Quantitative mapping of surface elastic moduli in silica-reinforced rubbers and rubber blends across the length scales by AFM

The surface elastic moduli of silica-reinforced rubbers and rubber blends were investigated by atomic force microscopy (AFM)-based HarmoniX material mapping. Styrene–butadiene rubbers (SBR) and ethylene–propylene–diene rubbers (EPDM) and SBR/EPDM rubber blends with varying concentrations of silica nanoparticles (0, 5, 10, 20, 50 parts per hundred rubber, phr) were prepared to investigate the effect of different composition on the resulting morphology, filler distribution and elastic moduli of a specific rubber or rubber blend sample. For SBR, the elastic modulus values varied from 0.5 MPa for unfilled SBR to 5 MPa for 50 phr reinforced SBR with the increase in the concentration of filler. For EPDM, the corresponding values increased from 1.4 MPa for unfilled EPDM to 4.5 MPa for 50 phr reinforced EPDM. Local stiff and soft domains in silica-reinforced SBR and EPDM rubbers and rubber blends were identified by HarmoniX AFM imaging. While the stiff silica particles show modulus values as high as 2 GPa, the rubber matrix reveals modulus values in the range of ca. 30 MPa for the rubber blends to ca. 300 MPa for the unfilled rubbers. The lower value of elastic modulus of the EPDM phase in the blend, compared to the blank EPDM compound can be attributed to the presence of Sunpar oil in the compound which has a very good affinity with EPDM and decreases the rubber modulus. The elastic moduli maps revealed an increase of the areal fraction of silica particles showing an intrinsic surface modulus value with rising silica content in the compound preparation mixture. HarmoniX AFM measurements revealed the formation of larger silica aggregates in EPDM in contrast to SBR where isolated silica particles were observed. For silica-reinforced rubber blends a phase separation into a soft (ca. 40 MPa) and a significantly harder phase could be observed (ca. 500 MPa–1.5 GPa) indicating the incorporation of silica particles in the SBR phase. Using HarmoniX AFM imaging significantly higher surface elastic moduli were observed compared to those obtained by bulk tensile testing. Possible reasons for the observed differences between bulk modulus values and those measured by AFM are discussed in detail, including the aspect of different averaging procedures like inherent to surface probing by AFM versus bulk tensile testing, different filler distributions in SBR and EPDM and the AFM modulus calibration procedures.     

The role of tackifiers on the auto-adhesion behavior of EPDM rubber

The article describes the effect of hydrocarbon (HC) and coumarone-indene (CI) resin tackifiers on autohesion behavior of ethylene propylene diene polymethylene (EPDM) rubber. The viscoelastic behavior and nature of compatibility of EPDM/tackifier blends were studied by means of dynamic mechanical analysis. Furthermore, scanning electron microscopy and atomic force microscopy were used to understand the compatibility of the EPDM/tackifier blends. The HC tackifying resin modified the viscoelastic properties of the EPDM rubber in such a way that it behaved as a plasticizer at lower frequency by reducing the storage modulus and filler at higher frequency by increasing the storage modulus. On the contrary, the CI modified EPDM rubber did not show similar behavior; the modulus enhanced throughout the entire frequency range. The viscosity of the matrix was found to be highly governed by the compatibility as well as amount of tackifier present in the blend. In order to explain the tack behavior, several tack governing factors such as green strength, creep compliance, entanglement molecular weight, relaxation time, self-diffusion coefficient, and monomer friction coefficient (ζ₀) were investigated. The tack strength increased with HC tackifier loading up to 24 parts per hundred grams of rubber (phr), beyond which a plateau region was observed. A maximum of 196% improvement was observed at 24 phr HC loaded sample as compared to gum EPDM rubber devoid of tackifier. Conversely, there was a marginal improvement of tack strength (36%) up to 8 phr loading for the system containing CI, beyond which it dropped.     

Effect of crosslinking on morphology and phase inversion of EPDM/PP blends

This study investigates the effect of cross-linking on morphology and phase inversion of EPDM/PP blends. Several EPDM/PP blends without and with cross-linking agent were prepared in a Haake batch mixer under constant conditions. The morphology was studied by electronic microscopy (SEM and TEM), and cross-linking was followed by EPDM gel content and swelling. The results showed that the position of the phase inversion region is essentially governed by composition, being independent of the viscosity ratio of the EPDM/PP blend. The TPVs’ morphology of the EPDM/PP blend, with 70 and 50 wt% of PP, consists of EPDM cross-linked particles dispersed in the PP matrix. For EPDM-rich composition (30 wt% of PP), the TPVs’ morphology appears to be co-continuous. Even though dynamic vulcanisation of the rubber phase always improves the dispersion of the EPDM phase, complete phase inversion (from fully dispersed PP in the EPDM matrix to EPDM fully dispersed in the PP matrix) was achieved only with low viscosity EPDM.     

Effect of ion bombardment on the optical properties of LDPE/EPDM polymer blends

Ion bombardment is a suitable tool to improve the physical properties of polymers. In the present study, the effect of ion bombardment on the optical properties of low density polyethylene (LDPE)/Ethylene propylene diene monomer (EPDM) blend (LDPE/EPDM) was studied. Polymer samples was bombarded with 130 keV He and 320 keV Ar ions at fluencies levels ranging from 1 × 10¹³ to 2 × 10¹⁶ ions/cm². The untreated and ion beam bombarded samples were investigated using ultraviolet-visible (UV-Vis) spectrophotometry. The optical band gap (E_g), was decreased from ∼2.9 eV for the pristine sample down to 1.7 eV for the samples bombarded with He and Ar ions at the highest fluences. Change in the optical gap indicates the presence of a gradual phase transition for the polymer blends. Activation energy has been investigated as a function of the ion fluences. With increasing ion fluence, a decrease in both the energy gap and the activation energy was observed. The number of carbon atoms (N) in a formed cluster is determined according to the modified Tauc's equation.     

Characterization of polypropylene–polyethylene blends made of waste materials with compatibilizer and nano-filler

Waste polypropylene and polyethylene were blended by a twin-screw extruder with two compatibilizers (PE-g-MAH and EPDM) and an additive (O-MMT). The mechanical properties were measured firstly. By adding O-MMT, the tensile strength showed a decline while the impact strength made a promotion. The phase morphology was observed by scanning electron microscopy (SEM) to explore the fracture toughness of blends. The blend with EPDM had a better compatibilization than PE-g-MAH. X-ray diffraction was used to investigate the crystallization behavior and the result showed no change by blending. Moreover, further measurements such as thermogravimetric (TGA) and differential scanning calorimetry (DSC) were taken to show the thermal stability and crystallization temperature of the blend. Additionally, the storage modulus and loss modulus are measured by dynamic mechanical analysis (DMA), the presence of O-MMT caused the increases of the storage modulus and loss modulus.     

NR/CSM/biogenic silica rubber blend composites

Biogenic silica (BSi) was added at different ratios to some polymer blends of polyisoprene rubber (NR) and chlorosulphonated polyethylene rubber (CSM) cured by conventional sulfur system. The reinforcing performance of the filler was investigated using rheometric, mechanical and swelling measurements, differential scanning calorimetry (DSC), thermogravimetric (TGA) and scanning electron microscopy (SEM) analysis. There was a remarkable decrease in the optimum cure time (t_c90) and the scorch time (t_s2), which was associated with an increase in the cure rate index (CRI), with filler loading up to 30 phr in the different blend ratios. The tensile strength and hardness was 4–5 Sh-A higher in the case for the different blend compositions, while the resistance to swelling in toluene became higher. SEM photographs show that the filler is located at the interface between the different polymers which induces compatibilization in the immiscible blends. DSC scans of the filled blends showed shifts in the glass transition temperatures Tg which can be attributed to the improve interfacial bonding between filler and NR/CSM matrix. A higher thermal stability of NR/CSM/BSi composites was detected.     

Morphological interpretations and micromechanical properties of polyamide-6/polypropylene-grafted-maleic anhydride/nanoclay ternary nanocomposites

Ternary nanocomposites were fabricated based on an optimized impact modified polyamide-6 (PA-6)/polypropylene grafted maleic anhydride (PP-g-MA) blend composition with varied concentrations (0–6 wt.% at a step of 2 wt.%) of organoclay, Cloisite 30B™. The morphological attributes such as state of intercalation/exfoliation/crystalline organization and fractured surface topography of the nanocomposites were characterized by transmission electron microscopy (TEM), wide angle X-ray diffraction (WAXD) and scanning electron microscopy (SEM) while the thermal characterizations were done by conducting differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The WAXD/DSC studies have revealed that the crystallinity of the nanocomposites remained unaffected. DMA revealed an increase in glass transition temperature (T_g) of the nanocomposites by ∼14–19 °C relative to the soft polypropylene (PP)-phase, by ∼7–12 °C relative to the neat matrix PA-6 and by ∼4–9 °C relative to the optimized impact toughened PA-6 matrix while simultaneously being accompanied by the appearance of a second phase T_g peak progressively at higher temperatures as a function of nanoclay content, indicating the reinforcement effects/restrictions imposed by the nanoclay layers to the polymer chain mobility. The bulk mechanical response of the nanocomposites such as tensile, flexural and impact properties were studied and its related micromechanics aspects have been investigated using composite theories such as Halpin-Tsai, Hui-Shia, Takayanagi and Pukanszky models to analyze the interfacial effects and its role on the stress transfer efficiency. SEM analysis of fractured surface indicated that the failure mode of the nanocomposites undergoes a switch-over from interfacial-effects assisted fibrillation controlled ductile deformation to nanoclay induced soft PP-phase stiffened semi-ductile response via shear-lips formation.     

Fabrication and mechanical properties of monolithic MoSi2 by spark plasma sintering

Fine MoSi₂ powders containing a small amount of Mo₅Si₃ have been prepared by self-propagating high-temperature synthesis (SHS), followed by spark plasma sintering (SPS) for 10 min at 1200-1500°C and 30 MPa. Dense MoSi₂ materials, in which the grain size is ∼7.5 μm, have been fabricated at 1300°C. They exhibit excellent mechanical properties: Vicker’s hardness H_v (10.6 GPa), fracture toughness K_IC (4.5 MPa m^1/2), and bending strength σ_b (560 MPa). The strength of 325 MPa can be retained up to 1000°C.     

Effect of BiFeO3 additions on the dielectric and piezoelectric properties of (K0.44Na0.52Li0.04)(Nb0.84Ta0.1Sb0.06)O3 ceramics

(1 − x) (K_0.44Na_0.52Li_0.04)(Nb_0.84Ta_0.1Sb_0.06)O₃ − x BiFeO₃ (x = 0, 0.002, 0.004, 0.006, 0.008, 0.01) lead-free piezoelectric ceramics were prepared by the conventional ceramic processing. The compositional dependence of the phase structure and the electrical properties of the ceramics were studied. A morphotropic phase boundary between the orthorhombic and tetragonal phases was identified in the composition range of 0.004 < x < 0.006. The ceramics near the morphotropic phase boundary exhibit a strong compositional dependence and enhanced piezoelectric properties. The ceramics with 0.6 mol.% BiFeO₃ exhibit good electrical properties (d₃₃ ∼ 246 pC/N, k_p ∼ 43%, T_c ∼ 285 °C, ?_r ∼ 1871, and tan δ ∼ 1.96%). These results show that the (1 − x) (K_0.44Na_0.52Li_0.04)(Nb_0.84Ta_0.1Sb_0.06)O₃ − x BiFeO₃ ceramic is a promising lead-free piezoelectric material for applications in different devices.     

Development of conducting polychloroprene rubber using imidazolium based ionic liquid modified multi-walled carbon nanotubes

A simplified and an eco-friendly approach to develop polychloroprene rubber composites with high electrical conductivity is reported. The usage of room temperature ionic liquid, 1-butyl 3-methyl imidazolium bis(trifluoromethylsulphonyl)imide and a low concentration (5 phr) of commercial grade multi-walled carbon nanotubes (MWCNTs) in polychloroprene rubber exhibited an electrical conductivity of 0.1 S/cm with a stretchability >500%. The physical (cation-pi/pi-pi) interaction between the ionic liquid and the MWCNTs is evidenced by Raman spectroscopy. Transmission electron microscopy images exhibit an improved dispersion of the BMI modified tubes in matrix at various magnification scales. The dependency of dynamic properties on the concentration of ionic liquid at constant loading of nanotubes supports the fact that ionic liquid assists in the formation of filler-filler networks. The tensile modulus of 3 phr loaded modified MWCNT/CR composite is increased by 50% with regard to that of the unmodified MWCNT/CR composite. Mooney-Rivlin plot displays the existence of rubber-filler interactions.     

Tropical wood polymer nanocomposite (WPNC): The impact of nanoclay on dynamic mechanical thermal properties

In this study, wood polymer nanocomposites (WPNCS) were manufactured from five Malaysian tropical wood species by vacuum-impregnation attended by in situ polymerization using phenol–formaldehyde resin and montmorillomite nanoclay. Percentage weight gain and density of wood polymer nanocomposites depended on wood species. Thermo-mechanical properties of wood samples were investigated by the dynamic mechanical thermal analysis (DMTA) over the temperature range of −100 °C to 200 °C. The intrinsic properties of the components, morphology of the system and the nature of interface between the phases were also determined through DMTA test. Storage modulus (E′) of WPNC samples exhibited significant improvement over the temperature range, in both glassy region and rubbery plateau in relation to their corresponding raw wood samples and wood polymer composites (WPCs). Furthermore, damping (loss tan δ) peaks of all wood species were lowered by PF-Nanoclay system treatment, an indication of improved surface interphase of wood. Dynamic Young’s modulus (E_d) of wood was also calculated using free–free vibration testing. A significant increment was obtained for the PF-Nanoclay impregnated WPNC samples.     

High-performance composites based on all-aromatic liquid crystal thermosets

In this study, a new high-performance liquid crystal ester-based thermoset for composite applications was investigated. All-aromatic liquid crystalline thermosets (LCTs) are a promising class of polymers that offer a unique combination of properties such as solvent resistivity, high modulus, high strength, low coefficient of thermal expansion and high after cure glass-transition temperatures (T_g ? 150 °C). Fully cured LCTs offer superior thermo-mechanical properties over high-performance thermoplastic polymers such as PPS, PEEK and PEI. For this study we used a 9000 g mol⁻¹ ester-based LCT based on cheap and readily available monomers, i.e. 4-hydroxybenzoic acid (H), isophthalic acid (I) and hydroquinone (Q), abbreviated by us as HIQ-9. Composite panels prepared from T300 carbon fiber (5-harness satin weave) showed in-plane shear strength of 154 MPa and an in-plane shear modulus of 3.7 GPa. The tensile strength and modulus were measured to be 696 MPa and 57 GPa, respectively. A post-mortem inspection showed that the interfacial strength was excellent and no delamination was observed in the test specimen. Preliminary results show that LCT-based composites exhibit a better combination of (thermo) mechanical properties over PPS and PEI-based composites.     

动态硫化EPDM／PP热塑性弹性体动态力学性能的研究

应用动态热力学分析仪测定了动态硫化EPDM／PP共混物的动态力不宪为,Tg峰的变化,表明P的非晶部分与EPDM具有部分互溶性,同时讨论了共混物动态模量的特点,研究了不同橡塑比,硫化剂和软化剂用量对动态硫化EPDM／PP共混物动态力学性能的影响。     

Structure-property relationship of SELF-sustained homogeneous ternary nanocomposites: Key issues to evaluate properties of rrP3HT wrapped MWNT dispersed in TPU

An interesting correlation between nature of wrapping, wrapping thickness and crystallinity of regioregular poly(3-hexyl thiophene) (rrP3HT) wrapped multi-walled nanotube (MWNT) arises due to different loading of rrP3HT and their combined effect on the properties of a ternary system prepared by uniform dispersion of wrapped CNT into thermoplastic polyurethane (TPU) are highlighted in the article. Data accumulated through different techniques demonstrate that 2.5 wt.% of rrP3HT with 0.5 wt.% of MWNT can be the ideal ratio of filler to achieve highest properties in these stable self-sustained homogeneous composites. Wrapping of rrP3HT on the wall of CNT through π-π and/or CH-π interaction is ascertained from shifting in peak position and I_asym/I_sym ratio of CC bond of rrP3HT in FTIR spectroscopy. Strong quenching of fluorescence intensity of rrP3HT in composite further support π-π interaction between rrP3HT and CNTs. SEM micrograph of rrP3HT/TPU blends suggest uniform globular dispersion of polythiophene into TPU matrix without any separate phase domain and addition of CNTs considerably reduce globule size. Single Tg(∼−40 °C, DMA, DSC, TMA) clearly ascertain the miscibility of composite. An ‘order to order transition’ through coil to rod transformation leads to strong, sharp red shifting (∼150 nm shift compared to pristine rrP3HT) in emission peaks of rr-poly (3-hexylthiophene) in blends. Further red shifting and highest quenching is observed in case of 2.5% rrP3HT loaded ternary system whereas blue shifting and quenching in case of 0.5 wt.% (non-uniform wrapping) and 5 wt.% (agglomerates) rrP3HT loading.     

Synthesis of novel zinc oxide microphone-like microstructures

Novel microphone-like ZnO microstructures were grown at a very high density via a simple thermal evaporation process using commercially available ZnO powder in ambient air at ∼ 1050 ± 20 °C in 1 h. The unique as-grown microstructures were characterized in detail in terms of their structural and optical properties. The structural properties of the synthesized products confirmed that they were wurtzite hexagonal phase for the as-grown products. Raman-scattering spectra exhibited a strong and dominated Raman-active E₂ (high) mode at 441 cm^− 1, confirming the wurtzite hexagonal phase for the as-grown microphone-like ZnO morphologies. The cathodoluminescence (CL) spectrum shows a suppressed near band edge emission at ∼ 380 nm and strong green emission at ∼ 500 nm.     

Carbon black–clay hybrid nanocomposites based upon EPDM elastomer

The present study explored the effect of nanoclay on the properties of the ethylene–propylene–diene rubber (EPDM)/carbon black (CB) composites. The nanocomposites were prepared with 40 wt% loading of fillers, where the nanoclay percentage was kept constant at 3 wt%. As the modified nanoclay contains the polar groups and the EPDM matrix is nonpolar, a polar rubber oil extended carboxylated styrene butadiene rubber (XSBR), was used during the preparation of nanocomposites to improve the compatibility. Primarily the nanoclay was dispersed in XSBR by solution mixing followed by ultrasonication. After that EPDM-based, CB–clay hybrid nanocomposites, were prepared in a laboratory scale two roll mill. The dispersion of the different nanoclay in the EPDM matrix was observed by wide-angle X-ray diffraction (WAXD) and high resolution transmission electron microscopy. It was found that the mechanical properties of the hybrid nanocomposites were highly influenced by the dispersion and exfoliation of the nanoclays in the EPDM matrix. Thermo gravimetric analysis, scanning electron microscopy and dynamic mechanical thermal analysis was carried out for each nanocomposite. Among all the nanocomposites studied, the thermal and mechanical properties of Cloisite 30B filled EPDM/CB nanocomposite were found to be highest.     

Modified phosphate pigments as high performance reinforcing materials for rubber vulcanizates

This study is focusing on the synthesis of novel modified micronized phosphate pigments as reinforcing materials for the vulcanizates of styrene-butadiene rubber (SBR), natural rubber (NR) and their blends. The metal phenyl phosphate pigments were prepared via co-precipitation process from the reaction of equimolar ratios of the disodium phenyl phosphate solution and the water soluble salts of the investigated metals. The white prepared phosphate pigments were introduced in the rubber formulations to replace carbon black the highly common and commercial reinforcing material in rubber vulcanizates. The rheometric characteristics, physico-mechanical properties in addition to the accelerated aging properties of the rubber vulcanizates were investigated, discussed and interpreted in the light of previous studies. The results showed that, phenyl phosphate pigments exercised a great effect on the rheological characteristics (scorch time, cure time…etc.), and achieved high performance and pronounced mechanical properties. The stress and strain at yield and at rupture of the loaded rubber with modified phosphates are better than that loaded with carbon black and Hisil e.g. tensile strength data were (20.0–23.4), 18.01 MPa and 15.05 for rubber blend vulcanizates loaded with 30 phr of modified phosphate pigments, carbon black and Hisil, respectively.     

Dielectric properties of a new ceramic system (1 − x)Mg4Nb2O9-xCaTiO3 at microwave frequency

The microstructures and the microwave dielectric properties of the (1 − x)Mg₄Nb₂O₉-xCaTiO₃ ceramic system were investigated. In order to achieve a temperature-stable material, CaTiO₃ (τ_f ∼ 800 ppm/°C) was chosen as a τ_f compensator and added to Mg₄Nb₂O₉ (τ_f ∼ −70 ppm/°C) to form a two phase system. It was confirmed by the XRD and EDX analysis. By appropriately adjusting the x-value in the (1 − x)Mg₄Nb₂O₉-xCaTiO₃ ceramic system, near-zero τ_f value can be achieved. A new microwave dielectric material, 0.5Mg₄Nb₂O₉-0.5CaTiO₃ applicable in microwave devices is suggested and possesses the dielectric properties of a dielectric constant ?_r ∼ 24.8, a Q × f value ∼82,000 GHz (measured at 9.1 GHz) and a τ_f value ∼−0.3 ppm/°C.     

Effect of liquid additives on morphology and properties of thermoplastic elastomers prepared from phase-modified EPDM elastomer and isotactic polypropylene blends

Thermoplastic elastomers (TPEs) were prepared from ternary blends of ethylene propylene diene poly methylene rubber (EPDM), isotactic polypropylene (PP), and low loadings (5–10 phr) of different types of interfacial phase modifiers (like maleated EPDM, styrene-ethylene-co-butylene-styrene block copolymer, and maleated PP). These showed much improved physico-mechanical properties compared to the binary blend of EPDM-PP. The effects of non-polar paraffin oil and polar di-octyl phthalate liquid additives (5–20 phr) were investigated in these phase-modified ternary and binary EPDM-PP blends. Only 5 phr of liquid additives provided synergistic improvement in physical properties (maximum stress, modulus, and elongation at break) and generated improved finer morphology of the ternary blends as revealed from scanning electron and atomic force microscopy studies. Enhanced physical properties and dynamic mechanical properties of these blends were explained with the help of better phase morphology and enhanced crystallinity of the blends.     

Woven hybrid biocomposites: Dynamic mechanical and thermal properties

The dynamic mechanical and thermal analysis of oil palm empty fruit bunch (EFB)/woven jute fibre (J_w) reinforced epoxy hybrid composites were carried out. The storage modulus (E′) was found to decrease with temperature in all cases, and hybrid composites had showed better values of E′ at glass transition temperature (T_g) compared to EFB and epoxy. Loss modulus showed shifts in the T_g of the polymer matrix with the addition of fibre as reinforcing phase, which indicate that fibre plays an important role in case of T_g. The Tan δ peak height was minimum for jute composites and maximum for epoxy matrix. Complex modulus variations and phase behaviour of the hybrid composites was studied by Cole-Cole analysis. Thermal analysis result indicates an increase in thermal stability of EFB composite with the incorporation of woven jute fibres. Hybridization of EFB composite with J_w fibres enhanced the dynamic mechanical and thermal properties.