Toughening of polypropylene with calcium carbonate particles

Polypropylene-CaCO₃ composites were prepared on a twin screw extruder with a particle content of 0-32 vol%. The influence of particle size (0.07-1.9 μm) and surface treatment of the particles (with and without stearic acid) on the toughening properties were studied. The matrix molecular weight of the polypropylene was also varied (MFI 0.3-24 dg/min). The experiments included tensile tests, notched Izod impact tests, differential scanning calorimetry (DSC), scanning electron microscopy and rheology experiments. The modulus of the composites increased, while the yield stress was lowered with filler content. This lowering of yield stress was connected to the debonding of the particles from the polypropylene matrix. From DSC experiments it was shown that the particle content had no influence on the melting temperature or crystallinity of the PP phase, also particle size showed no effect on the thermal properties. The impact resistance showed large improvement with particle content. The brittle-to-ductile transition was lowered from 90 to 40 °C with the addition of CaCO₃ particles. Notched Izod fracture energy was increased from 2 up to 40-50 kJ/m². The stearic acid coating on the particle surface showed a large positive effect on the impact strength. This was mainly due to the improved dispersion of the CaCO₃ particles. Aggregates of particles clearly had a detrimental effect on the impact behaviour of the composites. The smaller particle sizes (<0.7 μm) showed coarse morphologies and this lowered the toughening efficiency. The molecular weight of the polypropylene matrix had a profound effect on the toughening properties. A higher molecular mass shifted the brittle-to-ductile transition towards lower temperatures. At the higher filler loads (>20 vol%), however, still problems seem to occur with dispersion, lowering the toughening efficiency. Of all particle types used in this study the stearic acid treated particles of 0.7 μm were found to give the best combination of properties. From the study of the micro-toughening mechanism it was shown that at low strain the particles remain attached to the matrix polymer. At higher strain the particles debond and this leads to a change in stress state at the particle size level. This prevents crazing of the matrix polymer and allows extensive plastic deformation, resulting in large quantities of fracture energy.     

Toughening mechanisms of rubber modified thin film epoxy resins

An epoxy terminated polybutadiene (ETPB) was synthesized and utilized to enhance the toughening of an epoxy system, in both bulk and coating states. In the first step, the fracture energy of the modified samples was determined using a single edge notched type specimen in a three point bending (SEN3PB) geometry. The effective toughening mechanisms of bulk epoxy specimens were examined using scanning electron microscopy (SEM). The results showed that plastic void growth, cavitation and shear yielding mechanisms were the main toughening mechanisms of the bulk epoxy systems. In the next step, mechanical properties (i.e. impact resistance, flexibility, cupping resistance and hardness) and adhesion of the thin film specimens were evaluated in accordance to the amount of synthesized ETPB. The results showed that the mechanical properties of the ETPB modified epoxy resins considerably improved. In all cases, it was found that the improvement of the mechanical properties reached a maximum at 7.5 wt.% and then began to decrease with further increase in ETPB content. The effective toughening mechanisms in the modified thin films were also examined using SEM and compared to the bulk types. In contrast to the bulk types, the results showed that crack arresting and shear yielding were active mechanisms in thin films. The contribution of these mechanisms led to the improvement of adhesion and mechanical properties by energy dissipation.     

表面改性硅灰石增韧环氧树脂的研究

采用硬脂酸和两种硅烷偶联剂分别对硅灰石进行了表面改性,研究了不同改性剂的改性效果及不同用量的改性硅灰石对环氧树脂复合材料力学性能的影响;并对硅灰石增韧环氧树脂复合材料冲击断面形貌进行了分析。结果表明:硬脂酸改性硅灰石的改性效果最好,其改性表面接触角最大可达140°,与环氧树脂的相容性得到改善,复合材料的韧性明显提高。当硬脂酸改性硅灰石用量为环氧树脂质量的10%时,拉伸强度提高47.79%,冲击强度提高47.95%。     

Mechanical properties and toughening mechanisms of highly textured Ti3AlC2 composite material

Composite material consisting of Al₂O₃ and TiC in a matrix of highly textured Ti₃AlC₂ was fabricated in a two-step fabrication process. The Lotgering orientation factor for {00 l} planes of Ti₃AlC₂ in the textured top surface plane reached 0.71. Texture analysis showed an orientation relationship among Ti₃AlC₂, Al₂O₃ and TiC grains of [110] Ti₃AlC₂ // [110] TiC, (001) Ti₃AlC₂ // (111) TiC, and [110] Ti₃AlC₂ // [120] Al₂O₃, (001) Ti₃AlC₂ // (001) Al₂O₃. The texture grained material exhibited excellent mechanical properties, with compressive and flexural strengths of more than 2.5 times those of conventional coarse grained Ti₃AlC₂, and fracture toughness and hardness were 50% higher than those of conventional coarse grained Ti₃AlC₂. The microstructures of textured Ti₃AlC₂ and reported textured Ti₂AlC were investigated and compared to interpret the differences in mechanical behavior of the two textured MAX phases.     

PA6/PA6-g-MAH/云母复合材料的增韧研究

分别以乙烯-乙酸乙烯共聚物(EVA)、乙烯-1-辛烯共聚物(POE)、苯乙烯-丁二烯-苯乙烯共聚物(SBS)为增韧剂,研究了它们对聚酰胺6(PA6)/聚酰胺6接枝马来酸酐(PA6-g-MAH)/云母复合材料力学性能的影响。结果表明:以EVA为增韧剂所得复合材料的力学性能优于以POE或SBS为增韧剂所得复合材料;复合材料的冲击强度随EVA用量的增大而上升,当EVA用量为10%时,其冲击强度达到19.01 kJ/m2,较未经增韧改性的复合材料提高了5.29 kJ/m2;但复合材料的拉伸强度和弯曲模量均随增韧剂用量的增大而降低。     

Effects of nano-ZrO2 content on microstructure and mechanical properties of GNPs/nano-ZrO2 reinforced Al2O3/Ti(C,N) composite ceramics

Dense Al₂O₃/Ti(C,N) composite ceramics reinforced with GNPs/nano-ZrO₂ were fabricated by hot-press sintering. The effects of nano-ZrO₂ content on the microstructure and mechanical properties of the prepared Al₂O₃/Ti(C,N)/GNPs/ZrO₂ composites were investigated. Results showed that nano-ZrO₂ inclusions refined the matrix grains significantly and resulted in the formation of intra-granular structure. Excellent comprehensive mechanical properties were achieved via addition of combined GNPs and nano-ZrO₂. In particular, the fracture toughness of composites incorporating GNPs (0.4 wt%)/ZrO₂ (1 wt%) exceeded 11 MPa m^1/2, which was increased by more than 86 % compared with that of Al₂O₃/Ti(C,N) ceramic composites without GNPs/ZrO₂. The main toughening mechanisms have been identified as stress-induced phase transformation, crack bridging, deflection and pull-out of GNPs. The toughening effects originated from GNPs were enhanced with the introduction of nano-ZrO₂ because of not only the residual stress resulted from phase transformation but also the formation of intra-granular structure with uneven surface around GNPs.     

Microstructure and properties of a graphene platelets toughened boron carbide composite ceramic by spark plasma sintering

A kind of B₄C/SiC composite ceramic toughened by graphene platelets and Al was fabricated by spark plasma sintering. The effects of graphene platelets and Al on densification, microstructure and mechanical properties were studied. The sintering temperature was decreased about 125–300?°C with the addition of 3–10?wt% Al. Al can also improve fracture toughness but decrease hardness. The B₄C/SiC composite ceramic with 3?wt%Al and 1.5?wt% graphene platelets sintered at 1825?°C for 5?min had the optimal performances. It was fully densified, and the Vickers hardness and fracture toughness were 30.09?±?0.39?GPa and 5.88?±?0.49?MPa?m^1/2, respectively. The fracture toughness was 25.6% higher than that of the composite without graphene platelets. The toughening mechanism of graphene platelets was also studied. Pulling-out of graphene platelets, crack deflection, bridging and branching contributed to the toughness enhancement of the B₄C-based ceramic.     

Toughening of syndiotactic polypropylene with chalk

We hypothesized that polymer crystal anisotropy is advantageous for toughening of polymer composites involving easy slip network of oriented crystalline layers around filler particles. To this end, composites of syndiotactic polypropylene (sPP) with high concentration of submicrometer calcium carbonate particles were prepared and examined because usual sPP crystals exhibit high packing anisotropy. The specific orientation of sPP lamellae around chalk grains was found, which is supposed to facilitate the plastic deformation of polymer matrices. The compression molded bars of the composite exhibited markedly higher Izod impact strength than those of neat sPP. Toughening was even enhanced in the injection molded composite, for which 4.5‐fold increase in the impact strength was achieved. Injection‐induced orientation of the disordered form I sPP crystals was enhanced in the composite. The injection molded tensile specimens exhibited also a good drawability. Debonding at chalk–sPP interface occurred both during the impact and tensile tests facilitating the plastic deformation of sPP matrix. Chalk did not have any significant influence on the thermal properties of the composites but it affected the rheological behavior, increasing the loss and storage moduli, and the viscosity. Highly filled sPP composite exhibited solid‐like behavior in a molten state with the storage modulus exceeding the loss modulus in the entire frequency range. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43651.     

Microstructure and mechanical properties of B4C matrix composites prepared via hot-pressing sintering with Pr6O11 as additive

High-performance B₄C-PrB₆ composites were prepared via hot-pressing sintering with matrix phase B₄C and with 2–5 wt% Pr₆O₁₁ as additive. The effects of different sintering processes and Pr₆O₁₁ content on the microstructure and mechanical properties of the composites were studied in detail. It is found that increasing sintering temperature and pressure will contribute to the densification of B₄C-PrB₆ composites. Coarse grains are formed in B₄C without additives at high temperature conditions, resulting in the decrease of the densification. Pr₆O₁₁ can effectively hinder the formation of coarse grains and finally promote the densification of the composites. The main toughening mechanisms of composites was crack deflection. The composites with 4 wt% Pr₆O₁₁ prepared at 2050 °C and 25 MPa had the best comprehensive mechanical properties. The relative density, hardness, flexural strength and fracture toughness reached to 98.9%, 37.6 GPa, 339 MPa and 4.4 MP am^1/2, respectively.     

Enhanced toughness and strength of boron carbide ceramics with reduced graphene oxide fabricated by hot pressing

Boron carbide (B₄C) hybrids with different contents of graphene oxide (GO) were prepared by a heterogeneous co-precipitation method using cetyltrimethyl ammonium bromide (CTAB) as the cationic surfactant. The as-obtained mixtures were further hot-pressed at 1950 °C for 60 min under 30 MPa, by which B₄C–reduced GO (rGO) composites were fabricated. It was found that the addition of only 0.5 wt% rGO could alter the predominance of trans-granular fracture in monolithic B₄C ceramic material to mixed trans-granular and inter-granular modes in B₄C–rGO composites. The flexural strength and fracture toughness of the B₄C–2 wt% rGO were increased by 31% (from 350 to 455 MPa) and 83% (from 3.20 to 5.85 MPa·m^1/2), respectively, compared with those of pure B₄C. The improved mechanical properties are attributed to the mechanisms of pull-out and bridging of rGO and crack deflection, as evidenced by microstructural observations. The energy dissipation in the present B₄C–rGO composites was further verified using two micromechanical models.     

Toughening of polypropylene by combined rubber system of ultrafine full-vulcanized powdered rubber and SBS

A combined rubber system of ultrafine full-vulcanized powdered rubber (UFPR) and SBS was used for polypropylene toughening. The PP toughened with the combined rubber system shows not only higher impact strength as compared to each rubber component used alone but also good stiffness and heat resistance. Crystallization study shows that the UFPR is more efficient in promoting the crystallization of PP than SBS, leading to a higher crystallinity and an enhancement of stiffness and heat resistance of PP. The combined rubber system containing UFPR and a small amount of SBS still possesses a good nucleating ability. Transmission electron microscopy results indicate that the combined rubber system mostly forms an encapsulation structure of UFPR particles encapsulated by SBS phase. This morphology was also confirmed by scanning electron microscopy results through observing the fracture surfaces of toughened samples. A small amount of SBS was found to be helpful for a better dispersion of UFPR in PP matrix. The causes for the encapsulation morphology and the synergistic toughening effect were discussed. A tentative explanation was given by comparison of the solubility parameter of each component in the toughened samples.     

Effects of surface modification on rheological and mechanical properties of CNT/epoxy composites

Despite superior properties of carbon nanotubes (CNTs), physical properties of the CNT/epoxy composites are not improved significantly because interfacial bonding between the CNTs and the polymer matrix is weak. CNTs were treated by an acidic solution to remove impurities and modified subsequently by amine treatment or plasma oxidation to improve interfacial bonding and dispersion of nanotubes in the epoxy matrix. The functional groups on the surface of treated CNTs were investigated by X-ray photoelectron spectroscopy. The surface modified CNTs were embedded in the epoxy resin by ultra-sonication and the cured nanotube containing composites were characterized by field emission scanning electron microscopy. Rheological properties of nanotube containing epoxy resin and mechanical properties of the modified CNT/epoxy composites were improved because the modification of CNTs improved dispersion and interaction between the CNT and the epoxy resin.     

Toughening isotactic polypropylene and propylene-ethylene block copolymer with styrene-ethylene butylene-styrene triblock copolymer

Dynamic mechanical properties, low-temperature impact behavior, flexural modulus and heat distortion temperature (HDT) of isotactic polypropylene (i-PP) and propylene-ethylene block copolymer (Co-PP) toughened with styrene-ethylene butylene-styrene triblock copolymer (SEBS), at blending ratios of 0–30 phr, were studied and compared. A scanning electron microscopic morphology study of the impact-fractured surfaces demonstrated the changes in fracture mechanisms at various temperatures and SEBS contents. SEBS remarkably improves the impact endurance in the lower-temperature range when blended with Co-PP in comparison with i-PP, due to the increased compatibility in the interface between SEBS particles and the Co-PP matrix.     

Microstructure,mechanical properties and toughening mechanisms of graphene reinforced Al2O3-WC-TiC composite ceramic tool material

The low fracture toughness of Al₂O₃-based ceramics limited their practical application in cutting tools. In this work, graphene was chosen to reinforce Al₂O₃-WC-TiC composite ceramic tool materials by hot pressing. Microstructure, mechanical properties and toughening mechanisms of the composite ceramic tool materials were investigated. The results indicated that the more refined and denser composite microstructures were obtained with the introduction of graphene. The optimal flexural strength, Vickers hardness, indentation fracture toughness were 646.31?±?20.78?MPa, 24.64?±?0.42?GPa, 9.42?±?0.40?MPa?m^1/2, respectively, at 0.5?vol% of graphene content, which were significantly improved compared to ceramic tool material without graphene. The main toughening mechanisms originated from weak interfaces induced by graphene, and rugged fractured surface, grain refinement, graphene pull-out, crack deflection, crack bridging, micro-crack and surface peeling were responsible for the increase of fracture toughness values.     

Microstructure and mechanical properties of boron carbide/graphene nanoplatelets composites fabricated by hot pressing

In this study, boron carbide (B₄C)-graphene nanoplatelets (GNPs) composites, with enhanced strength and toughness, were fabricated by hot pressing at 1950 °C under a pressure of 30 MPa for 1 h. Microstructure analysis revealed that the GNPs are homogenously dispersed within the B₄C matrix. Raman spectroscopy and electron microscopy showed the orientation of the GNPs in the composites. The effects of the amount of GNPs on the microstructure and mechanical properties of the composites were also investigated. The optimal mechanical properties were achieved using 1 wt% GNPs. The relative density, Vickers hardness, flexure strength, and fracture toughness of the B₄C-GNPs composite ceramic were found to be 99.12%, 32.8 GPa, 508 MPa, and 4.66 MPa m^1/2, respectively. The main toughening mechanisms included crack deflection in three dimensions, GNPs pull-out, and crack bridging. The curled and semi-wrapped GNPs encapsulated individual B₄C grains to resist GNPs pull-out and to deflect propagating cracks.     

Synergistic effects of TiB2 and graphene nanoplatelets on the mechanical and electrical properties of B4C ceramic

Monolithic B₄C, B₄C–TiB₂, and B₄C–TiB₂–graphene nanoplatelets (GNPs) were fabricated by hot pressing (HP) at 1900 °C for 1 h under an axial pressure of 30 MPa. The microstructures and mechanical and electrical properties of the B₄C composites were investigated. The results show that the GNPs are distributed homogeneously in B₄C-based ceramic composites. Compared with monolithic B₄C, the TiB₂–GNPs-containing B₄C composite exhibits an approximately 68 % increase in flexural strength and a 169 % increase in fracture toughness due to the synergistic effects of TiB₂ particles and GNPs. The toughening mechanisms mainly include TiB₂ crack deflection, crack branching, transgranular fracture and GNPs crack deflection, crack bridging, and GNPs pull-out. Additionally, the electrical conductivity of the B₄C composite reinforced with dual fillers is three orders of magnitude higher than that of monolithic B₄C due to the establishment of a conductive network. The addition of GNPs can efficiently connect the isolated conductive TiB₂ particles in the B₄C matrix and provides an additional channel for electron migration.     

Influence of hBN content on mechanical and tribological properties of Si3N4/BN ceramic composites

Silicon nitride materials containing 1–5 wt% of hexagonal boron nitride (micro-sized or nano-sized) were prepared by hot-isostatic pressing at 1700 °C for 3 h. Effect of hBN content on microstructure, mechanical and tribological properties has been investigated. As expected, the increase of hBN content resulted in a sharp decrease of hardness, elastic modulus and bending strength of Si₃N₄/BN composites. In addition, the fracture toughness of Si₃N₄/micro BN composites was enhanced comparing to monolithic Si₃N₄ because of toughening mechanisms in the form of crack deflection, crack branching and pullout of large BN platelets. The friction coefficient was not influenced by BN addition to Si₃N₄/BN ceramics. An improvement of wear resistance (one order of magnitude) was observed when the micro hBN powder was added to Si₃N₄ matrix. Mechanical wear (micro-failure) and humidity-driven tribochemical reaction were found as main wear mechanisms in all studied materials.     

Toughening of unsaturated polyester and vinyl ester resins with liquid rubbers

A comprehensive study of toughening unsaturated polyster and vinyl ester resins by addition of liquid rubbers was carried out by considering the effects of cure temperature and gel time on final resin/rubber morphology. The objective was to produce a dispersed rubber phase consisting of particles less than 15 μm in diameter with the addition of limited amounts of rubber, so as not to seriously reduce the modulus and strength of the base resin. A variety of liquid rubbers was used including those based on poly(butadiene acrylonitrile), poly(epichlorohydrin), and two poly(acrylates). Fracture toughness of unmodified and rubber modified materials was measured using the compact tension (CT) test geometry. Significant improvements in fracture toughness were achieved with little to no change in Young's modulus or glass transition temperature. With modest rubber additions, the fracture toughness increased up to 62% for the polyester resin and up to 116% for the vinyl ester resin. In general, fracture toughness increases with increases in volume fraction of rubbery second-phase particles. However, results suggest that two-phase particles may be more effective tougheners than single-phase particles. The toughening mechanism appears to depend on the type of rubbery particle morphology present.     

Surface modification of TiO2 nano-particles with silane coupling agent and investigation of its effect on the properties of polyurethane composite coating

Surface modification and characterization of TiO₂ nano-particles as an additive in a polyurethane clear coat were investigated. For the improvement of nano-particles dispersion and increasing possible interactions between nano-particles and polymeric matrix, the surface of the nano-particles was modified with amino propyl trimethoxy silane (APS). Equivalent amount of APS for monolayer formation on the nano-particles surface was determined by means of elemental analysis (CHN). The grafting of APS on the TiO₂ nano-particles surface was characterized with TGA and FTIR techniques. Mechanical properties of coatings containing various amount of TiO₂ nano-particles were evaluated with DMA technique and tensile strength measurement. UV–vis spectroscopy was employed to evaluate the absorbance and transmittance of the nano-TiO₂ composite coatings in the wavelength range of 230–700 nm.