MECHANISMS OF TOUGHNESS IMPROVEMENT OF SEMI-CRYSTALLINE POLYMERS

Many normally ductile semi-crystalline polymers, such as polyamide-6 (or 6,6) (Nylon), high density polyethylene (HDPE), and isotactic polypropylene (iPP) are known to be brittle under impact loading.

Some general principles for improvement of toughness of semi-crystalline polymers that rely on the reduction of plastic resistance of the cavitated matrix are presented. As typical cases, the mechanisms of the dramatic toughness jumps achievable in both Nylon and HDPE through the incorporation of either flexible rubbery particles or rigid CaCO₃ particles are discussed. In both cases these result in the establishment of a material component of reduced plastic resistance in the form of a layer of oriented crystallization of well-defined thickness around the particles. The toughness jumps occur when the average interparticle ligament thickness is reduced below a critical value, specific to the particular polymer, and the component of reduced plastic resistance percolates through the structure.     

Reactive Compatibilization of Poly(Butylene Terephthalate)/Acrylonitrile-Styrene-Acrylate Blends by Epoxy Resin: Morphology and Mechanical Properties

The effect on the notched Izod impact strength of poly(butylene terephthalate) (PBT) by blending it with acrylonitrile-styrene-acrylate (ASA) was examined. Epoxy resin (ER) was demonstrated to be an efficient compatibilizer for the partially compatible blends of PBT/ASA. It requires only a very small amount of ER to improve the toughness of the PBT/ASA blends drastically. Furthermore, there exists an optimum proportion of ER added to achieve maximum notched Izod impact strength. Transmission electron microscopy (TEM) observation suggests that the ER in the PBT/ASA/ER blends suppressing the tendency of coalescence of ASA, leading to better dispersion of the ASA particles. Field emission scanning electron microscopy (FESEM) shows that ER enhances the phase dispersion and the interfacial adhesion between the PBT and ASA phases, it improves the compatibility between PBT and ASA. The compositions in the interphase was continuous, which results in multiphase composites with a graded interphase. It is suggested that enhanced interphase adhesion was necessary to obtain improved dispersion, fine phase morphology, and better toughness.     

Polyvinylidene Fluoride/Acrylonitrile Butadiene Rubber Blends Prepared Via Dynamic Vulcanization

Dynamically vulcanized blends based on polyvinylidene fluoride (PVDF)/acrylonitrile butadiene rubber (NBR) were prepared and characterized. The mixing torque and dynamic rheology analyses showed that the NBR phase increased the viscosity of the blends. Scanning electron microscopy (SEM) results showed that the NBR phase was in the form of spherical particles dispersed in the PVDF phase during dynamic vulcanization. Comparing PVDF-rich and NBR-rich blends, the size of the rubber particles in the NBR-rich blends were larger than those in PVDF-rich blends. Differential scanning calorimetry (DSC) results showed that the addition of the NBR phase reduced the PVDF crystallinity and T_m. Thermal gravimetric analysis (TGA) results showed that the dynamically vulcanized PVDF/NBR blends had a higher residual char mass than the neat PVDF and NBR. For PVDF-rich blends, the PVDF can be highly toughened by NBR; the Izod impact strength of the PVDF/NBR (70/30) blend was 77.5 kJ/m², which was about six times higher than that of pure PVDF. For rubber-rich blends, the PVDF component was beneficial to the mechanical properties of the blends, which can be used as thermoplastic elastomers.     

Electron and probe microscopy investigation of the surface of elastomers modified with antifriction fillers

The surface of frost-resistant elastomers (rubbers) based on nitrile-butadiene rubber and propylene- oxide rubber (pure and modified with fillers: ultrafine PTFE and carbon black) is investigated. Tribological tests show that the addition of carbon black produced the greatest effect: the friction coefficient decreases to 0.2 and remains virtually constant during cooling. Surface and subsurface defects are detected by SEM. These defects can affect the processes in the zone of friction and destruction of the sliding surface of rubber. It is demonstrated that the modification of propylene-oxide rubber results in surface smoothing; the effect is the most pronounced in the samples modified with carbon black. The potential to use scanning probe microscopy for local investigation of the surface of rubber is assessed. A conclusion is made about the adhesive properties of surfaces based on the obtained force–distance curves. The investigation of vibration parameters of a probe in contact with the surface provides an opportunity to estimate the surface elasticity. It is shown that the addition of carbon black results in an increase in hardness of the rubber samples and a drastic reduction in adhesion. At the same time, the introduction of ultrafine PTFE leads to a slight enhancement of the adhesion and hardness. It is concluded that carbon black is the best modifying additive for the studied elastomers.     

Calorimetric study of the Paranematic-to-Nematic transition of polydomain side-chain liquid-crystalline elastomers with different mesogen composition

The phase transition behaviour of various nematic side-chain liquid-crystalline elastomers with different mesogen composition has been explored by means of high-resolution ac calorimetry. Polydomain samples of the same crosslinking density and different type of mesogens have been investigated. The results show a strong dependence of the phase transition features upon the composition of the mesogen. The distance from the critical point, reflected in the sharpness of the heat capacity anomalies, increases when adding a shorter-length mesogen. The results provide new insight for the impact of mesogens on the thermodynamic behaviour and, thus, on the thermomechanical response of nematic liquid-crystalline elastomers.     

Influence of Mixing Technique on Microstructure and Impact Properties of Isotactic Polypropylene/ Poly(Cis-Butadiene) Rubber Blends

Isotactic polypropylene/poly(cis-butadiene) rubber (iPP/PcBR vol%: 80/20) blends were prepared by melt mixing with various mixing rotation speeds. The effect of mixing technique on microstructure and impact property of blends was studied. Phase structure of the blends was analyzed by scanning electron microscopy (SEM). All of the blends had a heterogeneous morphology. The spherical particles attributed to the PcBR-rich phase were uniformly dispersed in the continuous iPP matrix. With increase of the mixing rotation speed, the dispersed phase particle's diameter distribution became broader and the average diameter of the separated particles increased. The spherulitic morphology of the blends was observed by small angle light scattering (SALS). Higher mixing rotation speed led to a more imperfect spherulitic morphology and smaller spherulites. Crystalline structure of the blends was measured by wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS). The introduction of 20 vol% PcBR induced the formation of iPPβ crystals. Higher rotation speed led to a decrease in microcrystal dimensions. However, the addition of PcBR and the increase of mixing rotation speed did not affect the interplanar distance. The long period values were the same within experimental error as PcBR was added or the mixing rotation speed quickened. The normalized relative degree of crystallinity of the blends slightly increased under lower rotation speeds (30 and 45 rpm) and decreased under higher rotation speeds. The notched Izod impact strength of the blends was enhanced as a result of the increase of mixing rotation speed.     

Spontaneous ignition of ultra-fine magnesium powder without an original oxide coat at room temperature in O2/N2 mixture streams

To examine the pyrophoric characteristics of Mg powder, we generated ultra-fine Mg particles (average particle diameter: about 0.3 μm) without an original oxide coat in an Ar stream. The ignition of the powder was measured by using the impinging O₂/N₂ mixture streams over a wide range of the experimental parameters: pressure, oxygen concentration and velocity of the streams. The Mg powder was found to ignite even at room temperature. The spontaneous ignition temperatures in the range of 278  324 K were insensitive to all the experimental parameters. The ignition delay time had a tendency to decrease with increasing experimental parameters.The ignition process of the Mg powder was found to be controlled by the surface reaction rate without an oxide coat. We proposed a new ignition hypothesis considering a critical oxide thickness on the Mg powder particles at the transition temperature from protective to non-protective nature: that is, the ignition of the Mg powder occurs when the powder temperature rises above the transition temperature before surface reactions form a protective oxide coat with the critical thickness on the individual particle surfaces. According to this hypothesis, an ignition model of Mg powder cluster was developed, and the relation between the spontaneous critical ignition temperature and the ultra-fine powder size, depending on the critical thickness of the protective oxide coat, was clarified. The critical oxide thickness was estimated.     

Toughening Effect of Ethylene Propylene DieneTerpolymer-Graft-Styrene-Acrylonitrile Copolymer (EPDM-g-SAN) on SAN Resin

The reaction product EPDM-g-SAN, synthesized by suspension graft copolymerization of styrene (St) and acrylonitrile (AN) in the presence of ethylene-propylene-diene terpolymer (EPDM), was blended with a commercial styrene-acrylonitrile copolymer (SAN resin) to prepare AES blends with high impact strength. The effects of AN mass percentage in the St-AN comonomer mixture (f _AN), EPDM mass percentage in the feed of EPDM and St-AN (f _EPDM) and reaction time on monomer conversion ratio (CR), grafting ratio (GR), and AES notched Izod impact strength were characterized. The notched Izod impact strength of AES containing 15 wt% EPDM reached its maximum with f _AN of 40 wt% and f _EPDM of 45 wt%; this was attributed to the polarity of the SAN copolymer obtained being appropriate with that of the SAN resin matrix. The dependences of GR and the notched Izod impact strength of AES containing 25 wt% EPDM on the reaction time were in rough agreement. The effect of EPDM content on the AES notched Izod impact strength indicated that the brittle-ductile transition of AES occurred for an EPDM content from 12.5 to 15 wt%. TEM and SEM analysis showed that the phase structure of AES exhibited a “salami” like structure, and the toughening mechanism of AES was shear yielding of the SAN resin matrix, which endowed AES with excellent toughness.     

Unstable Fracture Behavior of Rubber Toughened Poly(Styrene-co-Acrylonitrile)

A linear elastic fracture mechanics (LEFM) approach was used to study fracture characteristics of ABS materials. The effects of crack (ligament) length and rubber content on the microscopic deformations taking place at the front of crack tip and in the bulk of the specimens were investigated. The results of fractography studies showed that, in addition to rubber content, the microscopic deformations are influenced by crack length. For some materials this manifests itself as a change in macroscopic response. The ligament length dependent behavior was increased for the samples with higher rubber contents. The results also showed that, although the elastic behavior with unstable crack growth is the dominant micromechanism of deformation, stable crack propagation still occurred in some compositions. All the fracture parameters, including fracture toughness, fracture energy, plastic zone size, and crack tip opening, increased with rubber content. The changes in microscopic and, as a consequence, in the macroscopic deformation behavior of a given specimen with ligament length were attributed to changes in yield stress of the sample and maximum stress on the ligament.     

A New Apparatus for Particle Impact Tests

Breakage and chipping of particles due to collision with a hard surface is a common occurrence in many conveying and handling systems, such as pneumatic conveying and jet‐mills. Studies of the breakage mechanism of particles due to impact and the effect of impact velocity and the number of impacts have been investigated in depth both experimentally and theoretically. In this paper, a new concept and apparatus are introduced for conducting particle impact tests. In most of the published test rigs, particles were accelerated towards a target. In our apparatus, the target moves and hits the particles. Using this concept, the machine can operate in a vacuum, which will reduce errors caused by air streams and turbulence. The performance of the new apparatus is analyzed and the breakage phenomenon is discussed, to some extent, for two materials. The results are presented in terms of the increase in the weight percentage of the feed broken and the decrease in the weight median size as the impact velocity or number of impacts increases.     

Numerical simulation on partial coalescence of a droplet with different impact velocities

Partial coalescence is a complicated flow phenomenon. In the present study, the coalescence process is simulated with the volume of fluid(VOF) method. The numerical results reveal that a downward high-velocity region plays a significant role in partial coalescence. The high-velocity region pulls the droplet downward continuously which is an important factor for the droplet turning into a prolate shape and the final pinch-off. The shift from partial coalescence to full coalescence is explained based on the droplet shape before the pinch-off. With the droplet impact velocity increasing, the droplet shape will get close to a sphere before the pinch-off. When the shape gets close enough to a sphere, the partial coalescence shifts to full coalescence. The effect of film thickness on the coalescence process is also investigated. With large film thickness,partial coalescence happens, while with small film thickness, full coalescence happens. In addition, the results indicate that the critical droplet impact velocity increases with the increase of surface tension coefficient but decreases with the increase of viscosity and initial droplet diameter. And there is a maximum critical Weber number with the increase of surface tension coefficient and initial droplet diameter.     

玻璃-橡胶混合颗粒的力学响应研究

通过直剪实验和离散元模拟, 研究掺杂了橡胶软球的玻璃体系的力学响应. 改变颗粒固体中橡胶颗粒的含量, 研究体系剪切强度以及剪胀变化等特性, 发现随着橡胶颗粒的增加, 会出现剪胀到剪缩的相转变现象, 且混合颗粒固体的弹性有了很大的提高. 实验研究发现, 随着体系中橡胶颗粒含量的增加, 剪切屈服强度值逐渐减小, 体积发生从剪胀到剪缩的相转变现象, 但临界剪切强度在一定橡胶颗粒含量范围内保持一致; 实验所采取的剪切速率下, 应力应变曲线能较好重合, 即实验处于率无关区域; 混合样品的屈服强度值随正压力的增大而增大. 离散元模拟也得到了上述结果, 另外模拟还发现, 随着橡胶颗粒含量的增加, 颗粒的平均配位数增大; 橡胶颗粒含量和正压力对剪胀-剪缩相转变的位置有影响, 橡胶颗粒含量较小时, 在较大的正压力下易发生相转变现象, 且剪胀-剪缩相转变点对应的平均配位数在5.6-5.9之间; 在橡胶颗粒含量小于30%时, 混合颗粒样品的残剪强度与不掺杂的颗粒体系相近; 大于30%时, 残剪强度随橡胶颗粒含量的增加而减小; 残剪强度随正压力加大而增加.     

Modelling self-assembling of colloid particles in multilayered structures

Simulations of particle multilayer build-up in the layer by layer (LbL) self-assembling processes have been performed according to the generalized random sequential adsorption (RSA) scheme. The first (precursor) layer having an arbitrary coverage of adsorption centers was generated using the standard RSA scheme pertinent to homogeneous surface. Formation of the consecutive layers (up to 20) was simulated by assuming short-range interaction potentials for two kinds of particles of equal size. Interaction of two particles of different kind resulted in irreversible and localized adsorption upon their contact, whereas particles of the same kind were assumed to interact via the hard potential (no adsorption possible). Using this algorithm theoretical simulations were performed aimed at determining the particle volume fraction as a function of the distance from the interface, as well as the multilayer film roughness and thickness as a function of the number of layers. The simulations revealed that particle concentration distribution in the film was more uniform for low precursor layer density than for higher density, where well-defined layers of closely packed particles appeared. On the other hand, the roughness of the film was the lowest at the highest precursor layer density. It was also predicted theoretically that for low precursor layer density the film thickness increased with the number of layers in a non-linear way. However, for high precursor layer density, the film thickness increased linearly with the number of layers and the average layer thickness was equal to 1.58 of the particle radius, which is close to the closely packed hexagonal layer thickness equal to 1.73. It was concluded by analysing the existing data for colloid particles and polyelectrolytes that the theoretical results can be effectively exploited for interpretation of the LbL processes involving colloid particles and molecular species like polymers or proteins.     

Influence of particle size on the low and high strain rate behavior of dense colloidal dispersions of nanosilica

Shear thickening is a non-Newtonian flow behavior characterized by the increase in apparent viscosity with the increase in applied shear rate, particularly when the shear rate exceeds a critical value termed as the critical shear rate (CSR). Due to this remarkable property of shear-thickening fluids (STFs), they are extensively used in hip protection pads, protective gear for athletes, and more recently in body armor. The use of STFs in body armor has led to the development of the concept of liquid body armor. In this study, the effect of particle size is explored on the low and high strain rate behavior of nanosilica dispersions, so as to predict the efficacy of STF-aided personal protection systems (PPS), specifically for ballistic applications. The low strain rate study was conducted on cone and plate rheometer, whereas the high strain rate characterization of STF was conducted on in-house fabricated split Hopkinson pressure bar (SHPB) system. Spherical nanosilica particles of three different sizes (100, 300, and 500 nm) as well as fumed silica particles of four different specific surface areas (Aerosil A-90, A-130, A-150, and A-200), respectively, were used in this study. The test samples were prepared by dispersing nanosilica particles in polypropylene glycol (PPG) using ultrasonic homogenization method. The low strain rate studies aided in determining the CSR of the synthesized STF dispersions, whereas the high strain rate studies explored the impact-resisting ability of STFs in terms of the impact toughness and the peak stress attained during the impact loading of STF in SHPB testing.     

Computational study of the laminar to turbulent transition over the SD7003 airfoil in ground effect

In this work, we present a numerical study of the laminar-turbulence transition flow around a symmetrical air-foil at a low Reynolds number in free flow and near the ground surface at different angles of attack. Finite volume method is employed to solve the unsteady Reynolds-averaged Navier–Stokes (RANS) equation. In this way, the Transition SST turbulence model is used for modeling the flow turbulence. Flow around the symmetrical airfoil SD7003 is numerically simulated in free stream and near the ground surface. Our numerical method can detect different aspects of flow such as adverse pressure gradient, laminar separation bubble and laminar to turbulent transition onset and the numerical results are in good agreement with the experimental data.     

激光驱动飞片冲击引爆炸药的计算

 在Gurney方程和考虑金属相变状态方程的基础上， 提出了一种激光驱动飞片运动的计算模型。这种模型能确定与炸药临界起爆相关的参数，诸如沉积的激光能量、烧蚀层和飞片的厚度以及飞片飞行的距离等等。计算的结果与实验相符。在本模型中可以对电离、烧蚀及二维效应作进一步的考虑。     

The Role of Interfacial Interactions in the Toughening of Precipitated Calcium Carbonate–Polypropylene Nanocomposites

This paper investigates the effect of the interphase properties and the interfacial interactions between matrix and filler on mechanical properties of precipitated calcium carbonate (PCC)–polypropylene nanocomposites. PCC particles were coated with stearic acid (SA). The weight ratio of SA on the particles (w _SA) ranged from 0 to 0.135 g SA/g PCC. The introduction of PCC particles resulted in an increase in stiffness and yield stress compared with the pristine polymeric matrix and, at the same time, it increased the impact resistance. The maximum improvement in the impact behaviour was achieved for the composites with w _SA =0.045 corresponding to the theoretical monolayer ratio. A decrease in interfacial interactions between monolayer coated PCCs and the matrix with respect to the uncoated particles was observed by using a semi-empirical equation developed by Pukànszky. The low degree of interfacial interactions between particulate filler and matrix allows a matrix–particle debonding phenomenon, as shown by scanning electron microscopy analysis. Extensive plastic deformations were evident as well, promoting an improvement in toughness. The thickness of the interphase between particles and matrix was evaluated by using the Shen–Li model which is based on the hypothesis of a non-homogeneous interphase. It results that the thickness increased in the order uncoated < monolayer coated < 3% SA coated ? 13.5% SA coated particles. The thinner and stronger interphase found for the composite with uncoated particles can be explained with the high interaction between matrix and filler and the consequent low mobility of the polymeric chains.     

Correspondence between two types of rating indices for the heavy weight floor impact sound insulation of residential buildings

Of the two types of rating indices for the heavy weight floor impact sound insulation, the method of utilizing a rubber ball impact source combined with A-weighted sound level and the method utilizing a tire impact source combined with L-rating curve, the advantage of the former has been reported. In order to extend the advantage, the possibility was studied of estimating the rating utilizing the rubber ball impact source, based on the measurement results utilizing the tire impact source, especially for the case of a double leaf wooden floor. The correlation between the indices is not high enough to estimate one of them directly from the other with an accuracy not incorrectly estimating the rating grade of 5 dB step. The use of predictor variables, such as the special specifications of the double leaf wooden floor, for example, the use of sound insulation sheet, and the floor impact sound levels in the 31.5-Hz, 63-Hz and 125-Hz bands, is possibly able to increase the accuracy. Three principal types of multiple regression equation were derived through the analysis of measurement results in existing residential buildings.     

Magnetorheological and deformation properties of magnetically controlled elastomers with hard magnetic filler

Viscoelastic and deformational behavior of soft magnetic elastomers with hard magnetic fillers under the influence of a magnetic field is studied by different experimental techniques. The magnetic elastomers used in this work were synthesized on the basis of silicone rubber filled with FeNdB particles and were magnetized in a field of 3 and 15 kOe. We have shown that due to high residual magnetization the materials demonstrate well pronounced non-elastic behavior already in the absence of any external magnetic field. In particular, in contrast to magnetic elastomers based on soft magnetic fillers their elastic modulus is strain-dependent. Under the influence of external magnetic field the storage and loss moduli of magnetic elastomers with hard magnetic filler can both increase and decrease tremendously.