ = −0.03H − 3200/T − 3, where σ is S/m and H is Shore A, over the temperature range of 100–150°C.     

Dynamic viscoelasticity of PUF under small strain and prediction of dynamic viscoelasticity in a wide frequency range

The dynamic viscoelasticity of polyurethane fiber (PUF) under small strain was studied with dynamic mechanical analysis and differential scanning calorimetry, and its viscoelasticity was predicted in a wide frequency range. The results revealed that the loss factor (tan δ) was about 0.05 and the phase angle (δ) was 2.86°, very close to the δ of a perfect elastomer in the range from −100°C to −80°C. The master curves superimposed by time-temperature superposition (TTS), the frequency range of the storage modulus master curve spanned 17 orders of magnitude from 10⁻⁷ Hz to 10¹⁰ Hz, and the loss modulus master curve spanned 13 orders of magnitude from 10⁻³ Hz to 10¹⁰ Hz. The apparent activation energy of the soft segment relaxation decreased with increasing temperature in the range from −70 to −26°C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47070.     

Deeper insights into the thermal properties of epoxy thermoset resins using torsion measurements

The glass transition temperature (T_g) of epoxy thermosets is a critical material property that depends on the component chemistry, the final cross-link density, and processing conditions. This study incorporates dynamic mechanical analysis (DMA) testing with a torsion clamp geometry on a TA Instruments DHR-2 and differential scanning calorimetry (DSC) to characterize five different two-component epoxy-amine systems. Investigation of the T_g dependence on DMA frequency and heating shows that lowering the frequency from 1 to 0.01 Hz results in a T_g very similar to that measured using DSC, while a heating rate of 0.3°C/min using DMA gives a T_g comparable to the DSC measured value at 30°C/min. The DMA technique reveals secondary relaxation transitions and peak broadening in the tan(δ) plots of poorly mixed epoxy blends, quantified using full width at half maximum (FWHM) of tan(δ) peaks, and are indicative of a non-homogeneous cross-linked network and off-ratio blending, respectively. The increase in the FWHM due to poor mixing ranges from 8% to 96%. These parameters are easily measurable and quantifiable in DMA, but are not observed in DSC. The additional DMA insights are valuable for process development and failure analysis, and can improve the understanding of epoxies.     

Effect of silane coupling agent on filler and rubber interaction of silica reinforced solution styrene butadiene rubber

In the present article, the influence of bis‐(triethoxysilylpropyl)‐tetrasulfide (TESPT) content on the viscoelastic behavior of silica filled Solution Styrene Butadiene Rubber (SSBR) was carefully studied in terms of loss tangent spectrum and bound rubber content. The results showed that both relative tan δ area and tan δ_max of filled SSBR with TESPT were detected to present maximum value at 2.5 wt% TESPT(with respect to silica loading). Larger tan δ area and tan δ_max meant more chains participating in the glass transition in the present system, which is reflected by the variation of effective filler volume with TESPT content. The interaction between filler and rubber can be improved remarkably when a little amount of TESPT up to 2.5 wt% was incorporated, whereas as the TESPT content exceeds 2.5 wt% the filler–rubber interaction was weakened, which was also proven by TEM images and Payne effect. The bound rubber content of this SSBR system studied presents the same tendency as tan δ_max. Once TESPT linked with rubber chains, the condensation reaction between silica and SCA is somewhat hindered because of the difficulty in diffusion of large molecules after SCA is chemically bonded with rubber molecules. The network structure of the filled SSBR was analyzed by applying elasticity model. The consecutive increase of crosslink density compensated the reduction of topological tube‐like constrains and thus tensile strength continued to ascend with TESPT content, but sacrificed the ultimate strain. POLYM. COMPOS., 34:1575–1582, 2013. © 2013 Society of Plastics Engineers