Off‐line and in‐line analysis of phase morphology and evolution during solidification process of PP/PEOc blend in an internal mixer

Phase morphology and evolution during solidification process of polypropylene and poly(ethylene‐co‐octene) (PP/PEOc) blend in an internal mixer was investigated by means of scanning electron microscopy (SEM) and in‐line back small‐angle laser scattering (BSALS). The average particle diameter (d_p) and the average characteristic length (L_m) were calculated by the pattern analysis of SEM micrographs to describe morphological variation with temperature during solidification process under the natural cooling condition. Furthermore, a fractal dimension (D_f) based on the probability density of the character length was calculated in this study to describe the distribution of main sizes of the dispersed phase particles. Structure parameters, such as heterogeneity distance (lc) and integral invariant (Q), were also calculated using BSALS to describe solidification process. The results obtained from BSALS were in agreement with those obtained from SEM, which means BSALS was valid to study the phase morphology and evolution during solidification process of polymer blend. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Dependence of the Mechanical Sensitivity on the Fractal Characteristics of Octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine Particles

Three fabrication methods were used to synthesize HMX powders with different particle sizes and microscopic morphologies. All as‐prepared samples were characterized by laser granularity measurements and scanning electron microscopy (SEM). The mechanical sensitivity and thermal stability of the different HMX powders were characterized using mechanical sensitivity tests and differential scanning calorimetry (DSC). Size distribution data and SEM images were used to find the size fractal dimension (D) and surface fractal dimension (D_s) of HMX samples, which were calculated by the least‐squares method and fractal image processing software (FIPS), respectively. The parameters D and D_s quantize two important properties of HMX particles, namely the complexity of the particle size distribution and the irregularity of the particle surface, which affect the thermal conductivity of the particle group if it is exposed to stimuli such as impact, friction or heating. The fractal dimensions reveal the dependence of the mechanical sensitivity of HMX on the powder size, size distribution and microscopic morphology. The results indicate that the proportion of fine particles in HMX powder increases as the D value increases, which causes decreased impact sensitivity. This occurs because hot spot formation leading to an explosion is more difficult because of the improved thermal conductivity of the particle group. Similarly, the surface roughness of HMX particles increases with an increase in D_s, causing an increase in friction sensitivity because of the excessive accumulation of frictional heat. In addition, thermal analysis results indicate that the maximum thermal decomposition rate of HMX decreases with increasing D and D_s.     

Temporal evolution of phase morphology of polypropylene/poly(ethylene octene) elastomer binary polymer blends by phase contrast microscope

Blend films of polypropylene/poly(ethylene‐octane) at various mixing times are prepared by freezing‐microtome. The temporal evolution of their phase morphologies is investigated by phase contrast microscope (PCM). The digital image analysis, which contains the analysis in both real and wave‐number space, is introduced to deal with the PCM graphs. The characteristic length, L in real space, the average domain spacing, and the average chord lengths in wave‐number space, are used to express the domain sizes of two phases. The temporal evolution of phase morphology reaches the dynamic equilibrium between breakup and coalescences of domains at the late stage of mixing. In addition, two different fractal dimensions are defined to discuss the symmetry of the distribution of dispersed phase domains and the distribution uniformity: D_f for the symmetry and D_c for the uniformity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Fractal analysis of polypropylene composite filled with nano‐calcium carbonate

Polypropylene (PP) and nano‐calcium carbonate (CaCO₃) composites were prepared by melt mixing in a corotating twin‐screw extruder. Transmission electron microscopy study and particle size analysis revealed the dispersion and the size distribution of CaCO₃ in PP. With the increase of loading of filler, CaCO₃ nanoparticles densely aggregated together and the dispersion of filler became bad. The fractal dimensions of the composites were determined using fractal concept. The fractal dimensions of D and D_k described the irregularities of the shape of an object and the distributions of particle populations, respectively. The D and D_k values were influenced by the content of filler, i.e., the D values increased, and the D_k values decreased with the increase of loading of filler. When the loading of filler was low, the values of D and D_k of PP composites differ slightly than the counterparts of PP/PP‐g‐MA (50 wt %) blend. For 20 wt %, they were almost identical. This fact showed that the fractal dimension was correlated with the dispersion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Analysis of phase morphology and dynamics of immiscible PP/PA1010 blends and its partial-miscible blends during melt mixing from SEM patterns

The formation and evolution of the phase morphology of polypropylene (PP) with Nylon1010 (PA1010) blends before and after adding the compatibilizer, polypropylene grafted maleic anhydride (PP-g-MAH), during melt mixing are investigated by the pattern analysis of scanning electron microscope (SEM). The average particle diameter DP_AV, characteristic length Λ and the average characteristic length Λm are calculated to discuss the melt mixing process. It is proved, by the figure-estimation theory, that the distribution of Λ is log-normal distribution. Furthermore, the phase morphology during melt mixing is discussed in depth by the parameters of the log-normal distribution. The results demonstrate that the structure of the dispersed phase during melt mixing evolves with dynamical self-similarity through the competition of break-up and coalescence of dispersed phase. A fractal dimension, based on the probability density of the character length, is calculated in this study. The results show that the fractal dimension is an effective parameter to characterize the melt mixing process of polymer blends.     

Morphology and properties of nylon6 and high density polyethylene blends in absence and presence of nanoclay

The morphology and properties of nylon6/HDPE blends without and with nanoclay has been reported. Scanning electron microscopy study of the (70/30 w/w) nylon6/HDPE blends with small amount (0.1 phr) of nanoclay indicated a reduction in the average domain sizes (D) of dispersed HDPE phase and hence better extent of mixing compared to the blend without any nanoclay. X‐ray diffraction study and transmission electron microscopy revealed that nanoclay layers were mostly located in nylon6 matrix of the (70/30 w/w) nylon6/HDPE blend. However, the same effect of nanoclay on the morphology was not observed in (30/70 w/w) nylon6/HDPE blend where HDPE became the matrix. In (30/70 w/w) nylon6/HDPE blend, addition of nanoclay increased the D of dispersed nylon6 domains by preferential location of the clays in side the nylon6 domains. Thus, the clay platelets in the matrix phase acted as barrier that restricted the coalescence of dispersed domains during melt‐mixing. Addition of PE‐g‐MA in both the compositions of nylon6/HDPE blend effectively reduced the D of dispersed phases. Storage modulus and thermal stability of the blend were improved in presence of small amount of clay, whereas addition of PE‐g‐MA lowered the mechanical and thermal properties of the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Poly(ethylene‐graft‐ethylene oxide) (PE‐PEO) and poly(ethylene‐co‐acrylic acid) (PEAA) as compatibilizers in blends of LDPE and polyamide‐6

In a blend of two immiscible polymers a controlled morphology can be obtained by adding a block or graft copolymer as compatibilizer. In the present work blends of low‐density polyethylene (PE) and polyamide‐6 (PA‐6) were prepared by melt mixing the polymers in a co‐rotating, intermeshing twin‐screw extruder. Poly(ethylene‐graft‐polyethylene oxide) (PE‐PEO), synthesized from poly(ethylene‐co‐acrylic acid) (PEAA) (backbone) and poly(ethylene oxide) monomethyl ether (MPEO) (grafts), was added as compatibilizer. As a comparison, the unmodified backbone polymer, PEAA, was used. The morphology of the blends was studied by scanning electron microscopy (SEM). Melting and crystallization behavior of the blends was investigated by differential scanning calorimetry (DSC) and mechanical properties by tensile testing. The compatibilizing mechanisms were different for the two copolymers, and generated two different blend morphologies. Addition of PE‐PEO gave a material with small, well‐dispersed PA‐spheres having good adhesion to the PE matrix, whereas PEAA generated a morphology characterized by small PA‐spheres agglomerated to larger structures. Both compatibilized PE/PA blends had much improved mechanical properties compared with the uncompatibilized blend, with elongation at break (ε_b) increasing up to 200%. Addition of compatibilizer to the PE/PA blends stabilized the morphology towards coalescence and significantly reduced the size of the dispersed phase domains, from an average diameter of 20 μm in the unmodified PE/PA blend to approximately 1 μm in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2416–2424, 2000     

Real Space and Wave‐Number Space Studies of the Phase Structure and Morphology of iPP/PEOc Blends Using Scanning Electron Microscopy

The influence of blend composition on the phase structure and morphology of poly(propylene)/poly(ethylene‐co‐octene) blends was studied using SEM. A diameter d_g was defined and calculated in real space to discuss the phase structure and morphology of iPP/PEOc blends. The figure‐estimation method was introduced to determine the distribution width of d_g. It was shown that the distribution of d_g obeys a log‐normal distribution and the distribution width σ of d_g was calculated. In wave‐number (h) space, the correlation distance, a_c, was defined by applying light scattering theory to power spectrum images obtained by 2D Fourier transformation. Moreover, a fractal dimension, D_c, was introduced to describe the uniformity of the spatial distribution.

     

Fractal analysis of morphology of PE/PA blends: Composition

Composition effect on the phase morphology in polyethylene (PE) with polyamide (PA) blends was investigated by pattern analysis of scanning electron micrographs. The average diameter denoted as d_g is defined to discuss the morphology of the blends and further, different fractal dimensions, D_M and D_N, were introduced to characterize the phase morphology. Scale function S_N(r) and S_M(r) are defined to study the selfsimilarity of the phase morphology. The plots of S_N(r)/S_N(r)m (the maximum of S_N(r)) versus r/rm (the maximum of r) and S_M(r)/S_M(r)m (the maximum of S_M(r)) versus r/rm showed the selfsimilar formation of the phase pattern. Furthermore, we calculated the fractal dimension D of different PE/PA blends. The results showed that the fractal dimension was an effective parameter to describe the spacial distribution of dispersed particles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A comparative study of dispersing a polyamide 6 into a polypropylene melt in a Buss Kneader,continuous mixer,and modular intermeshing corotating and counter‐rotating twin screw extruders

We have made a study of the development of phase morphology of an immiscible blend(75/25)(polypropylene–polyamide‐6) for different types of continuous mixers including (i) Buss Kneader, (ii and iii) modular intermeshing corotating and counter‐rotating twin screw extruders, and (iv) NEX‐T Kobelco Continuous Mixer. Comparisons are made using different screw configurations for each machine. Generally, in comparison of the different machines, the intermeshing counter‐rotating twin screw extruder produced the finest dispersed morphology. Using a droplet breakup kinetic model, we interpreted the blend dispersed phase droplet breakdown rate and coalescence rate. In comparison with our earlier study of the continuous mixing of agglomerates of CaCO₃ particles the polymer droplet breakup rate was smaller than that of the particle agglomerates and the coalescence rates of droplets were many times greater than the particle reagglomerates rates. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effect of core‐shell morphology evolution on the rheology,crystallization, and mechanical properties of PA6/EPDM‐g‐MA/HDPE ternary blend

In this article, polyamide 6 (PA6), maleic anhydride grafted ethylene‐propylene‐diene monomer (EPDM‐g‐MA), high‐density polyethylene (HDPE) were simultaneously added into an internal mixer to melt‐mixing for different periods. The relationship between morphology and rheological behaviors, crystallization, mechanical properties of PA6/EPDM‐g‐MA/HDPE blends were studied. The phase morphology observation revealed that PA6/EPDM‐g‐MA/HDPE (70/15/15 wt %) blend is constituted from PA6 matrix in which is dispersed core‐shell droplets of HDPE core encapsulated by EPDM‐g‐MA phase and indicated that the mixing time played a crucial role on the evolution of the core‐shell morphology. Rheological measurement manifested that the complex viscosity and storage modulus of ternary blends were notable higher than the pure polymer blends and binary blends which ascribed different phase morphology. Moreover, the maximum notched impact strength of PA6/EPDM‐g‐MA/HDPE blend was 80.7 KJ/m² and this value was 10–11 times higher than that of pure PA6. Particularly, differential scanning calorimetry results indicated that the bulk crystallization temperature of HDPE (114.6°C) was partly weakened and a new crystallization peak appeared at a lower temperature of around 102.2°C as a result of co‐crystal of HDPE and EPDM‐g‐MA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Bubble size and radial gas hold‐up distributions in a slurry bubble column using ultrafast electron beam X‐ray tomography

Gas hold‐up and bubble size distribution in a slurry bubble column (SBC) were measured using the advanced noninvasive ultrafast electron beam X‐ray tomography technique. Experiments have been performed in a cylindrical column (D_T = 0.07 m) with air and water as the gas and liquid phase and spherical glass particles (d_P = 100 μm) as solids. The effects of solid concentration (0 ≤ C_s ≤ 0.36) and superficial gas velocity (0.02 ≤ U_G ≤ 0.05 m/s) on the flow structure, radial gas hold‐up profile and approximate bubble size distribution at different column heights in a SBC were studied. Bubble coalescence regime was observed with addition of solid particles; however, at higher solid concentrations, larger bubble slugs were found to break‐up. The approximate bubble size distribution and radial gas hold‐up was found to be dependent on U_G and C_s. The average bubble diameter calculated from the approximate bubble size distribution was increasing with increase of U_G. The average gas hold‐up was calculated as a function of U_G and agrees satisfactorily with previously published findings. The average gas hold‐up was also predicted as a function of C_s and agrees well for low C_s and disagrees for high C_s with findings of previous literature. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1709–1722, 2013     

Morphology and properties of nylon 6 and high density polyethylene blends in presence of nanoclay and PE‐g‐MA

In this study, we report the synergistic effect of nanoclay and maleic anhydride grafted polyethylene (PE‐g‐MA) on the morphology and properties of (80/20 w/w) nylon 6/high density polyethylene (HDPE) blend. Polymer blend nanocomposites containing nanoclay with and without compatibilizer (PE‐g‐MA) were prepared by melt mixing, and their morphologies and structures were examined with scanning electron microscopy (SEM) and wide angle X‐ray diffractometer (WAXD) study. The size of phase‐separated domains decreased considerably with increasing content of nanoclay and PE‐g‐MA. WAXD study and transmission electron microscopy (TEM) revealed the presence of exfoliated clay platelets in nylon 6 matrix, as well as, at the interface of the (80/20 w/w) nylon 6/HDPE blend–clay nanocomposites. Addition of PE‐g‐MA in the blend–clay nanocomposites enhanced the exfoliation of clays in nylon 6 matrix and especially at the interface. Thus, exfoliated clay platelets in nylon 6 matrix effectively restricted the coalescence of dispersed HDPE domains while PE‐g‐MA improved the adhesion between the phases at the interface. The use of compatibilizer and nanoclay in polymer blends may lead to a high performance material which combines the advantages of compatibilized polymer blends and the merits of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fractal Analysis of TATB‐Based Explosive AFM Morphology at Different Conditions

The morphology of in situ heated and stockpiled TATB‐based explosive (TBE) was characterized by atomic force microscopy (AFM). The AFM images were analyzed by a fractal method and conventional methods. The result of the fractal analysis indicated that in the thermal process of TBE the binder chains were gradually activated with increasing temperature and resulted in a spread of binder and a decrease in the fractal dimension of the surface. The crystallinity of the binder increased with extending time above the glass transition temperature (T_g), which caused the surface structure dimension (D_f) to be more complicated.     

Computer simulation of fractal dimensions of fat crystal networks

The rheological properties of fat-structured products are determined by the microstructure of their fat crystal networks, which can be quantified by using microscopical and rheological techniques. Of particular interest to this study is the quantification of the fractal dimension of the network using these two techniques. Fractal dimensions determined by polarized light microscopy include box-counting, particle-counting, and Fouriertransform fractal dimensions, whereas the fractal dimensions determined by small deformation dynamic rheology exploit the dependence of the storage modulus on the solids' volume fraction. This work reveals that different microscopy fractal dimensions are sensitive to different microstructural factors within the fat crystal network, and thus have different physical meanings. The boxcounting fractal dimension, D _b , increases with increases in crystal size and area fraction of the fat crystals, whereas the particlecounting fractal dimension, D _f , is sensitive to the radial distribution pattern of fat crystals; and the Fourier-transform fractal dimension, D _FT, decreases with increasing crystal size. In the studies on the macroscopic physical properties of fat crystal networks, it is necessary to find the determining structural characteristics and then use the fractal dimensions that are most closely related.     

Self‐assembled structures in blends of disordered and lamellar block copolymers: SAXS,SANS and TEM study

BACKGROUND: The phase behaviour of copolymers and their blends is of great interest due to the phase transitions, self‐assembly and formation of ordered structures. Phenomena associated with the microdomain morphology of parent copolymers and phase behaviour in blends of deuterated block copolymers of polystyrene (PS) and poly(methyl methacrylate) (PMMA), i.e. (dPS‐block‐dPMMA)₁/(dPS‐block‐PMMA)₂, were investigated using small‐angle X‐ray scattering, small‐angle neutron scattering and transmission electron microscopy as a function of molecular weight, concentration of added copolymers and temperature. RESULTS: Binary blends of the diblock copolymers having different molecular weights and different original micromorphology (one copolymer was in a disordered state and the others were of lamellar phase) were prepared by a solution‐cast process. The blends were found to be completely miscible on the molecular level at all compositions, if their molecular weight ratio was smaller than about 5. The domain spacing D of the blends can be scaled with M_n by D ～ M_n^2/3 as predicted by a previously published postulate (originally suggested and proved for blends of lamellar polystyrene‐block‐polyisoprene copolymers). CONCLUSIONS: The criterion for forming a single‐domain morphology (molecularly mixed blend) taking into account the different solubilization of copolymer blocks has been applied to explain the changes in microdomain morphology during the self‐assembling process in two copolymer blends. Evidently the criterion, suggested originally for blends of lamellar polystyrene‐block‐polyisoprene copolymers, can be employed to a much broader range of block copolymer blends. Copyright © 2008 Society of Chemical Industry     

Morphology-processing relationships in polyethylene-polyamide blends

Blends of polyethylene (PE) and polyamide (PA) were prepared by a melt mixing process. The dependence of the number average size A_n of the dispersed phase on hydrodynamic conditions not only of shear rate but also temperature, inter-facial tension, viscosity of the blends (WU's treatment), and dispersed phase concentration were studied. The analysis of PE-PA blend morphology shows A_n to be the result of a balance between coalescence and disruption of the particles in the melt, and to display a strong increase in particle size when the minor component concentration is enhanced. These observations can be explained by a change in the rheology of the system. These assumptions are confirmed by the insertion in the blend of an ethylenemaleic anhydride (EMA) copolymer that yields EMA-g-PA graft copolymer during mechanical processing. Formation of this graft copolymer has been indicated by a strong particle size reduction and its concentration was measured by infrared experiments. The EMA-g-PA copolymer seems to decrease the blend interfacial tension and to deter the coalescence process.     

Effect of supercritical carbon dioxide on morphology development during polymer blending

Supercritical carbon dioxide (scCO₂) was added during compounding of polystyrene and poly(methyl methacrylate) (PMMA) and the resulting morphology development was observed. The compounding took place in a twin screw extruder and a high‐pressure batch mixer. Viscosity reduction of PMMA and polystyrene were measured using a slit die rheometer attached to the twin screw extruder. Carbon dioxide was added at 0.5, 1.0, 2.0 and 3.0 wt% based on polymer melt flow rates. A viscosity reduction of up to 80% was seen with PMMA and up to 70% with polystyrene. A sharp decrease in the size of the minor (dispersed) phase was observed near the injection point of CO₂ in the twin screw extruder for blends with a viscosity ratio, ηPMMA/ηpolystyrene, of 7.3, at a shear rate of 100 s^?1. However, further compounding led to coalescence of the dispersed phase. Adding scCO₂ did not change the path of morphology development; however, the final domain size was smaller. In both batch and continuous blending, de‐mixing occurred upon CO₂ venting. The reduction in size of the PMMA phase was lost after CO₂ venting. The resulting morphology was similar to that without the addition of CO₂. Adding small amounts of fillers (e.g. carbon black, calcium carbonate, or nano‐clay particles) tended to prevent the de‐mixing of the polymer blend system when the CO₂ was released. For blends with a viscosity ratio of 1.3, at a shear rate of 100 s^?1, the addition of scCO₂ only slightly reduced the domain size of the minor phase.     

Electroconductive polyblend fibers of polyamide‐6/polypropylene/polyaniline: Electrical,morphological, and mechanical characteristics

Melt spun drawn fibers were prepared using a ternary blend of PP/PA6/PANI‐complex (polypropylene/polyamide‐6/polyaniline‐complex). Their electrical and mechanical properties were compared to those of binary blend fibers of PP/PANI‐complex. The results of the morphological studies on 55:25:20 PP/PA6/PANI‐complex ternary fibers were found to be in accordance with the predicted morphology for the observed conductivity vs. fiber draw ratio. The scanning electron microscopy (SEM) micrographs of the ternary blend illustrated at least a three‐phase morphology of a matrix/core‐shell dispersed phase style, with widely varying sizes of droplets. This resulted in a dispersed morphology that, in some parts of the blend, approached a bicontinuous/dispersed phase morphology due to coalescence of the small droplets. The matrix was PP and the core‐shell dispersed phase was PA6 and PANI‐complex, in which a part of the PANI‐complex had encapsulated the PA6 phase and the remaining was solved/dispersed in the PA6 core, as later confirmed by X‐ray mapping. When the ternary blend fibers were compared to the binary fibers, the formers were able to combine better conductivity (of an order of 10^?3 S cm^?1) with a greater tensile strength only at a draw ratio of 5. This indicated that the draw ratio is more critical for the ternary blend fibers, because both conductivity and tensile strength depended on the formation of fibrils from the core‐shell dispersed phase of the PA6/PANI‐complex. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Controlling micro‐ and nanofibrillar morphology of polymer blends in low‐speed melt spinning process. Part III: Fibrillation mechanism of PLA/PVA blends along the spinline

The effects of spinning conditions on the fibrillation process of poly(lactic acid) (PLA) and poly(vinyl alcohol) (PVA) polymer blends in an elongational flow within the fiber formation zone are systematically and thoroughly investigated. By considering the relationship between the changes in filament parameters with the focus on the maximum axial strain rate (ASR) and tensile stress at maximum ASR and the morphological evolution of the dispersed PLA phase along the spinline, the fibrillation process from rod‐like to nanofibrillar structures of the dispersed PLA phase in a binary blend with PVA matrix is elucidated. The final morphology of the dispersed PLA phase in PLA/PVA blends is controlled by the changes in the spinning conditions. The lengths and diameters of the PLA fibrils are caused not only by the deformation of their initial sizes but also by the combination of the deformation, coalescence, and break‐up process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44259.