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1.
The crystallization behavior of the blends of isotactic polypropylene (iPP) and poly(ethylene-co-octene) (PEOc) under quiescent condition and shear flow were studied by differential scanning calorimetry (DSC) and rheology, respectively. The DSC curves of the iPP phase in the blends showed similar crystallization exothermic peaks to that of pure iPP itself, indicating that the addition of PEOc up to a percentage of 30 in weight almost had no influence on the crystallization behavior of iPP at quiescent condition. The rheological results of isothermal flow-induced crystallization (FIC) of iPP in the blends showed that the crystallization kinetics of iPP was enhanced with the increase of shear rate, similar to that of pure iPP, but the presence of PEOc enhanced the effect of shear on the crystallization kinetics of iPP significantly in the cases of shear rates larger than 0.2 s−1, which was due to that PEOc played an important role to promote the nucleation of iPP. The rheological results also implied that the characteristic relaxation times of blends were longer than that of pure iPP during the FIC process, indicating a different relaxation mechanism which might be related to the occurrence of interface relaxation and chain relaxation of the PEOc phase in the blends. 相似文献
2.
Deepak S. Langhe Jong K. Keum Eric Baer 《Journal of Polymer Science.Polymer Physics》2011,49(2):159-171
A layer multiplying coextrusion process was used to produce multilayered polypropylene/polystyrene (PP/PS) films with various nucleating agents. When heated into the melt, the thin PP layers broke up into submicron PP droplets that exhibited fractionated crystallization. If the initial PP layers were 20 nm or less, the resulting droplets exhibited exclusively homogeneous nucleation. If a nucleating agent was added, the systematic departure from homogeneous nucleation provided insight into the nature of the heterogeneous nucleation. In this study, we used thermal analysis, atomic force microscopy (AFM), and wide angle X‐Ray scattering (WAXS) to examine the effect of two nucleating agents. We confirmed with WAXS and AFM that a soluble sorbitol nucleating agent for the PP α‐form operates in three concentration regimes as proposed in a previous study. Morphologically, homogeneous nucleation of the submicron droplets produced a granular texture. The correlation length from small‐angle X‐Ray scattering (SAXS) suggested that the grains contained 1–3 mesophase domains. Drawing on classical nucleation theory, the critical size nucleus of an individual mesophase domain was estimated to be about 2 nm3, which was considerably smaller than the mesophase domain. This pointed to mesophase crystallization that included the processes of nucleation and growth. Additional experiments were performed with nucleating agents for the PP β‐form. However, they were not effective in nucleating crystallization of the droplets, presumably because they were essentially insoluble in PP and the nucleating particles were too large to be accommodated in the PP droplets. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011 相似文献
3.
Summary: Static mixers (Sulzer Chemtech; SMX) were used to prepare silica/ MMA-co-BA miniemulsions that were polymerized to produce nanocomposite latexes. Acceptable conditions for the formulation of polymerizable nanodroplets were found and subsequently used to produce silica/poly(MMA-co-BA) nanocomposites. The droplet size distribution of the resulting miniemulsions was narrow enough that it could be successfully polymerized. It was found that the droplet size depends on the silica content and increases with increasing the silica concentration. It was also shown that there is a relationship between the droplet size and the viscosity of the dispersed phase. The majority of droplets were nucleated upon polymerization when less than 15% silica was used. However, when the silica content exceeded 15%, the ratio of the number of particles in the final latex to the number of droplets (Np/Nd) increased to value much higher than 1 indicating the occurrence of homogeneous nucleation. 相似文献
4.
Y. Jin A. Hiltner E. Baer R. Masirek E. Piorkowska A. Galeski 《Journal of Polymer Science.Polymer Physics》2006,44(13):1795-1803
A dispersion of isotactic polypropylene (PP) nanoparticles was produced by interfacially‐driven breakup of PP nanolayers. Layer‐multiplying coextrusion was used to fabricate an assembly of 257 alternating PP nanolayers about 12 nm thick sandwiched between thicker polystyrene (PS) layers. Characterization by thermal analysis and wide‐angle X‐ray diffraction (WAXD) confirmed that PP crystallized primarily in the smectic form when confined as nanolayers. When the layered assembly was heated into the melt, the PP nanolayers broke up to form a dispersion of PP droplets in a PS matrix. After solidification, particle size analysis revealed that 90% of the PP was present as 30 nm nanoparticles. The particles were small enough and numerous enough that most did not contain a primary nucleus. When cooled from melt at 10 °C min?1, the droplets crystallized by homogeneous nucleation at 40 °C. The droplets were found to be in the smectic form by WAXD. Because crystallization occurred below the temperature of the smectic to α‐form transformation, the intermediate smectic form was stable and did not convert to the α‐form until heated above 70 °C. This result provided direct evidence for an intermediate smectic phase in the process whereby homogeneous nucleation leads to α‐form crystals in confined nanoparticles. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1795–1803, 2006 相似文献
5.
The crystalline structures and crystallization behaviors of iPP containing β nucleation agent TMB-5 (iPP/TMB-5) were investigated by synchrotron radiation wide angel X-ray diffraction (SR-WAXD), differential scanning calorimeter (DSC) and polarized light microscope (PLM). It was found that α-crystallization lagged behind β-crystallization at normal temperatures, but the discrepancy reduced with increasing temperature. TMB-5 could not induce β-iPP when the nucleation agent is wrapped up with α-crystal that crystallized at high temperatures. The polymorphic composition of iPP/TMB-5 was susceptible to the introductory moment of shear. New crystallization process of β-nucleated iPP was proposed to understand the experimental phenomena which could not be explained by those reported in the literature. It was supposed that polymer crystallization initiated from mesophase, and the formations of iPP crystals involved the organization of helical conformation ordering within mesophase. It was proposed that the iPP melt contained mesophases with stereocomplex-type ordering of right-handed and left-handed helical chains which could be disturbed by shear or TMB-5, leading to different polymorphic structures. 相似文献
6.
《中国化学快报》2020,31(12):3216-3220
For drop-on-demand (DOD) inkjet printing, stable and single ink droplet formation without satellite dots is the key to improve the print quality. The formation of stable and single droplet is influenced by filament break up and the polymer chain’s coil–stretch transition behavior. In this paper, the droplet formation behaviors of polyfluorene (PFO) ink at various driving voltages (V), polymer chain’s coil–stretch transition mechanism and its effects on single ink droplet formation are investigated. It indicates that when 58 < V ≤ 63 V, a single and stable droplet is formed with a pulse time of 38.5 μs. At this stage, the Weissenberg number (Wi) < 0.5, the PFO molecular chain is coiled to guarantee stable and single droplets. When V > 63 V, Wi > 0.5, the PFO molecular chain is stretched because of the high hydrodynamic forces, resulting unwanted satellite droplets. When 55 < V ≤ 58 V, the droplet shrinks into the nozzle, which indicates that the kinetic energy supplied by the deformation of the piezoelectric transducer isn't enough to force the droplet to be jetted from the nozzle. 相似文献
7.
Andreas Mauracher Matthias Daxner Stefan E. Huber Johannes Postler Michael Renzler Stephan Denifl Paul Scheier Andrew M. Ellis 《Angewandte Chemie (International ed. in English)》2014,53(50):13794-13797
The formation of dianions in helium nanodroplets is reported for the first time. The fullerene cluster dianions (C60)n2? and (C70)n2? were observed by mass spectrometry for n≥5 when helium droplets containing the appropriate fullerene were subjected to electron impact at approximately 22 eV. A new mechanism for dianion formation is described, which involves a two‐electron transfer from the metastable He? ion. As well as the prospect of studying other dianions at low temperature using helium nanodroplets, this work opens up the possibility of a wider investigation of the chemistry of He?, a new electron‐donating reagent. 相似文献
8.
Xiaoxue Chang Chunhao Sun Leguan Ran Ran Cai Ruiwen Shao 《Molecules (Basel, Switzerland)》2022,27(15)
Revealing the evolutional pathway of the nucleation and crystallization of nanostructures at the atomic scale is crucial for understanding the complex growth mechanisms at the early stage of new substances and spices. Real-time discrimination of the atomic mechanism of a nanodroplet transition is still a formidable challenge. Here, taking advantage of the high temporal and spatial resolution of transmission electron microscopy, the detailed growth pathway of Pb nanodroplets at the early stage of nucleation was directly observed by employing electron beams to induce the nucleation, growth, and fusion process of Pb nanodroplets based on PbTiO3 nanowires. Before the nucleation of Pb nanoparticles, the atoms began to precipitate when they were irradiated by electrons, forming a local crystal structure, and then rapidly and completely crystallized. Small nanodroplets maintain high activity and high density and gradually grow and merge into stable crystals. The whole process was recorded and imaged by HRTEM in real time. The growth of Pb nanodroplets advanced through the classical path and instantaneous droplet coalescence. These results provide an atomic-scale insight on the dynamic process of solid/solid interface, which has implications in thin-film growth and advanced nanomanufacturing. 相似文献
9.
Djikaev YS 《The journal of physical chemistry. A》2008,112(29):6592-6600
The thermodynamics of surface-stimulated crystal nucleation demonstrates that if at least one of the facets of the crystal is only partially wettable by its melt, then it is thermodynamically more favorable for the nucleus to form with that facet at the droplet surface rather than within the droplet. So far, however, the kinetic aspects of this phenomenon had not been studied at all. In the present paper, a kinetic theory of homogenous crystal nucleation in unary droplets is proposed by taking into account that a crystal nucleus can form not only in the volume-based mode (with all its facets within the droplet) but also in the surface-stimulated one (with one of its facets at the droplet surface). The theory advocates that even in the surface-stimulated mode crystal nuclei initially emerge (as subcritical clusters) homogeneously in the subsurface layer, not "pseudo-heterogeneously" at the surface. A homogeneously emerged subcritical crystal can become a surface-stimulated nucleus due to density and structure fluctuations. This effect contributes to the total rate of crystal nucleation (as the volume-based mode does). An explicit expression for the total per-particle rate of crystal nucleation is derived. Numerical evaluations for water droplets suggest that the surface-stimulated mode can significantly enhance the per-particle rate of crystal nucleation in droplets as large as 10 microm in radius. Possible experimental verification of the proposed theory is discussed. 相似文献
10.
Oxygen Reduction Mediated by Single Nanodroplets Containing Attomoles of Vitamin B12: Electrocatalytic Nano‐Impacts Method
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Dr. Wei Cheng Prof. Dr. Richard G. Compton 《Angewandte Chemie (International ed. in English)》2015,54(24):7082-7085
We report the use of single Vitamin B12 nanodroplets to mediate the reduction of oxygen in neutral buffer. Electron transfer to single Vitamin B12 nanodroplets is observed using the nano‐impacts method and shown to be quantitative. The mechanism of mediated oxygen reduction by single VB12 droplets is revealed as via both CoII and CoI reduced from CoIII in VB12 through one or two electron transfer followed by the four‐electron reduction of oxygen. 相似文献
11.
C. Kim S. Yurgenson J. A. Northby 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,40(1):119-122
A beam of helium nanodroplets, with sizes ranging up to N = 107 or more atoms, is produced by fragmentation of a low entropy supersonic expansion. It subsequently is excited by electron impact, producing various charged and metastable droplet states depending on the electron energy. We will describe experiments with negatively charged cluster ions, which are observed for low energy impacts when N >2×105. In these experiments, after a flight time in high vacuum of several milliseconds the droplets pass through a weak transverse field above an electron multiplier. A signal from spontaneously detached electrons is observed, which suggests that the ion, while long lived, is inherently metastable. Furthermore, when the beam is crossed with an infrared light beam above the detector, the detachment rate is significantly increased. The wavelength dependence of this light induced signal has a broad peak near 1.5μm. By deflection measurements it is found that the spontaneous detachment signal comes preferentially from smaller clusters, while the light induced signal comes predominantly from larger ones. By stopping potential measurements one can conclude that both kinds of detached electrons have energies below 1eV, with photo detached electrons the more energetic. 相似文献
12.
Monomer droplet nucleation in the seeded miniemulsion polymerisation of styrene under monomer-flooded and monomer-starved conditions was studied. The miniemulsion feeds were added to the reactor either batchwise or semibatchwise. The droplets preserved longer under flooded conditions. As a result, the batch operation led to a larger number of particles (Np) than the semibatch operation. For the miniemulsion droplets containing predissolved polymer, the final Np was independent of the way that the feed was added to the reactor and was equivalent to the number of monomer droplets in the original miniemulsion feed. The size distribution of the final latexes, however, was influenced by the operation type. For the batch operation, the rate of polymerisation (Rp) with the miniemulsion feeds was higher than that with the conventional monomer emulsion feed because of the monomer droplet nucleation. But for the semibatch operation, the opposite was true because of Rp controlled by the rate of monomer diffusion from rather stable miniemulsion droplets to the growing polymer particles. 相似文献
13.
Within the framework of Gibbsian thermodynamics, a binary droplet is regarded to consist of a uniform interior and dividing surface. The properties of the droplet interior are those of the bulk liquid solution, but the dividing surface is a fictitious phase whose chemical potentials cannot be rigorously determined. The state of the nucleus interior and free energy of nucleus formation can be found without knowing the surface chemical potentials, but the latter are still needed to determine the state of the whole nucleus (including the dividing surface) and develop the kinetics of nucleation. Thus it is necessary to recur to additional conjectures in order to build a complete, thermodynamic, and kinetic theory of nucleation within the framework of the Gibbsian approximation. Here we consider and analyze the problem of closing the Gibbsian approximation droplet model. We identify micro- and Gamma-closure conjectures concerning the surface chemical potentials and excess surface coverages, respectively, for the droplet surface of tension. With these two closure conjectures, the Gibbsian approximation model of a binary droplet becomes complete so that one can determine both the surface and internal characteristics of the whole nucleus and develop the kinetic theory, based on this model. Theoretical results are illustrated by numerical evaluations for binary nucleation in a water-methanol vapor mixture at T=298.15 K. Numerical results show a striking increase in the droplet surface tension with decreasing droplet size at constant overall droplet composition. A comparison of the Gibbsian approximation with density functional calculations for a model surfactant system indicate that the excess surface coverages from the Gibbsian approximation are accurate enough for large droplets and droplets that are not too concentrated with respect to the solute. 相似文献
14.
Manka A Pathak H Tanimura S Wölk J Strey R Wyslouzil BE 《Physical chemistry chemical physics : PCCP》2012,14(13):4505-4516
We report homogeneous ice nucleation rates between 202 K and 215 K, thereby reducing the measurement gap that previously existed between 203 K and 228 K. These temperatures are significantly below the homogenous freezing limit, T(H)≈ 235 K for bulk water, and well within no-man's land. The ice nucleation rates are determined by characterizing nanodroplets with radii between 3.2 and 5.8 nm produced in a supersonic nozzle using three techniques: (1) pressure trace measurements to determine the properties of the flow as well as the temperature and velocity of the droplets, (2) small angle X-ray scattering (SAXS) to measure the size and number density of the droplets, and (3) Fourier Transform Infrared (FTIR) spectroscopy to follow the liquid to solid phase transition. Assuming that nucleation occurs throughout the droplet volume, the measured ice nucleation rates J(ice,V) are on the order of 10(23) cm(-3) s(-1), and agree well with published values near 203 K. 相似文献
15.
Polypropylene(PP)/polybutene-1(PB) alloys within reactor were prepared by MgCl2-supported Ziegler-Natta catalyst with sequential two-stage polymerization technology.First,propylene homo-polymerizations were carried out to form isotactic polypropylene(iPP) particles containing active catalyst.Then,butene-1 was subsequently polymerized to form polybutene-1 phase inside the iPP particles.Finally,iPP/PB alloys with spherical shape and adjustable PB content were synthesized.The catalytic activity and catalytic stereospecificity of the Z-N catalyst in the two-stage polymerization process are discussed.The composition and physical properties of the PP alloys were characterized by FT-IR,13C-NMR,SEM,DSC and XRD.It was found that the in-reactor PP alloys are mainly composed of PP and PB with a little amount of poly(butene-co -propylene) random copolymers and poly(butene-block-propylene) block copolymers.SEM measurements verified that the PB phases with size in the range of 300-400 nm dispersed in the PP matrix uniformly.The incorporation of PB upon the PP matrix affects the properties of final products greatly. 相似文献
16.
Matrix/fiber composites of β-form isotactic polypropylene(iPP) matrix and α-iPP or PA6 fibers were prepared by laminating technique under different preparation temperatures. The mechanical properties and interfacial morphologies of these composites were studied by tensile test, optical microscopy and scanning electron microscopy, respectively. The experimental results show that the tensile yield load and tensile modulus of β-iPP/PA6 matrix/fiber systems increased significantly at the expense of elongation at break. These mechanical properties show essentially no dependence on the sample preparation temperature. On the other hand, the mechanical properties of iPP matrix/fiber single polymer composites depend strongly on the sample preparation temperature. At low sample preparation temperature, e.g., 172 ℃, the solid α-iPP fiber induces α-iPP crystallization, leading to the formation of α-iPP transcrystalline layer around the fiber. This results in a remarkable increment of the tensile yield load and tensile modulus. The elongation at break is also much better than that of the iPP/PA6 matrix/fiber system. It reflects a better interfacial adhesion of the single polymer composite compared with the iPP/PA6 composite. At higher sample preparation temperature, e.g., 174 ℃ or 176 ℃, the partial surface melting of the oriented fiber allows interdiffusion of iPP molecular chains in the molten fiber and matrix melt. The penetration of matrix chains into the molten iPP fiber results in some iPP molecular chains being included partially in the recrystallized fiber and the induced β-transcrystalline layers. This kind of configuration leads to an improvement of interfacial adhesion between the fiber and matrix, which causes a simultaneous increase of the tensile yield load, tensile modulus and elongation at break of β-iPP. 相似文献
17.
Katharina Landfester 《Journal of Dispersion Science and Technology》2013,34(1-3):167-173
Liquid nanodroplets within a size range of 50 to 500 nm can easily be prepared by shearing a system containing oil, water and a surfactant. The growth of the nanodroplets can effectively be suppressed by using a strong hydrophobe as an additivie to the oil and an effective surfactant. The hydrophobe acts as an osmotic agent which stabilizes the system against Ostwald ripening. The growth of the droplets by collision is controlled by the density of the surfactant layer. Freshly prepared miniemulsions are “critically stabilized” and show a slow, but pronounced growth, whereas a miniemulsion in “equilibrium” exhibits constant droplet size on longer time scales. Polymerization of the oil droplets of such miniemulsions turns out to be very promising and extends the possibilities of classical emulsion polymerization. Since each droplet can be considered a small reactor in which polymerization reactions take place, the process allows one to create new particle structures, e.g. polyaddition reactions can take advantage of unusual monomers, the incorporation of materials which are not soluble in the continuous phase, and the formation of nanocapsules. 相似文献
18.
Z. H. Cao G. R. Shan N. Sheibat‐Othman J.‐L. Putaux E. Bourgeat‐Lami 《Journal of polymer science. Part A, Polymer chemistry》2010,48(3):593-603
Nanocapsules with an oily core and an organic/inorganic hybrid shell were elaborated by miniemulsion (co)polymerization of styrene, divinylbenzene, γ‐methacryloyloxy propyl trimethoxysilane, and N‐isopropyl acrylamide. The hybrid copolymer shell membrane was formed by polymerization‐induced phase separation at the interface of the oily nanodroplets with water. It was shown that the size, size distribution, and colloidal stability of the miniemulsion droplets were extremely dependent on the nature of the oil phase, the monomer content and the surfactant concentration. The less water‐soluble the hydrocarbon template and the higher the monomer content, the better the droplet stability. The successful formation of nanocapsules with the targeted core‐shell morphology (i.e., a liquid core surrounded by a solid shell) was evidenced by cryogenic transmission electron microscopy. Both nanocapsules and nanoparticles were produced by polymerization of the miniemulsion droplets. The proportion of nanoparticles increased with increasing monomer concentration in the oil phase. These undesirable nanoparticles were presumably formed by homogeneous nucleation as we showed that micellar nucleation could be neglected under our experimental conditions even for high surfactant concentrations. The introduction of γ‐methacryloyloxy propyl trimethoxysilane was considered to be the main reason for homogeneous nucleation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 593–603, 2010 相似文献
19.
The solution of the kinetic equation of nucleation on macroscopic wettable condensation nuclei was constructed for the initial (incubation) stage. The solution thus constructed determines the times of relaxation to quasi-steady-state distribution of droplets generating on droplet nuclei in the vicinity of maximum of the work of droplet heterogeneous formation as well as the relaxation to quasi-equilibrium droplet distribution throughout the entire region located to the left of this vicinity at the droplet size axis. The dependence of relaxation times on the height of activation barrier of nucleation, size of nuclei, their nature, and characteristics of matter comprising condensate was elucidated. It was shown when the non-steady-state rate of nucleation becomes actually equal to the quasi-steady-state rate of nucleation. 相似文献
20.
Novel compartment microparticles prepared with double emulsion droplets as templates provide a protected internal space for material encapsulation. The effect of three-phase flow rate on the micro-droplet generation of double emulsion mechanism is available for reference to produce precise size and highly monodisperse particles. The influence of three-phase flow rate on the formation mode and size of the emulsion droplets is investigated by combination of experiment and numerical simulation. The size of compound droplets decreases and frequency increases with the increasing outer fluid flow rate. The monodispersity of the double emulsion reduces due to transition from dripping to narrowing jetting regime. Outer droplet size increases with the increasing flow rate of the middle fluid, whereas inner droplet size is the opposite. The frequency increases and then stabilizes, which leads to a widening regime. When Q2/Q1 > 6, the multi-core type double emulsion droplets are produced. Droplet coalescence occurs when surfactants is not involved. As Q1 increases, there is an increasing tendency for inner drop size. The outer drop size is proportional to the sum of the inner and middle flow rate, and that is irrelevant to Q1/Q2. For drop size, the ratio of core-shell and internal structure is precisely controlled by adjusting three-phase flow rate respectively. 相似文献