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ABSTRACT: The structural information of commercial styrene-co-butyl acrylate latex particles along radial direction was observed via the contrast-variation technique using synchrotron
small-angle X-ray scattering (SAXS). By manipulating the electron density of the dispersion medium, the microstructural parameters
of the latex dispersion were evaluated based on quantitative discussion of the scattering intensity distribution profiles.
Four isoscattering points could be identified in the contrast-variation measurements, located at the scattering vectors corresponding
to the position of the sharp minima of the scattering curve of homogenous spheres. This suggests that the shape and structure
of particles were not affected by adding a certain amount of sucrose and salt. This phenomenon was attributed to the existence
of the thin surface layers around particle core in the system. The data indicate that the latex particles exhibit a core–shell
structure, and the average thickness of the shell is about 2nm.
KeywordsContrast variation–SAXS–Isoscattering points–Core–shell structure
Journal of Coatings Technology and Research 04/2012; 8(4):489-496. · 1.12 Impact Factor
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ABSTRACT: Small-angle X-ray scattering data of melt-drawn high-density polyethylene (HDPE) have been analyzed by direct model fitting to projections on the drawing direction. On the basis of the assumption of an infinite paracrystalline lattice as proposed by Hosemann and a rectangular density profile, several additional assumptions have been tested. It turned out that to achieve good fits we have to introduce a finiteness of the lattice for the used samples. Transition zones between crystalline and amorphous regions also improve the model but are of less importance. The most suitable model has been tested on data from an annealing and subsequent cooling process. We show that the additional parameters gained in the modeling approach compared to peak analysis or correlation function analysis lead to a better understanding of the structures and processes in the samples.
The Journal of Physical Chemistry B 12/2011; 115(47):13803-8. · 3.70 Impact Factor
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ABSTRACT: Thermogravimetric analysis and a synchrotron small-angle X-ray scattering technique were employed to characterize the structural evolution of a polymeric latex dispersion during the first three stages of film formation at different temperatures and relative humidities. Three intermediate stages were identified: (1) stage I*, (2) stage I**, and (3) stage II*. Stage I* is intermediate to the conventionally defined stages I and II, where latex particles began to crystallization. The change of drying temperature affects the location of the onset of ordering, whereas relative humidity does not. Stage I** is where the latex particles with their diffuse shell of counterions in the fcc structure are in contact with each other. The overlapping of these layers results in an acceleration of the lattice shrinkage due to a decrease of effective charges. Stage II* is where the latex particles, dried well above their T(g), are deformed and packed only partially during film formation due to incomplete evaporation of water in the latex film. This is because of a rapid deformation of the soft latex particles at the liquid/air interface so that a certain amount of water is unable to evaporate from the latex film effectively. For a latex dispersion dried at a temperature close to its minimum film formation temperature, the transition between stages II and III can be continuous because the latex particles deform at a much slower rate, providing sufficient surface area for water evaporation.
Langmuir 09/2011; 27(21):12807-14. · 4.19 Impact Factor
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ABSTRACT: The influence of solvent annealing on microscopic deformational behavior of a styrene/n-butyl acrylate copolymer latex film subjected to uniaxial tensile deformation was studied by small-angle X-ray scattering. It was demonstrated that the microscopic deformation mechanism of the latex films transformed from a nonaffine deformation behavior to an affine deformation behavior after solvent annealing. This was attributed to the interdiffusion of polymeric chains between adjacent swollen latex particles in the film. It turns out that solvent annealing is much more efficient than thermal annealing due to a much slow evaporation process after solvent annealing.
Langmuir 08/2011; 27(19):12197-200. · 4.19 Impact Factor
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ABSTRACT: Using in situ atomic force microscopy (AFM) and grazing incidence ultrasmall-angle X-ray scattering (GIUSAX), the composition dependence of phase separation, dewetting, and interplay between them in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] ultrathin films (1Rg, radius of gyration) on silicon oxide substrate was investigated. It was found that phase behaviors depended crucially on the composition in blend. First, dewetting morphologies in SAN50 and SAN70 were still under the control of Uq0/E, which was introduced in our previous work [ Polymer 2009, 50, 4456] to distinguish different dewetting pathways. Here, Uq0 and E described the initial amplitude of the surface undulation and original thickness of film, respectively; second, composition produced significant influences on its gradient in composition fluctuation, resulting in the accelerated (or suppressed) dewetting; last, this kind of acceleration or suppression affected the following interplay between phase separation and dewetting so much. Using two samples of “dewetting/wetting–phase separation” and “wetting–dewetting/phase separation” with different components, we discussed the interplay mechanism of them in detail. In conclusion, our results indicate that dewetting, phase separation, and the following interplay between them are sensitive to composition in blend. Furthermore, composition gradient plays an important role in them.
06/2011;
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ABSTRACT: Structural rearrangement in a latex powder during dry sintering at temperatures higher than the minimum film formation temperature was investigated by means of synchrotron small-angle X-ray scattering. Two major effects were identified: (1) Deformation of latex particles leads to a closure of voids between them and an extensive perfectioning of the face centered cubic colloidal crystalline ordering. Such an improvement of the colloidal crystalline structure involves preferential crystal growth along certain crystallographic directions as was evidenced by the measured unmatched relative diffraction intensity distribution of the crystallographic (111) and (220) planes. (2) Interdiffusion of polymeric chains between adjacent particles promotes a nanometer sized aggregation of nonpolymeric materials previously located in the interstices between particles. Size and size distribution of the aggregates at different dry sintering conditions were evaluated by using a model considering spheres dispersed in the system.
Langmuir 05/2011; 27(13):8458-63. · 4.19 Impact Factor
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ABSTRACT: Film thickness dependence of complex behaviors coupled by phase separation and dewetting in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] films on silicon oxide substrate at 175 °C was investigated by grazing incidence ultrasmall-angle X-ray scattering (GIUSAX) and in situ atomic force microscopy (AFM). It was found that the dewetting pathway was under the control of the parameter U(q0)/E, which described the initial amplitude of the surface undulation and original thickness of film, respectively. Furthermore, our results showed that interplay between phase separation and dewetting depended crucially on film thickness. Three mechanisms including dewetting-phase separation/wetting, dewetting/wetting-phase separation, and phase separation/wetting-pseudodewetting were discussed in detail. In conclusion, it is relative rates of phase separation and dewetting that dominate the interplay between them.
Langmuir 09/2010; 26(18):14530-4. · 4.19 Impact Factor
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ABSTRACT: The structural evolution of a colloidal crystal fiber during heating and annealing was followed by in situ synchrotron small-angle X-ray scattering. The polymer dispersion (with a particle size of 118 nm) from which the fibers were formed by directed drying contained emulsifier and salt. A cellular structure formed upon drying in which the percolating phase (the "membrane phase") is composed from these components; this membrane phase gives rise to the scattering contrast on which the present observations build. Changes of the lattice constant of the colloidal crystallites and the intensity evolution of the scattering from the crystalline and the amorphous phases during heating and annealing indicate characteristic temperatures where the system exhibits pronounced structural changes. The first characteristic temperature was identified as 125 degrees C above which residue water in the membrane material was evaporated leading to shrinkage of the colloidal crystalline lattice. At a temperature above about 140 degrees C the membrane material was expelled out of the crystalline domains. This effect is accompanied by the progressive interdiffusion of polymer chains between adjacent latex particles and leads to further thermal shrinkage of the colloidal crystals. The second characteristic temperature is defined by a rapid increase in isotropic scattering. This effect is attributed to the formation of increasingly large domains of the membrane material and the concomitant disappearance of the membrane phase from the former crystal domains.
Langmuir 08/2010; 26(16):13216-20. · 4.19 Impact Factor
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ABSTRACT: The phase transformation of form III isotactic poly(1-butene) was investigated as a function of temperature. The polymer was isothermally precipitated from a dilute solution in iso-amyl acetate and observed with real-time synchrotron small- and wide-angle X-ray scattering techniques. The results confirmed that the polymorphic transition of form III was strongly dependent on temperature. The phase transformation from form III to form I' proceeded at a temperature of ca. 80 degrees C. This was accompanied by the presence of two distinctly different lamellar periodicities arising from form III and I' crystals, respectively. The coexistence of form III and I' crystals can persist up to 103 degrees C, followed by melting and recrystallizing into form II crystals. Finally, the reflections resulting from form II crystals disappeared at 118 degrees C.
The Journal of Physical Chemistry B 05/2010; 114(18):6001-5. · 3.70 Impact Factor
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ABSTRACT: The effect of shear on the crystallization behavior of the poly(ether ether ketone) (PEEK) has been investigated by means of ex situ wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering, and differential scanning calorimetry (DSC). The changes of the intensity of WAXD patterns along shear direction of the PEEK induced by short-term shear were observed when the samples crystallized at 330 °C. The results showed that the dimensions of the crystallites perpendicular to the (110) and (111) planes reduced with the increase of shear rate, whereas the dimensions of the crystallites perpendicular to (200) plane increased with the increase of shear rate. Moreover, increasing shear rate can lead to the increase of the crystallinity as well as the average thickness of the crystalline layers. Correspondingly, a new melting peak at higher temperature was found during the subsequent DSC scanning when the shear rate was increased to 30 s−1. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 220–225, 2010
Journal of Polymer Science Part B Polymer Physics 12/2009; 48(2):220 - 225. · 1.53 Impact Factor
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ABSTRACT: Deformation behavior of polyethylene/modified montmorillonites with polymerizable surfactant (PE/P-MMT) nanocomposite with strong interfacial interaction was studied by means of morphology observation and X-ray scattering measurements. The orientation of PE chains was accompanied by the orientation of well-dispersed MMT platelets due to the presence of strong interfacial interaction, and both of the orientations were parallel to the deformation direction. The high degree of orientation of MMT platelets and PE chains resulted from the synergistic movement of PE matrix and MMTs, which originated from the presence of a network-like structure. Meanwhile, the existence of MMT platelets with good mobility during deformation and strong interfacial interaction with PE matrix could further improve the break energy of material by restraining the initiation and growth of cavities during deformation. In contrast, PE/MMT nanocomposite with no strong interfacial interaction and poor dispersed state of MMT sheets showed the weaker orientation of both PE chains and MMT platelets, and a strong cavitation during deformation.
The Journal of Physical Chemistry B 09/2009; 113(43):14118-27. · 3.70 Impact Factor
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ABSTRACT: The deformation mechanism of styrene/n-butyl acrylate copolymer latex films with fiber symmetric crystalline structure subjected to uniaxial stretching was studied using synchrotron small-angle X-ray scattering technique. The fibers were drawn at angles of 0, 35, and 55° with respect to the fiber axis. In all cases, the microscopic deformation within the crystallites was found to deviate from affine deformation behavior with respect to the macroscopic deformation ratio. Moreover, the extent of this deviation is different in the three cases. This peculiar behavior can be attributed to the relative orientation of the (111) plane of the crystals, the plane of densest packing, with respect to the stretching direction in each case. When the stretching direction coincides with the crystallographic (111) plane, which is the case for stretching directions of 0 and 55° with respect to the fiber axis, the microscopic deformation deviates less from affine behavior than when the stretching direction is arbitrarily oriented with respect to the crystallographic (111) plan. The dependence of tilting angle and d-spacing of selected (111) or (220) planes from the microscopic crystalline draw ratio are fully in accordance with theoretical considerations.
07/2009;
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ABSTRACT: The final structure of molten syndiotactic polypropylene (sPP) sheared under different conditions was investigated by synchrotron small-angle x-ray scattering (SAXS) and wide-angle x-ray diffraction (WAXD) techniques to elucidate the shear effects on sPP crystalline structure. The results obtained from the WAXD show that there is no variation on crystalline form but a little difference on the orientation of the 200 reflection. The SAXS data indicate that the lamellar thickness and long period have not been affected by shear but the lamellar orientation is dependent on shear. The experimental data of sPP crystallization from sheared melt may indicate a mesophase structure that is crucial to the shear effects on the final polymer multiscale crystalline structures.
The Journal of chemical physics 05/2009; 130(16):164909. · 3.09 Impact Factor
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ABSTRACT: The reversible transitions of the lamellae of a crystalline-crystalline diblock copolymer from the melt to crystallites were studied using simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) measurements with synchrotron radiation. A symmetric poly(ethylene oxide)-poly( varepsilon -caprolactone) diblock copolymer was chosen for this study. We showed in the course of the block copolymer crystallisation that the time-resolved integrated intensity I (int) was proportional to the product of the volume fractions of the PEO and PCL phases and the scattering contrast due to the electron density difference. These results demonstrated that simultaneous SAXS/WAXS measurements could be used to monitor the crystallisation process in two domains of different sizes at the same time.
The European Physical Journal E 12/2008; 27(4):357-64. · 1.94 Impact Factor
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ABSTRACT: The structural evolution of a single-layer latex film during annealing was studied via grazing incidence ultrasmall-angle X-ray scattering (GIUSAXS) and atomic force microscopy (AFM). The latex particles were composed of a low-Tg (-54 degrees C) core (n-butylacrylate, 30 wt %) and a high-Tg (41 degrees C) shell (t-butylacrylate, 70 wt %) and had an overall diameter of about 500 nm. GIUSAXS data indicate that the q(y) scan at q(z) = 0.27 nm(-1) (out-of-plane scan) contains information about both the structure factor and the form factor. The GIUSAXS data on latex films annealed at various temperatures ranging from room temperature to 140 degrees C indicate that the structure of the latex thin film beneath the surface changed significantly. The evolution of the out-of-plane scan plot reveals the surface reconstruction of the film. Furthermore, we also followed the time-dependent behavior of structural evolution when the latex film was annealed at a relatively low temperature (60 degrees C) where restructuring within the film can be followed that cannot be detected by AFM, which detects only surface morphology. Moreover, compared to AFM studies GIUSAXS provides averaged information covering larger areas.
Langmuir 11/2008; 25(7):4230-4. · 4.19 Impact Factor
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Macromolecular Chemistry and Physics 06/2008; 209(16):1721 - 1729. · 2.36 Impact Factor
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ABSTRACT: A facile, efficient way to fabricate macroscopic soft colloidal crystals with fiber symmetry by drying a latex dispersion in a tube is presented. A transparent, stable colloidal crystal was obtained from a 25 wt % latex dispersion by complete water evaporation for 4 days. The centimeter-long sample was investigated by means of synchrotron small-angle X-ray diffraction (SAXD). Analysis of a large number of distinct Bragg peaks reveals that uniaxially oriented colloidal crystals with face-centered cubic lattice structure were formed. The measurement of evaporation rates under different conditions indicates that the water evaporates primarily through the optically clear regions (i.e., via the solid material) even when the region is more than 2 mm thick.
Langmuir 04/2008; 24(5):1617-20. · 4.19 Impact Factor
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ABSTRACT: A polymer dispersion consisting of soft latex spheres with a diameter of 135 nm was used to produce a crystalline film with face-centered cubic (fcc) packing of the spheres. Different from conventional small-molecule and hard-sphere colloidal crystals, the crystalline latex film in the present case is soft (i.e., easily deformable). The structural evolution of this soft colloidal latex film under stretching was investigated by in-situ synchrotron ultra-small-angle X-ray scattering. The film exhibits polycrystalline scattering behavior corresponding to fcc structure. Stretching results not only in a large deformation of the crystallographic structure but also in considerable nonaffine deformation at high draw ratios. The unexpected nonaffine deformation was attributed to slippage between rows of particles and crystalline grain boundaries. The crystalline structure remains intact even at high deformation, suggesting that directional anisotropic colloidal crystallites can be easily produced.
Langmuir 10/2006; 22(20):8285-8. · 4.19 Impact Factor
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Yongfeng Men
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ABSTRACT: A polymer dispersion consisting of soft latex spheres with a diameter of 135 nm was used to produce a crystalline film with face-centered cubic (fcc) packing of the spheres. Different from conventional small-molecule and hard-sphere colloidal crystals, the crystalline latex film in the present case is soft (i.e., easily deformable). The structural evolution of this soft colloidal latex film under stretching was investigated by in-situ synchrotron ultra-small-angle X-ray scattering. The film exhibits polycrystalline scattering behavior corresponding to fcc structure. Stretching results not only in a large deformation of the crystallographic structure but also in considerable nonaffine deformation at high draw ratios. The unexpected nonaffine deformation was attributed to slippage between rows of particles and crystalline grain boundaries. The crystalline structure remains intact even at high deformation, suggesting that directional anisotropic colloidal crystallites can be easily produced.
09/2006;
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ABSTRACT: Samples made from linear polyethylene were drawn at room temperature and subsequently annealed at high temperatures below the melting point. The structural changes of the crystalline lamellae and lamellar superstructures as well as the single chain radius of gyration were studied by means of combined small- and wide-angle X-ray scattering and small-angle neutron scattering (SANS). After drawing, the polymeric chain segments in the crystalline phase are preferentially oriented along the drawing direction with a high degree of orientation whereas the lamellae in the samples are found to be slightly sheared exhibiting oblique surfaces as evidenced by X-ray scattering. SANS indicates that the chains are highly elongated along the drawing direction. Annealing the deformed samples at temperatures where the mechanical alpha-process of polyethylene is active leads to a thickening of both crystalline lamellae and amorphous layers. The chains in the crystalline phase retain their high degree of orientation after annealing while the lamellae are sheared to a larger extent. In addition, there is also lateral growth of the crystalline lamellae during high-temperature annealing. Despite the structural changes of the crystalline and amorphous regions, there is no evidence for global chain relaxation. The global anisotropic shape of the chains is preserved even after prolonged annealing at high temperatures. The results indicate that the mobility of polyethylene chains-as seen, e.g., by 13C NMR-is a local phenomenon. The results also yield new insight into mechanical properties of drawn PE, especially regarding stress relaxation and creep mechanisms.
The Journal of Physical Chemistry B 10/2005; 109(35):16650-7. · 3.70 Impact Factor
