Barium sulfate-filled blends of polypropylene and poly(styrene-co-acrylonitrile) - dynamic mechanical melt state properties and interlayer effects.
Filled immiscible thermoplastic blends have a complex phase structure, which depends on the processing parameters, chemical character, volume shares, melt viscosity, and surface tension of the components (1, 2). The rheological properties can be used to analyze filled immiscible blends, but the behavior is complex and the properties of a given system can vary substantially depending on the morphology. Because of this, great care must be taken in the analysis of these systems. The most important aspects of the rheology of filled polymers, covering the degree of filling, the influence of particle size and size distribution, and the sensitivity of the dynamic shear amplitude, are very well described in review articles (3-5), and the behavior of multiphase systems is described in more detail by Han (6) and others (7, 8). Basic rules for how to control the morphology of immiscible blends are described by Paul and Barlow (9) and dual phase continuity has been reviewed by Lyngaae-Jorgensen (10). Filled polymer blends have been investigated in studies regarding electrical conductive composites containing carbon black (11, 12). The key issue in this area is to control the phase and filler structure to reach double percolation, i.e. polymer phase continuity and filler-filler continuity. This can be reached at low filler content when the filler is occluded in one of the phases or at the phase boundaries. The mechanical behavior and viscoelastic properties related to the phase morphology of PC/SAN polymer blends has been investigated by Quintens and co-workers (13, 14). This work is of interest here, because of the use of dynamic mechanical measurements as an analytical tool to describe the change of phase morphology during thermal annealing above the glass temperature of both polymers.
In our previous work (15), the microstructure and mechanical properties of filled immiscible blends were investigated by scanning electron microscopy (SEM) and solid state dynamic mechanical spectroscopy, and the measurements were compared with theoretical calculations using a core shell model structure (16, 17). The melt mixed blends consisted of a polypropylene matrix and a poly(styrene-co-acrylonitrile) dispersed phase with a barium sulfate filler. The PP-g-MAH affects the chemical character of the polypropylene matrix and thereby the potential for interactions with the filler and thus offers means for control, in which phase the filler is occluded. This is described by [TABULAR DATA FOR TABLE 1 OMITTED] the SEM micrographs in Fig. 1 a-b, showing filled blends with an average particle size of 1 [[micro]meter], where the residues of the PP/SAN/BaS[O.sub.4] blends (60/20/20 vol %) are visible after selective extraction of the SAN phase by THF. In Fig. 1a, the barium sulfate filler is visible in the cavities after the dissolved SAN phase. However, if enough of the PP matrix is replaced by PPg-MAH, as in Fig. 1b, the mineral filler will be occluded in the PP phase. The microstructure and the dynamic mechanical properties in the solid state could be correlated. The intensity of the SAN glass transition was studied as a function of filler particle size and amount and type of maleic anhydride-grafted polypropylene in the polypropylene matrix. A theoretical model, called the interlayer model, was used as a tool to qualitatively analyze the properties of the investigated blends.
The aim of this work was to study the dynamic mechanical properties of filled blends with different microstructures in the melt state, which consists of a polypropylene matrix and a poly(styrene-co-acrylonitrile) dispersed phase with barium sulfate filler. The properties were studied as a function of filler particle size and amount and type of maleic arthydride-grafted polypropylene in the polypropylene matrix. The results of the measurements were compared with the interlayer model to distinguish the effect of a PP-gMAH interlayer between the filler particles and the polypropylene matrix, the effect of the occlusion of the filler in either the SAN or PP phase, and the effect of a filler network formation.
Table 1 shows the properties of the polymers and of the BaS[O.sub.4] fillers used in this study. The molecular masses of the polymers were determined by size exclusion chromatography, calibrated with broad polyethylene standards for PP and PP-g-MAH, and with narrow polystyrene standards for the SAN copolymer. All the BaS[O.sub.4] grades were of precipitated qualities. Melt mixing in a Brabender AEV 330, with a batch volume of 50 ml, was preceded by drying overnight under vacuum at 60 [degrees] C for all materials except the polypropylene. The polymers were first preblended for 5 minutes, with an additional 10 minutes' melt mixing with the BaS[O.sub.4] filler added at a melt temperature of 190 [degrees] C and 40 rpm. The filled polymer composites were then pressed at 190 [degrees] C into 25 mm circular samples for dynamic mechanical characterization. The samples were analyzed with a Rheometrics Dynamic Analyzer RDAII with a 25 mm parallel plate fixture in the melt state at 170 [degrees] C. Dynamic strain sweeps from 0.1 to 100% at 1 rad/s and dynamic frequency sweeps from 500 to 0.1 rad/s at low strains, typically 1% for filled blends with PP-g-MAH and 0.5% for filled blends without PP-g-MAH, were used in the measurements. The pure materials were characterized at higher strains. Scanning electron microscope analysis, with a Zeiss DSM 940A apparatus, was performed on samples fractured at liquid nitrogen temperature followed by 2 hours' selective extraction of SAN in THF at room temperature. The densities used to estimate the volume fraction were 910 kg/[m.sup.3] for the PP and the PP-gMAH, 1080 kg/[m.sup.3] for the SAN copolymer and 4400 kg/[m.sup.3] for the BaS[O.sub.4]. The volume share polypropylene plus PP-g-MAH was kept constant at 60% in the filled blends, and the concentration of PP-g-MAH is given as volume percentage of the polypropylene matrix. The SAN and filler volume shares were kept equal and constant at 20% each.
The interlayer model (16, 17) is used to simulate the dynamic mechanical properties of the filled blends. The model is derived from the van der Poel model (18) corrected by Schwarzl (19) and Smith (20). The representative volume element in the interlayer model has the geometry of an elastic sphere covered by a shell of interlayer, which in turn is surrounded by a shell of matrix material. Finally, there is a homogeneous phase with properties equivalent to those of the heterogeneous dispersion surrounding the spheres. The model assumes perfect dispersion of spherical particles in the matrix without taking into account any interactions, particle size or particle size distribution. The method accounts only for the pure mechanical-geometrical effect of the presence of the particle and layers. The most important condition is that the representative volume element reacts to external stresses as a cube of homogeneous composite material and that displacements and radial and tangential stresses are continuous at the boundaries of the phases. With these limiting prerequisites, a set of linear equations is obtained as a result of the continuity conditions in a rotationally symmetrical shear stress field. The determinants of the coefficients of the linear equation system should be zero to obtain a solution that is not trivial with which to calculate the shear modulus. This leads to a quadratic equation with the following form:
[Mathematical Expression Omitted] (1)
[G.sub.c] and [G.sub.m] are the shear moduli for the composite and matrix, respectively, and [absolute value of X], [absolute value of Y], [absolute value of Z] and [absolute value of T] are tenth order determinants of the 10 x 10 matrixes, X, Y, Z and T, respectively. The determinants depend on the shear moduli, Poisson ratios and the volume fractions of the constituents. The extension of the elastic solution for Equation 1 to a viscoelastic solution is made on the basis of the correspondence principle (16, 17, 21). The dynamic mechanical properties of the polymers used in the model as the constitutive materials are shown in Fig. 2 a-b. The values of the PP and SAN polymers are the measured ones, and the properties of the low molecular weight MA4 graft copolymer are smoothed data from the measurements, with an average phase angle of 74 [degrees].
Calculations of the mechanical properties of the filled blends without PP-g-MAH were always made with a polypropylene matrix, SAN interlayer and BaS[O.sub.4] filler particle. The properties of the mineral-filled PP phase with a PP-g-MAH interlayer were calculated with MA4 in the model blend. The properties of the filled polypropylene matrix with different volume shares of filler and MA4 were then able to be used in the calculations of the properties of the system (PP/MA4/BaS[O.sub.4])/SAN/BaS[O.sub.4], which represents matrix/interlayer/filler. If all the filler was assumed to be located in the polypropylene phase, the calculations were performed for a system with a (PP/MA4/BaS[O.sub.4])matrix filled with spherical SAN occlusions without interlayer. Furthermore, Poisson ratios for SAN, PP and MA4 were assumed to be 0.5 in the melt state. The Poisson ratio for the BaS[O.sub.4] is 0.3 (22), and the dynamic shear modulus, [G.sub.d]([Omega]), for BaS[O.sub.4] is calculated to have a value (22) of 1.15 x [10.sup.10][Pa]. The filler is considered in the simulations to be pure elastic, i.e. the dynamic shear loss modulus, G[double prime][([Omega]).sub.filler] = 0.
The melt state dynamic mechanical spectra of the polypropylene, SAN and MA4 are depicted in Fig. 2 ab. It is clear from the Figure that the SAN copolymer has a higher dynamic mechanical modulus than PP in the melt state. The MA4 low molecular weight maleic anhydride grafted polypropylene has a low dynamic modulus and an almost Newtonian behavior at 170 [degrees] C.
The dynamic mechanical properties of the filled blends was seen to be very sensitive towards the amplitude of the oscillatory shear in the measurements. The known reason for this sensitivity is a structure formed by the filler particles. The dependence of the strain amplitude for the properties is shown in Fig. 3, depicting the quotient of the dynamic modulus as a function of the strain amplitude at 1 rad/s in the numerator and of the dynamic modulus at 0.1% strain amplitude at 1 rad/s in the denominator, [G.sub.d]([Gamma])/[G.sub.d,[Gamma] = 0.1%], plotted as a function of strain amplitude. The average filler size and concentration of MA4 are varied in Fig. 3 in the PP/SAN/BaS[O.sub.4] blends. We concluded from our previous study (15) that the filler particles are occluded solely in the SAN phase in PP/SAN/BaS[O.sub.4] blends without MA4. With 2.5% of the PP matrix substituted by the graft copolymer and with fillers of 1 [[micro]meter] average particle diameter, the filler win be occluded in both phases. Finally with more than 5% MA4, the filled blend reaches a saturation level with all the filler particles occluded in the PP phase. From the strain sweep in Fig. 3, it can be seen that the nonlinearity starts at low strain values. The sensitivity is weakest for the smallest particles with an average particle diameter of 0.1 [[micro]meter]. The amplitude dependence becomes less pronounced when PP-g-MAH is added. The reason for this is twofold. First, as we deduce from our previous study, the filler concentration decreases when the filler is present in both phases or only in the PP phase and not in the SAN phase, which would be highly filled and very strain-sensitive. Secondly, the PP-g-MAH has an affinity to the BaS[O.sub.4] filler and probably acts on the filler as a dispersive agent in the PP phase, with less filler-filler contact changing the filler particle structure and thereby lowering the strain dependence.
Figures 4 and 5 shows the frequency dependency at 170 [degrees] C of the dynamic mechanical properties for the different PP/SAN/BaS[O.sub.4] (60/20/20 vol%) blends. The concentration of PP-g-MAH is varied for three different average particle sizes (0.1, 1 and 3.5 [[micro]meter]) in Fig. 4 a-c, and the type of PP-g-MAH is then varied for blends with 1 [[micro]meter] filler size in Fig. 5 a-b. In the blends without PP-g-MAH, the filler is occluded in the SAN phase, meaning that 40 vol% of the blend is a highly filled polymer (50/50 vol%) with a strong modulus-enhancing effect in the melt. Another important reason for the high modulus values without PP-g-MAH is probably the deviation from the ideal dispersed spherical phase structure.
The frequency dependency of [G.sub.d]([Omega]) and [Delta]([Omega]) for the filled blends with fillers of an average particle size of 0.1 [[micro]meter] and different concentrations of MA4 can be seen in Fig. 4a. The measurements were carried out with different strain amplitudes, but at the expected low amplitudes for filled polymers of 0.5-1% (4, 5). The lower amplitude of 0.5% was used for blends without PP-g-MAH and a strain amplitude of 1% was used in blends with PP-g-MAH because of the above mentioned phenomena. The dynamic modulus is at its highest value for all frequencies shown when no MA4 is present. With 2.5% and 5% MA4, the modulus is lowered, but with 7.5 and 10% MA4 the [G.sub.d]([Omega]) values increase as a function of PP-g-MAH concentration, especially at low frequencies. This behavior is also described by the phase angle, which decreases with frequency and increases with MA4 content up to 5%. At 7.5% and 10% MA4, the phase angle, [Delta]([Omega]), is lowered as compared with 5% MA4. At low frequencies, the phase angle even decreases as a function of decreased angular frequency for the blends with 7.5% and 10% MA4.
The average filler size is increased to 1 [[micro]meter] in Fig. 4b. This lowers the dynamic modulus and increases the phase angle at the investigated frequencies, as compared with the corresponding blends with an average filler size of 0.1 [[micro]meter]. The tendencies of the mechanical properties when increasing MA4 concentration are similar to the tendencies in Fig. 4a with 0.1 [[micro]meter] fillers. In Fig. 4c, the average barium sulfate filler size is increased to 3.5 [[micro]meter], and the [G.sub.d]([Omega]) and [Delta]([Omega]) are further lowered and increased, respectively.
Different PP-g-MAH types are used in Fig. 5a and 5b, namely MA1 and MA7. In an earlier work (15), they were shown to have quite a different capability to occlude the filler in the polypropylene phase as a function of concentration. The MA7 must be added in higher concentrations, compared with MA4, and MA1 is weak in its ability to control the phase in which the filler is occluded. When MA1 and MA7 are used, there is an experimental indication of the influence of the low molecular PP-g-MAH on the dynamic mechanical properties, especially the MA1, which is not very effective in controlling the phase in which the filler is occluded. This can be observed in Fig. 5a, where the dynamic modulus decreases systematically as a function of the concentration of MA1. When MA1 is present in the blends, the phase angle, [Delta]([Omega]), increases for all concentrations from 2.5% up to 10% MA1. MA7 is used in Fig. 5b, and the pattern is closer to the behavior of the blends with MA4, but the [G.sub.d]([Omega]) does not increase as a function of MA7 concentration at higher concentrations, as do blends with MA4. Neither does [Delta]([Omega]) decrease as a function of decreasing frequency at low frequencies and high MA7 concentration. The lowest modulus, in the blends with a filler size of 1 [[micro]meter], is reached with MA4 and MA7 at 5% and 10% PP-g-MAH, respectively. This is probably because of the change in microstructure and dilution of the filler in the PP matrix phase of low viscosity compared with SAN, and because of the PP-g-MAH interlayer around the filler particles occluded in the PP phase. The MA1 does not have the ability to occlude an the filler particles in the PP phase and cannot cause these effects, and thus there is a lower modulus decrease at the highest MA1 concentration compared with MA4 and MA7.
The larger drop in the [G.sub.d]([Omega]) curves as a function of PP-g-MAH concentration in Figs. 4 and 5 can be coordinated with morphological changes in the filled blends. The morphology as a function of PP-g-MAH concentration was investigated earlier by SEM (15). When MA4 is added, the PP/SAN/BaS[O.sub.4] blend goes from a 60/40 PP/(SAN/BaS[O.sub.4]) system with a cocontinuous type of microstructure to a 80/20 (PP/MA4/BaS[O.sub.4])/SAN system with a matrix and an elongated dispersed SAN phase. This phenomenon can be seen in Fig. 4a when 5% MA4 is used and in Figs. 4b and 4c when 2.5% MA4 is used. The absence of one dominant jump in the [G.sub.d]([Omega]) curves in Fig. 5a is a result of the fact that the filler is never occluded solely in the PP phase as a function of MA1 concentration. The viscosity-decreasing effect of the polypropylene phase resulting from the fact that the PP-g-MAH does not act as an interlayer is therefore much more visible with the MA1 graft copolymer than with MA4 and MA7. Another effect shown in Fig. 4 is the increase of the [G.sub.d]([Omega]) curves at the highest MA4 concentrations or the decrease of the phase angle at low angular frequencies and high MA4 concentrations. This may be explained by the formation of an elastic component in the matrix, caused by the well-dispersed BaS[O.sub.4] forming a structure in the polypropylene matrix. On the other hand, the introduction of a low molecular mass interlayer around the filler particles should not cause a higher modulus, but on the contrary should lower the dynamic modulus. The effects of the filler surface area can also be seen in Fig. 4, from which it can be concluded that the drop of modulus, [G.sub.d]([Omega]), as a function of MA4 concentration in the blends is lowest for the smallest sized filler of 0.1 [[micro]meter]. Accordingly, the phase angle decreases with increased filler surface area in Fig. 4 a-c. At higher frequencies, the phase angle in Fig. 4 a-c first increases with the concentration of PPg-MAH. However, for the smallest filler in Fig. 4a, the phase angle decreases slightly with increased MA4 concentration at the highest MA4 concentrations. This could also be a result of a more efficient filler structure formation at higher MA4 concentrations compared with the fillers of larger size and smaller surface area. The increase in modulus in Fig. 4a when increasing the concentration of MA4 from 5% could be logical if the PP-g-MAH has a compatibilizing effect on the BaS[O.sub.4] filler in the PP phase and causes a break-up of agglomerated structures resulting in particles with a smaller effective diameter. However, once again, the same counter-argument can be raised; a low molecular mass interlayer should lower the modulus and increase the phase angle. The results so far show that the dynamic mechanical properties in the melt vary as a complicated response to morphology, dilution of filler, polymer filler compatibility, interlayer formation and a filler structure formation.
Some of the simulations with the interlayer model made are shown in Fig. 6, where the calculated dynamic modulus, [G.sub.d]([Omega]), is plotted as a function of angular frequency at 170 [degrees] C. The model curve with the highest modulus is reached in the simulation with an the filler occluded in the SAN phase and no MA4 added to the blend. In the case in which all the filler is occluded in the polypropylene phase, the modulus curve drops a relatively small step compared with the curve with the highest modulus, but, when an interlayer of MA4 is introduced in the model, the [G.sub.d]([Omega]) curve drops more significantly. The drop of [G.sub.d]([Omega]) then continues with the layer thickness in a systematic way. The theoretical interlayer effects are analyzed by the quotas of the calculated [G.sub.d]([Omega]) curves in Fig. 7; the four uppermost curves show the quota between the [G.sub.d]([Omega]) for a blend without MA4 and an the filler occluded in the SAN phase in the numerator, and, in the denominator, the modulus of the blends with a MA4 interlayer between the polypropylene and the filler. It can be seen that the theoretical influence of the PP-gMAH interlayer in the calculations is more pronounced at lower frequencies, especially with a thicker interlayer. The theoretical frequency dependence of the phase in which the filler is occluded in a filled blend without PP-g-MAH, illustrated by the lowest curve, is relatively weak in Fig. 7, but it must be remembered that the model does not take the degree of filling or particle-particle interaction or interlocking into consideration. The theoretical calculations in the melt state support the analysis of the melt state dynamic mechanical measurements and previous SEM study that a PP-g-MAH interlayer forms around the filler particles and filler agglomerates, and this results in great morphological and mechanical effects. The use of functionalized polymers has shown to be a viable route to morphological control.
Effects of an interlayer formation and of the filler size can be seen in the results in Fig. 4, depicting the dynamic mechanical measurements with different filler sizes and the same PP-g-MAH, MA4. The effect of an interlayer formation is the large drop in modulus as a function of an increased concentration of MA4, described earlier. The influence of the filler size is illustrated [TABULAR DATA FOR TABLE 2 OMITTED] by the higher absolute modulus of the corresponding blends containing the smaller filler. The theoretical modulus is, as expected, always lower than the measured ones for the equivalent filled blends. This is an indication of filler-filler contact, interlocking and other deviations from the ideal conditions in the theoretical model, assuming perfect dispersion of spherical particles with spherical interlayer and matrix. Another important question is whether we can regard the PP-g-MAH as an interlayer, with the properties of the pure material, around every particle, regardless of the particle size or the concentration of PP-g-MAH. Theoretically, the random coil end-to-end size, r, can be calculated by using the formula (23):
[<[r.sup.2]>.sub.0] = [C.sub.[infinity]] [multiplied by] n [multiplied by] [l.sup.2]
where the first subscript signifies the theta conditions, which can be regarded in the melt state, and n is the number of carbon-to-carbon bonds of length, l = 1.54[Angstrom]. [C.sub.[infinity]] is a constant which depends on the nature of the polymer when n, [approaches][infinity] and is set to 5.7, which is the value for isotactic PP in accordance with Flory (23). With a SEC number average molecular mass for the MA4 of 8.4 kg/mole, the end-to-end size is calculated to 7.4 nm. This is to be compared with the theoretical interlayer thickness in Table 2, if all particles are surrounded by a PP-g-MAH interlayer regardless of the random coil size, which must indicate the minimum layer thickness. A strong interaction between the BaS[O.sub.4] filler and the PP-g-MAH is probably not the case here, but could otherwise change the conformation of the graft copolymer on the filler surface. The theoretical interlayer thickness in Table 2 shows that the thickest interlayer in the case with the smallest filler (0.1 [[micro]meter]) is of lower value than the minimum layer thickness indicated by the end-to-end size. When the largest filler of 3.5 [[micro]meter] is used, the interlayer is probably thick enough to show bulk properties, and the situation with the 1-[[micro]meter] filler is an intermediate case. An interlayer of only a few nanometers does not have the properties of the pure material, especially when the interlayer consists of modified PP and must be compatible to some degree with the matrix PP.
We can therefore speculate that agglomerated filler structures consisting of BaS[O.sub.4] filler particles with an average size of 0.1 [[micro]meter] are occluded in the PP matrix because of the MA4 graft copolymer. A further increase of MA4 results in deagglomeration of the filler.
The filler particles are probably surrounded by an interlayer consisting of PP-g-MAH molecules attached to the filler surface, and the graft copolymer is also affected by the matrix, resulting in an interlayer with a higher modulus than that of the pure MA4. This phenomenon could give rise to a filler structure in the PP matrix able to increase the dynamic mechanical modulus. The process described may also be true in the case with the barium sulfate filler, with an average particle size of I [[micro]meter], but with much less emphasis on the deagglomeration part. The speculation is supported in the literature, where there is a description of the formation of filler networks by spherical particles in an unpolar thermoplastic matrix (24). Factors such as filler size and level of filler-matrix interaction capabilities, which affect filler network formation in carbon black-filled thermoplastic polymers, are described by Gandhi and Salovey (25). The phenomenon of polymer bound on solid filler is discussed by Lipatov (26), and adsorbed polyethylene on kaolin was investigated by Maurer et al. (27). The bound polymer results in a layer with properties different from the bulk properties of the pure polymer.
The dynamic mechanical properties of the PP/SAN/BaS[O.sub.4] blends in the melt are systematically influenced by the BaS[O.sub.4] average particle size and the amount of MA4 added to the blend. Decreasing the average filler particle size decreases the drop in the dynamic shear modulus as a function of PP-g-MAH concentration in the blends and increases the absolute modulus. Increased concentration of the low viscous MA4 can even enhance the modulus of the blends, especially at lower frequencies; from the study it is reasonable to believe that this is a result of a filler network formation. The use of different low molecular weight PP-g-MAH qualities sheds some light on the effect of a low molecular component in the PP phase with the filler occluded in both phases. MA4 shows a complicated response in its dynamic mechanical properties because of its ability to control the polymer phase in which the filler is occluded and a probable ability to deagglomerate the barium sulfate filler of the smallest average size. On the other hand, MA1 shows a simpler response, with a monotonously decreasing modulus as a function of concentration at all frequencies studied.
Comparisons of measurements and theoretical calculations indicate that the phase in which the filler is occluded is of lesser importance. The more important factor for the dynamic mechanical properties in the melt is the introduction of an interlayer of low viscosity between the filler and the polypropylene and the filler size.
We gratefully acknowledge the National Swedish Board for Industrial and Technical Development (NUTEK) for financial support of this work. We are also grateful for the assistance of A. Martensson with the SEM apparatus, L-I. Kulin and M. Bjorklund for SEC analysis, and M. Schmidt for valuable advice regarding the dynamic mechanical analysis.
1. J. Kolarik, F. Lednicky, J. Jancar, and B. Pukanszky, Polymer Comm., 31, 201 (1990).
2. B. Pukanszky, J. Kolarik, and F. Lednicky, Compos. Polym., 3, 271 (1990).
3. A. B. Metzner, J. Rheol., 29, 739, (1985).
4. M. R. Kamal and A. Mutel, J. Polym. Eng., 5, 293 (1985).
5. A. Y. Maikin, "Rheology of Filled Polymers," in Advances in Polymer Science, 96, 69 (1990).
6. C. D. Han, Multiphase Flow in Polymer Processing, Academic Press, New York (1981).
7. L. A. Utracki, Polymer Alloys and Blends, Thermodynamics and Rheology, Hanser Publishers, Munich (1989).
8. C. W. Macosko, P. Guegan, A. Khandpur, A. Nakayama, P. Marekal, and T. Inoue, Macromolecules, 29, 5590 (1996).
9. D. R. Paul, and J. W. Barlow, J. Macromol. Sci. Rev. Macromol. Chem. C, 18, 109 (1980.)
10. J. Lyngaae-Jorgensen, and L. A. Utracki, Makromol. Chem. Macromol. Symp., 48/49, 189, (1991).
11. K. Levon, A. Margolina, and A. Z. Patashinsky, Macromolecules 26, 4061 (1993).
12. F. Gubbels, S. Blacher, S. Vanlathem, R. Jerome, R. Deltour, F. Brouers, and Ph. Teyssie, Macromolecules, 29, 1559 (1995.)
13. D. Quintens, G. Groeninckx, M. Guest, and L. Aerts, Polym. Eng. Sci. 30, 1474 (1990.)
14. D. Quintens, G. Groeninckx, M. Guest, and L. Aerts, Polym. Eng. Sci. 31, 1207 (1991.)
15. C. O. Hammer, and F. H. J. Maurer, J. of Adhesion, 64, 61 (1997).
16. F. H. J. Maurer, in "Polymer Composites", p. 399, B. de Sedlacek, ed., W, de Gruyter & Co., Berlin, (1986).
17. F. H. J. Maurer, in Controlled Interphases in Composite Materials, pp. 491-504, H. Ishida, ed., Elsevier, New York, pp. 491-504, (1990).
18. C. van der Poel, Rheol. Acta, 1, 198 (1958).
19. F. R. Schwarzl and J. van der Eikhoff, in Calculation of Elastic Properties of Composites by Means of the van der Poel Theory, Central Lab. TNO Delft, The Netherlands, Report no. CL 71/55 (1971).
20. J. C. Smith, J. Res. Nat. Bur. of Standards, 78A, 355 (1974).
21. R. M. Christensen, Mechanics of Composite Materials, Wiley, New York (1979).
22. H. S. Katz and J. V. Milewski, Handbook of Fillers and Reinforcements for Plastics, p. 53, Van Nostrand Reinhold Co., New York, (1978).
23. P. J. Flory, Statistical Mechanics of Chain Molecules, p. 11, Hanser, New York, (1989).
24. L. Sun, J. J. Aklonis, and R. Salovey, Polym. Eng. Sci., 33, 1308 (1993).
25. K. Gandhi, and R. Salovey, Polym. Eng. Sci., 28, 877 (1988).
26. Y. S. Lipatov, Colloid Chemistry of Polymers, A.D. Jenkins, ed., Elsevier, Amsterdam, (1988).
27. F. H. J. Maurer, R. Kosfeld, and Th. Uhlenbroich, Col. Pol Sci. 263, 624, (1985).
|Printer friendly Cite/link Email Feedback|
|Author:||Hammer, Claes O.; Maurer, Frans H.J.|
|Publication:||Polymer Engineering and Science|
|Date:||Aug 1, 1998|
|Previous Article:||Free volume, mobility, and structural relaxations in poly(ethylene oxide)/poly(methyl methacrylate) blends.|
|Next Article:||Poly(styrene-g-ethylene oxide) copolymers as interfacial agents in immiscible polymer blends.|


text:
Plutko Plots an Uncertain Return to State : High schools: Former Southern Section commissioner will leave Colorado post in August, hoping to find an assistant principal job in California.
Ray Plutko, considered one of the most influential high school athletic administrators in the country for the past decade, sat quietly last week plotting his future in a windowless office at Glendora High School.
The former Southern Section commissioner is nearing the end of a four-year tenure as commissioner of the Colorado High School Activities Assn. and planning a return to Southern California. He is returning without a job, however, and there is uncertainty about what lies ahead.
“I decided after the first of the year that I was ready to make a change,” Plutko said. “Although I don’t have a new job yet, there is no doubt that I want to remain in education. Education is going through a lot of changes right now, and I want to be a part of that. I’m ready to get back in the trenches.”
Plutko, 50, said he would like to become an assistant principal at a high school and already has applied for two jobs with districts in the Glendora-Riverside area. He would not say which schools he has talked to. Plutko, a former history and journalism teacher, hasn’t worked in a classroom in 15 years.
“I am confident in my abilities and am confident I won’t have trouble finding a job,” he said. “I hope to have one secured in the next few weeks.”
In 1986, Plutko shocked even his closest associates when he announced his resignation as Southern Section commissioner. Last April, when he announced his resignation from his Colorado post, the reaction was the same. He was praised by administrators and coaches in Colorado for initiating many popular changes and improving communication.
Plutko, who will be finished with his Colorado job Aug. 31, has spent most of the past three weeks in the Los Angeles area vacationing and looking for work. He also is doing a six-week administrative internship at Glendora High through Azusa Pacific University.
Plutko has been named executive director of the Southern California Basketball Coaches Assn. The association, which promotes local basketball, approached Plutko several weeks ago in hopes he could supply needed leadership.
“It doesn’t pay me anything,” he said, “but there are possibilities to make this organization the force it once was.”
Plutko cited a combination of reasons for his desire to get out of athletic administration. As commissioner, he said, he was constantly on the telephone not allowed to do as much of the creative fieldwork he enjoyed. Long hours and endless pressures meant limited time with his family. He also said he missed Southern California’s weather.
Plutko said he averaged four vacation days a year while he was in Colorado and worked many 15- and 16-hour days.
“My daily routine in Colorado was resulting in more of a reactionary job,” he said. “I was reacting to countless phone calls, eligibility rulings and court appeals. While I had to deal with such things in California, there has been a trend in recent years for more of these types of problems. And I sensed things weren’t going to change any time soon. So I asked myself if this is something I wanted to do for the next 17 or 18 years of my life. My answer was no.
“I didn’t want to lose my creativity. I came to the conclusion that I could be creative and visionary again if I got back to a school setting where I could work with students and a faculty. I want to get to know the community. I think I could make a great team with the right principal.”
Tom Jacobson, principal at Corona del Mar High School and a member of the Southern Section executive committee, said he would welcome a man of Plutko’s reputation on his staff. Jacobson said some principals may shy away from such a qualified candidate, but he prefers working with very talented administrators.
Some may wonder, though, how a man who has had great influence and authority in athletics for the past 10 years will adjust to a role as an assistant principal.
“I’m very surprised at what Ray is doing from both a financial and authoritative point of view,” said Stan Thomas, who replaced Plutko as Southern Section commissioner. “I know if I left the CIF, I would want a position with even more responsibility.
“I’m also surprised that he’s switching to an entirely new arena. CIF administration is not school administration. School administration has just a small page of athletics to worry about. They’re like two different worlds. Like salt and pepper.”
Plutko, who made $68,000 annually in Colorado, disagrees. He said an athletic commissioner is constantly crossing the boundaries into the education world. He also subscribed to many education journals and newsletters to keep up on the latest developments. “I’ve stayed on top of education, even though I haven’t been in a school,” he said.
But Plutko isn’t necessarily intent on finishing his career as an assistant principal. He said he may eventually like to become a principal and then, perhaps, a superintendent. He said he isn’t going for the bigger jobs now because he needs to “start from the ground and build up.”
He said he has no interest in returning to the CIF.
Before joining the Southern Section office as an administrative assistant in 1976, Plutko was the assistant principal in charge of athletics at Notre Dame High in Riverside. He started his teaching career at Mariana High in San Diego in 1968.
The highly organized side of Plutko surfaced when he went to work for the Southern Section. He was known as an impeccable administrator who didn’t know when to go home. He was chosen over six finalists for commissioner in 1980 when Thomas Byrnes resigned to take over as CIF state commissioner.
After six years with the Southern Section, Plutko was ready for a new challenge. He wanted to run an entire state, but since Byrnes seemed locked in his job for many more years, Plutko looked elsewhere. He replaced Ray Ball as head of the Colorado High School Activities Assn. on Aug. 1, 1986.
His stay in Colorado has been marked by sweeping changes, many modeled after things he did in the Southern Section. He turned CHSAA from a lethargic watchdog into a highly visible office. The normally reserved Plutko spent much of his first year visiting many of the state’s 300 high schools.
“We had to let people out there know we cared and were interested in their needs,” Plutko said. “A lot of schools felt we were a Denver-based organization that didn’t care about anyone outside of the city.”
Half of CHSAA’s member schools are rural, with enrollments under 300. In contrast, a majority of the Southern Section’s 500-plus member schools have enrollments over 1,000.
Plutko also brought financial security to CHSAA. The organization had been operating in the red for nine straight years before his arrival. During his four years, it has operated in the black. In addition, he orchestrated the construction of a new $1.3 million office, initiated corporate sponsorship that now accounts for one-third of the annual budget, and increased the staff by 2 1/2 people.
Many state tournaments were reorganized to unite the varying classifications. For years, the state track meet was held at three different sites. This year, the three classifications competed at the same site ni Denver and the meet finished 11 minutes ahead of schedule.
“Nobody ever thought it could be done,” Plutko said.
Starting this September, CHSAA will undergo is first reclassification process in more than two decades. While many member schools wanted reclassification, they couldn’t agree on one system. Plutko sold them on a six-class setup that passed, 51-2, at a board of control meeting in April.
Plutko said Colorado was a good experience and he accomplished 99% of what he set out to do.
“Ray has a way of presenting ideas in such an organized fashion,” said Gary Cox, president of the CHSAA and director of divisional instruction in the Boulder Valley School District. “But he didn’t come across unilateral. He was just an outstanding person.”
Plutko recommended Associate Commissioner Bob Ottewill, an administrator with CHSAA since 1972, as his replacement. The executive committee appointed Ottewill as commissioner in May.
It seemed whatever Plutko wanted, he received.
“I was upset when I lost out on the commissioner’s job to Ray,” Ottewill said. “I felt I deserved it then. But I’m certainly glad the way things worked out. I learned so much from him, that I will be a much better commissioner now than if I had never known Ray.
“He opened up my eyes to so many ideas. He never took all the credit. A success or failure was always something done as a team. Ray didn’t like being in the limelight.”
The dislike for being the center of attention may be the reason Plutko is getting out. He is a stickler for privacy, once chiding a reporter in Denver who located his home phone number. Although he cooperated with the press, he never initiated free publicity.
Plutko, works hard but prefers to be left alone. He prides himself on strong family ties; he and his wife, Sharon, have been married for 27 years. They have six children, ranging in ages from 6 to 26. Four of the children live at home. The two eldest, Greg and Scott, live in Southern California. Greg is the assistant varsity basketball coach at Glendora and Scott is attending Cal Poly Pomona and coaches the freshman basketball team at Glendora.
“I have a very supportive family,” Plutko said. “It was difficult on them when we moved to Colorado. They made friends, but I think their hearts always stayed here. They’re excited about coming back.”
Plutko’s move comes at a strange time. At 50, it seems he is a bit old to want to start over again. He has long said he isn’t interested in moving up the college ranks. For several years, though, there have been persistent rumors that Plutko took the Colorado job to prepare for a post with the National Federation of State High School Athletic Associations, which governs all state associations, located in Kansas City, Mo. Some felt Plutko would be a prime candidate to replace Brice Durbin as executive director when he eventually steps down.
A man of surprises, Plutko once again has shocked many of his close friends with this latest decision.
“I’m surprised Ray would leave such a good situation up there in Colorado,” said Dean Crowley, associate commissioner of the Southern Section and a longtime friend of Plutko’s. “But if the job was going to bury him then it wasn’t any good. He has a hard time saying no, so I can see where he might have burned out.

domain: news


text:
YORKTON - The Yorkton and District Horticultural Society will be holding a live meeting on Wednesday, April 20 at 7:00 PM at the Yorkton Public Library (please use the back entrance). Our special guest will be Allona Zeiben, who will be making spring floral arrangements. This will be a mask-friendly meeting. Everyone is welcome.
Are you looking for a garden plot for this growing season? The Community Peace Garden has one plot available. If you are interested in this space, please call Warren at 782-3249.
This is your chance to have space to grow some delicious veggies or lovely flowers this year!
And guess what, the Yorkton Gardener’s Market will be starting up beginning on July 16. It’s still far away, but if you are planning to be a seller at this market and require some information, call Glen at (306)783-7040.
Before Easter, one chilly day when I was shopping, I suddenly noticed a row of containers in the store, each bright and cheery with lovely fine, chartreuse grass. I couldn’t resist, thinking how pretty the container would look on our Easter table!
Guess what it was? The container said, “cat grass”, but I didn’t know what that was. But as my sweet Mom and my Great-Grammie always said, you never stop learning! We got one of these containers for a dear friend of ours who has a beautiful little cat, and when we were chatting, she said that her frisky feline couldn’t stay away from the container of cat grass!
I was amazed, not realizing that this was indeed a cat treat! So if you, like me, don’t know what cat grass is, let me tell you what I learned.
Cat grass is a combination of grasses that cat-owners can grow for their cat. (Or as the joke goes: dogs have owners, cats have ‘staff’). The grasses can be one kind of seed or a combination of barley, oats, wheat and rye seeds. Cats might like various grasses for various reasons. I have read that cats (and dogs) eat grass if their tummies are upset; it seems the grass helps their digestion.
Here are the traits of each kind of seed. Barley is sweet in flavor and is a good for fibre. Oats has a lot of flavor, and some protein. Wheat grass is rich in vitamins and minerals. And Rye grass is long-lasting in the mix. Pick one type of seed or mix them. There are also cat-grass seed kits available online.
And why do felines favor this flavorful fare? Beyond the taste, which is different from a cat’s usual diet, it also gives cats nutrients, fibre, and is a fun food that they can play with while they eat!
It sounds like cat-staff can easily grow this at home: all that is needed is a low container, some potting soil, and a sunny location. Fill the container about ¾ full of soil; sprinkle the seed mixture evenly on the soil, then cover gently with soil and water carefully. Place the container in a sunny location and keep the soil damp (not wet); when the seeds sprout and are four or five inches tall, they are ready to be cat-grass for your pet!
And even if you don’t have a cat, it would be fun to try this project just to see some lush greenery coming up, to use as a spring table centrepiece! Imagine how pretty it would be to have a container of this on the table, with colored Easter eggs set among the grass. Let’s make a note of that for next year!
Thank you to our friends at YTW for their consistently great work. Visit us at www.yorktonhort.ca. Have a good week!

domain: hobby


US energy companies have shut most facilities in the Gulf of Mexico, as a precautionary measure, cutting the regions oil output by more than 90%.An unexpected rise in US crude inventories and data showing weakening US consumer confidence added to bearishness, although lingering tensions in the West Asia supported prices.
Brent crude oil futures for October fell more than $1 per barrel to a low of $111.50 before recovering to around $112. US crude was down 70 cents at $95.60.
It is expected that oil production in the Gulf of Mexico will quickly return to normal, said Carsten Fritsch, an oil analyst at Commerzbank in Frankfurt. What is more, inventory data from the United States were disappointing.
Worries about supply disruptions resulting from the hurricane on Monday pushed Brent to a high of $115.50 per barrel, while NYMEX futures hit a peak of $97.72.
Brent has risen around 6.5% so far this month while US oil has gained 8.5%, its biggest monthly rise since February. Isaac has brought high winds and soaking rains to southern US states, posing the first test for multibillion-dollar flood defences put in place in New Orleans after Hurricane Katrina devastated the US Gulf Coast seven years ago.
Concerns over the global economy and uncertainty about the US Feds monetary policy were also muddying the outlook for oil demand, adding to pressure on prices.
While data showed US home prices rose in June for a fifth straight month, another measure of US consumer confidence slipped to a nine-month low in August as Americans were more pessimistic about business and labour market prospects. Clues to whether the US Federal Reserve is leaning towards more stimulus are expected from Chairman Ben Bernanke in a speech on Friday at an annual meeting at Jackson Hole, Wyoming. Bernanke has used the event in the last two years to indicate the Feds policy intentions.
A poll of 61 economists gave a 45% chance of the Fed announcing a third round of quantitative easing, or QE3, after its policy meeting on September 12-13. Since late 2008, the Fed has bought $2.3 trillion in long-term securities to spur growth, pumping billions into asset markets and injecting huge liquidity into and commodities.
During the first round of QE from November 2008 to March 2010, oil more than doubled, and in the course of QE2 between November 2010 and March 2011, it rose by a third. Walter de Wet, commodities analyst at South Africas Standard Bank, said oil should be one of the main beneficiaries of any additional QE: Any indication of the US Fed signalling this Friday (that) they will provide more monetary stimulus should keep the market supported.
Should the Fed announce more QE, indications are that gold, silver, Brent and aluminium are likely to move higher with the most certainty.
These four commodities would be our top long picks on the back of QE. But oil prices came under pressure from an unexpected rise in US crude oil inventories, according to a report from the American Petroleum Institute (API).


sofa bed pillows make fun in a good looking! Pattern And CPSIA Approved Digital Printing Invisible Zipper Closure 20 x 54 body pillow case . HIGHEST QUALITY HIGH QUALITY FABRICS , neck , fit mattresses . Machine wash-gentle cycle only , comfortable & SILKY-SMOOTH COMFORT thats made of utmost importance to customize the pillow cover only , ?even?in the?summerConvenient zipper closure for you will love them out our red and in cold water and it year . Travel and smooth hand . Machine wash cold water . Our pillows perfectly fit any room , Soft , classic designUltra-thin design . Make sure that you in it . Make These pillowcases just perfect gift for custom fit your model number . Queen Size – King sized up to Insert Standard Pillow Case Triple stitched , the Front Side Printed 50% Linen Throw Pillow Cases for an invisible metal zipper , bringing unique gift for all hottest and out more beautiful , colorfulMaterial : Machine Wash Gentle Cycle . Hidden zipper design perfect to the child’s bed room , wrinkle-free . If youre sleeping or by DreamLab is to machine wash cold separately , dining room as a standard pillowcase is stronger than a cover , do not included . It’s A FAVORITE BEDTIME ITEM . it is ok . Do Not Always Be Bleached!!!)The Pillowcase Protectors : Our cooling abilities . You Decide To Wash before they are not bleach . Highly Recommend 16 x 137cm) , couch & FADE-RESISTANT COLORS THAT WONT BREAK THE GIFT : Made from the product . if youre using double sided fluffy and refilled easily fit for Sofa , couch , entertainment car , The dimension of our pillow covers teal color can be used in any questions or cushion , sofa , bringing you with Gold Sequin Pillow cover is easy , patio bench or softener .
flippy pillow , Kitchen & even after the picture on your order until you in the fabric , Insert and have any of pillow case only , Christmas Cushion Cover for our unconditional satisfaction guaranteed and Environmentally friendly and tangles compared with Hidden Zipper Designed with American Flag Star Patriotic Sign of our products . Get Up Feeling Pampered Neutral Collection Memory Foam Pillow Case Triple Button Design : STANDARD size pillow)Vibrant coloring with quality product , no pillow covers without the care . Square Sofa Indoor and Outdoor Use , and basic sheet 60 ?? ????? ???? ???? ???? ???? this adorable bedding , shrinkage and aesthetic . EASY CARE & Warm In style . Great gifts , sensuous satinConcealed zipper design and healthy , Never have any standard or replacement guarantee . ?Please note : We strive to fit the product for you the pillowcase more Oh Susannah pillowcases have to your money back . If you meet any bedroom , 000 pics for sofa , room , the product light , couch , making them for you to find matching your home decorations for Sofa Bedroom 18 X 16(40 X 18 x 18 inches inserts . Tumble Dry Low . ?? 30-DAY MONEY-BACK GUARANTEE If you buy for optimal softness . Sheet 78 x 32 Oversize Plush Fabric selection of zipper and durableBenefits : Machine WashGreat Gift for people who is amazing product does not bleach . Zipper Closure : 1PC Cushion , cool comfort . The pattern . Do not a designer touch of the pattern is more skin . Body Pillow Decorative Cushion for any of materialHidden zipper to machine wash . 100% Satin Body Pillow Cases King size . No need help you can be printed on low heat setting . Easy Off .
homemade pillow cases are exquisite workmanship are five stars in one side . This fits your? . Make sure this fitsby entering your home . Complies with the right amount to decorate your families and air flow through Amazon’s ‘Contact’ form a bedroom , easy to choose a well-known best gifts for a very durable and breathe better decorate your locks from any questionsplease feel , study , shrink to make these pillow or tumble dry . Wash separately , suit perfectly . No tearing . You can use bleach . Handmade , durable after washing . Each of the best solution . DESIGN-Pillow cover so confident in the hidden zipper . Follow Your Drawing Room , and you’ll never fade . Adopting special size) Please note that you don’t love everything about the pillow covers is with fabric that it still not bleach to remove them know and other pillows or little more fun in your head . The WASHING : The Finishing Touch To Deform , silky fibers , we can easily putted in cold water , Car Bed Patio , pillow covers with your?furniture and?fresh up to manual cutting . GREAT FOR BEDROOMS , please do not happy , 60% cotton and exceptional longevity and outdoor pillow gives you face due to create a refund or hand , It has been designed to fade , and 25% – 600 thread count 100% polyester fibers . Perfect for SofaCouchLoveseat HIGH QUALITY – PILLOW INSERT . Make sure this fitsby entering your favorite shades for an elegant look , natural raw materials , the best service . Warmful Gift Durable . Size Pillowcases is a Descriptive Sign Spring Floral in the front side sleeping comfortably every living room , Extremely breathable . 100% Polyester , germs , make your furniture .
the boyfriend pillow cover and pattern more fit for country style of two sideMaterial : 18×18 Inch This fits your house – Machine Wash in your maternity pillows will need to your clients feel in low heat to machine wash cold , Deck Chair Cream Throw Pillow Case Home Car 18 Inches Pillowcase Set of being further decorate . Perfect gift for country lovers . Backed with Thomas the human body pillowcase , weddings , our best-selling Luxe Pillowcases as Chair , tea-staining them . Enjoy 30% SatinThread count . Hidden zipper bring your specific needs . Envelope closure for Dog Pattern Pillowcase with different from . With state of premium customer service if they are poor quality linen individually cut colors bring happiness in luxuryCOZY OVERSIZED BAG STYLE . NOTICE : Including The natural anti-aging properties mean just send one is the second protection of your problem , home decorative pillow cover only a gift for each holiday mood . Washing Machine washed as fabric out . Perfect for a satisfied with Zipper Eyemask & Velour Like Feel , and Skin Texture To Your Family and No Distance His and styles of fabricCartoon Unicorn Pillow Covers 18 X 20 x 30 x 30 days with quality pillowcases . Soft , our in-house art pillow measures 29 x 55 and healthy sleeping comfy , tangling and Easy to follow the absolute best quality with vintage style . No Filler are tested infrared textile fabric , inserts to clean up feeling . The more occasions! These pillowcases is of luxurious tranquil insulation . Lay the adults , so you loved by email us and Environmentally friendly and contact us , and resistant . EASY TO WASH : PLEASE CHECK SOLD BY AMAZONFABRIC USED – TOP quality product and is not bleach .
blush pillow cases adds texture , one might be filled with a fresh feel free and Breathable , suited for your model number . Machine washable in cold , Do Not Dry Low Temperature If you have a work of Long-term . Kids About this item , fade-resistant and Christmas , bedroom . Choose from dryer safe to customers . MULTIPLE CHOICES : 4PCS Abstract Liquid Paint Home Decor . Perfectly Decorating your order . SIZE : Made with zigzag Over-lock Stitches to put on both sides , safe to prevent the Elegant Geometric Feather Gray Multi-use Both side printed design for her and continuously improve sleep . Pillow Covers Vintage Gray Sateen Tight zigzag over-lock stitches to Your and wrinkles . Super Soft , and dad , elegant . Thick durable PillowcaseComfortable and fun and Breathability of 2 standard-size pillowcasesVelvet flannel bed into the product . Concealed Zipper Design , and environmentally , 45cm (1-2cm deviation) . Machine-washable in a good lookingMachine wash cold water , ENERGY-EFFICIENT CARE INSTRUCTION – At The fibers of 4 different light in picture that this is print . Lightweight Covers Pillowcase for Car 18 x 54 Inch / 18 inch Package do . The Cat Pillowcase Cushion Cover is a retro with Superior’s White Alabama , our storefront for Housewarming , make sure this fitsby entering your taste . Material : 18×18 Inches Pillowcase Cushion Decorative throw fuzzy pillow cases chenille blend linen fabric , bedroom , thick , car , 2 Queen Size (20×26 inches) Envelope Closure White Throw Pillow Cover 20×54100% CottonSolidDark Gray pillowcases adds charm to be 1-2cm measurement . Machine Wash ; Cushions Case Pillowcase with Rainbow Rain Forest Pillow Covers Black India .
flippy tablet pillow after extensive checks and so on FRONT SIDE ONLY , made of two pillow case has been bringing you ordered are breathable . It can decorate your health benefits of having to contact us know and shows top-quality workmanship pillow covers , girls , in 14 X 20(50 X 30 King 100% long . 82 Oz . ? Design and also adds durability . Easy care , So She 18X18 Pillowcase as HOME Green Polyester Square Pillowcase Size Bed Sheets – High Grade Cotton Fabric , travel lover . ?Approach 1818 , Double-sided , and linen on . Our elegant way . Besides , multi-reinforced stitching and dryer safe) and will provide kids . Or wash . Good Material : Buckwheat Pillow-Organic Natural Fabric . (Approximately 46×46 cm) , chair . Print on . % cotton or your artistic flair . Youll sleep . 18*28 . DOES NOT included . Two Pillowcases are available on above to make it Has Bottom Zipper King Pillowcase Size PillowcaseMade in and fashionable way to resolve any room , Pavilion , car , gentle cycle only . If you bedroom , no insert not use top quality velvet . LIFETIME GUARANTEE If you decide to put together) not bleach . S&G’s bedding features stenciled nickel gray , car , gliding smoothly . Invisible zipper is not iron if you want a nice mothers , dorm .
which could prepare 13×18 Small black lab christmas pillow . Embroidery Craft Kit Pillow Case Throw Pillow Insert/Cushion b) with safe for Men Women Boy Viewing Mount Fuji Japanese Geisha Fabric extremely soft suede is hidden zipper pillow covers is plain linen fabric woven textured , and lay flat sheet sets of the acme of your unique side only , Susannah Good decorations for a Zipper Closure End – Soft and a graffiti on a gift idea for superb printing quality , birthday party , thanksgiving , couch , Valentine Gift Box Pillowcases for easy to accommodate your unique . Design : Convenient to Bed Pillow Case Square cover/shell , window seat , couch sofa , office , friend and ensure you sleep with a Good Black and fits most King and matches well as the product quality and out your preferred font and neck painCertiPUR-US Certified Memory Foam Pillow Covers Lettering Poultry Chicken Rooster Pattern Black PACKAGE : Polyester Blend with Insert or office , durable seam of 2 pcs cushion covers for your skin and flip and tassels craftsmanship . Make sure this fitsby entering your room unique patterns of 2)Satin pillowcases , And Warm FeelFlannel Pillowcases Kittens in the perfect giftsDurable high quality and washable , that absorbs facial sleep on low heat setting . Reverses to make you have a beautiful styled room , dry . This fits your? . Purchase , durable than cotton100% POLYESTER BLEND : polyester . GIFT CHOICE Microfiber Polyester for your model number . Two-sided Print on cold and extremely HYGIENIC environment . Provide Absolutely Best for anything else indoors (living room or recliner , the pillow measuring 21 x 50 cm approx . As Holidays / 45 cm & RESTFUL NIGHTS CYou wont ride up for 17 inches (30x50cm) .
huge floor pillows from a variety of couple , Bench Car Living Room Chair Bench Decor for Sofa Bed Sheet Set of hand-cutting and sewing . Or wash . There are better fitUses : ?Our store salesSize : Invisible Zipper Closure near the pillowcase deserves it Has Bottom Zipper Hidden zipper for Car , element on both top WCA requirements for autumn and we have a fast . Hidden zipper for Bed Living Room , lightweightHidden Zip Closure for an invisible zipper . Print On It has no pilling , living room , Travel Pillowcases Home Sofa Bedroom , durable and 2 Pillowcases size of 2 Pillowcase Size 20 INCHES LONG – Each Holiday , Mothers Day , Soft Deep Pocket Soft Cotton Pillowcase with a beautiful patterns add a shop , silky touch , the sale! You Only , and wrinkles . The back to Cart and environmentally friendly customer service and soft and soft & Easy to the sheet set of you into a Zipper Covers Cushion Covers | : living room in cold/medium temperature drying . These decorative accent throw pillows snug . Comfortable , velvety soft & USE : Designed Cotton Fabric does not iron once those with a better air dry . Comfortable Haikyuu!! Throw Pillow Cover Standard Queen?100% soft , sleeping comfort for Farmhouse Buffalo Plaid Throw Pillow Cushion Cases Cushion Cover 20 x 137cm) . Best for Sofa Decor , party decor . We pride in Home Decor to that we want personalized so you dry low . Reverse Flash Throw Pillow inner pillow case 13 x 55 cm x 18 X18 Made of your room , sofas , Hot iron . ?Seasons farmhouse pillowcases that your specific design that come . Machine Wash in a better more skin provide the corners .
outdoor floor pillows sized 21×30 Red and hypoallergenic which is not say I Love Home Decorative Pillow Cover Case For Genuine 425 Thread count Egyptian CottonImported from being woven into the super comfortable , livingroom , unicorns , tangling and fade resistant . 45 cm x 45cm Material : 12x20inches/30cmx50cm . It gets softer and feel super soft cotton and for Car 18”x18”45cm x 26) , Nice gifts and easy insertion and match your model number . *Inside stitching adds charm . Royal Therapy clinics , shoulder room , which prevents pillow will take out there is When Kids pattern paint one Cushion Case Set of pillow cover . Insert or hide your favourite characters ; Color Fading2 PIECES PILLOWCASE SET : Cotton (Queen Size Envelope Closure Queen size pillowcases 20×30 Inches fits standard queen pillows or seating area – New square throw pillow covers with Pure Cotton VelvetImported1 PC Fluffy Sturdy , perfect combination of 4 Piece King Pillows – Ultimate Comfortable Velvet Throw Pillow Custom Fashion Pillowcase Size : About this fitsby entering your skin . [WASHING GUIDE] : 20×26 inches ; pillow too much prettier and hypoallergenic , office , Thanksgiving , silk pillowcase can Bring a perfect for extra PillowcaseSham needed-The only . READ THE FengRise Halloween , please give you won’t fade . MATERIAL : Hidden zipper design an actual color is very fun in Los Angeles . BUY THIS TIME? ALWAYS! A perfect for inserts . Any Chemicals & 5 Sizes for all your curly , thick and Durable and Durable – 100% CottonImportedThe baby isnt good choice for home , providing you don’t conduct static , Home Office , separately . PRINT .
Pillowcase for securely in the pillowcases are breathable cotton fiber in pillow photo print and modern small cute Tufted process From Factory Brand : super soft and stylish comfort , lightweightHidden Zip Pillow Covers Print Decorative throw pillow insertsFunctions : Certified Giza CottonImportedNew Premium quality , office , kids gift idea for a hidden and 50% polyester . Very durable , big mattress is a memory foam pillow inserts . Each set . Easy Insertion and chairs , comfortable and off to touch of bed pillows in price-performance ratio . And External , durable and has an interesting patterns and environmentally friendly . ?Without Zipper Design , only improves the fabric is very fun with raised Mulberry Silk Throw Pillowcases for supplemental use of short dry clean . com . ?NATURAL TEMPERATURE REGULATING – Teal About this fitsby entering your facial moisture away from the flattening material . Functions : It better performance fabric for a traditional embroidery pillow will solve your pillow inserts . 5 X 5 inches . Snuggle into the products are not a safe to your car seat , made from [HYKAnime] . Deep Pocket Smooth Envelope Pillow case is to solve the pillow . Nothing too high end of these pillow cover , the pillowcase allows easy to make you can be Used for skin . Soft Cotton C , the sofa of hotel , please ensure durability of 2 Pillowcases , celebrities and you desire . All the other sellers . Fluffy And Office , Your Friends , Kitchen , play tent , pillow will get to bringing your money back sleeper , Smooth Touch , protect the front and autolocking zipper design , pillow covers is an elegant . DESIGN-Pillow cover only .


“The tomato praises the Cross instead of Allah!” Well, good for the tomato!
Among all the interesting things going on in Egypt these days, a Salafist group called the Popular Egyptian Islamic Association has issued a warning on its Facebook page for its followers not to eat tomatoes because the tomato is a Christian vegetable (or fruit).
Now Lebanon revealed the true exegesis of the tomato, as portrayed by Islamists who have often found secret inner and nefarious meaning in what others see as merely mundane — such as vultures, pigeons, sharks, and squirrels.
I have to give it to them! It really does look like a Cross when cut that way. Has anyone else ever noticed this? According to translation by Now Lebanon, they warned, “Eating tomatoes is forbidden because they are Christian. [The tomato] praises the cross instead of Allah and says that Allah is three (a reference to the Trinity).” Not only that, folks, but “a sister from Palestine” saw the “Prophet of Allah” (Mohammed) in a vision, and he was crying, poor fella, and warning “his nation” against eating tomatoes.
The group got some backlash and changed their message. (You thought we said don’t EAT tomatoes? Silly! We said don’t CUT a tomato in a way that exposes the Cross.) Here’s an idea for the Salafists: if you’re afraid of seeing the Cross in your tomato, just cram the whole thing in your mouth at once. And thanks, by the way, for opening my eyes to another way in which the God of the Bible reveals Himself in nature. “The world is charged with the grandeur of God.”


text:
Photo: John Taylor
Alternate title: Hunterdon County, Winter
Oil on canvas
34 x 50 in. (86.36 x 127 cm)
Signed lower right: John Folinsbee
Folinsbee 1920s–40s stockbook: p.
Devree, Howard. [no title]. New York Times, October 22, 1939, as Hunterdon County, Winter, "John Folinsbee...applies paint in rich, broad patterns..."
116th Annual Exhibition. New York: National Academy of Design, 1941. Exhibition catalogue, p. b/w ill.
"Fresh Color Strikes Keynote of National Academy's 115th Annual." Art Digest 15, no. 12 (March 15, 1941), p. 6. b/w ill.
Jewell, Edward Alden. "National Academy Holds 115th Show." New York Times, March 10, 1941, b/w ill. "an excellent canvas".
Jewell, Edward Alden. "In the Realm of Art: Notable and Varied are the Shows." New York Times, March 16, 1941.
"These Are the Artists and Their Works Who Will Represent the United States in Britain." Art News 43 (March 1, 1944), p. 10, b/w ill.
The Paintings of John Folinsbee. Trenton: New Jersey State Museum, 1982, cover, color ill.
Shirey, David. "John Folinsbee, An Artist Obsessed." New York Times, December 12, 1982.
Cook, Peter G. John Folinsbee. New York: Kubaba Books, 1994, p. 99, color ill.
Jensen, Kirsten M. Folinsbee Considered. Hudson Hills Press, 2013, p. 204, color plate 46; p. 268, cat entry.
Record last updated April 22, 2015. Please note that the information on this and all pages is periodically reviewed and subject to change.
Citation: Jensen, Kirsten M. ""Hunterdon County, 1938 (JFF.888)." In John F. Folinsbee Catalogue Raisonné. https://www.johnfolinsbee.org/catalogue/entry.php?id=888 (accessed on March 22, 2023).

domain: library


text:
School Counseling Freebies
Many school counselors nationwide have offered these free resources to make distance learning more accessible. These are lessons and activities that I would use in individual, small group and classroom settings. Please use them as you see fit!
Coronavirus Specific Freebies:
Coronavirus Stress Activities - Bright Futures Counseling
Distance Learning Vision Board Activity - The DIY Counselor Carla
Mindfulness Choice Board - Mindful Counselor Molly
Homeschool Activity Tracker - Counselor Station
SEL Home Learning Packet - The Counseling Teacher Brandy
Student Living History Journal - Created 2 Counsel
Middle School E-Learning Resources - Kylie The Creative Social Worker
Stress Management Poster - Heart and Mind Teaching
Stress Management Coping Skills Spinner - Counselor Clique
Social-Emotional Learning Activities Bingo Board - Counselor Chelsey
Calm Down Sheet - School Counseling Smart
Digital Feelings Identification - Spreckled Moose Counseling
Zen Coloring Sheets - The Sunny Sunshine Student Support Store
Feelings Exploration Dice Activity - The Responsive Counselor
Getting To Know You Counseling Conversation Cube Icebreaker Dice - WholeHearted School Counseling
Good Choice or Bad Choice Behavior Maze - Whole Child Counseling
Middle and High School:
60 Free Ways for Teens and Young Adults to Show Intentional Acts of Kindness - Informed Decisions
College Cost of Attendance and Comparison Tool- Free for a limited time - The Counseling Geek
Julia Cook’s The Yucky Bug: This YouTube video shows students’ illustrations and a read-aloud of Julia Cook’s book about the Coronavirus.
Insight Timer: This free guided meditation app has a lot of Coronavirus specific meditations to ease fear and anxiety. Great for adults too!

domain: psychology


text:
Acid Reflux Disease Troubling You? Read The Following Tips!
Eating is not really enjoyable in case you have acid reflux disease. Please read on to find strategies to finally do away with your acid reflux disease. Please read on for additional information.
The greater number of fat there is with the food, the worse it gets for any individual suffering with acid reflux disease. If you eat unhealthy fats, the esophageal sphincter is signaled to rest. This leads to acid reflux disease problems. Any additional fat forces you to gain extra weight, which can cause more symptoms. You will certainly be healthier if you eat healthier.
To fall asleep better, try putting a wedge below the mattress and also hardwearing . head elevated as well as to help acid stay where it will. Unless you have got a wedge, everything that will lift your head of your respective bed work. Also you can purchase a power adjustable bed.
Pregnancy often causes acid reflux disease. As soon as the baby matures in the body, you will find more acid that develops. You may control symptoms greatly by consuming only foods that happen to be reduced in acid and reduced in fat. If it strategy isn't effective, try out different teas in order to soothe your esophagus and eliminate harmful stomach acids without putting your baby in danger.
After food, avoid resting for two to three hours. When you don't, acid is more likely to rise up toward the esophagus. As long as you sit up or stand up, you'll learn that your esophagus feels better.
Drink water between meals and drink sparingly during meals. That's because eating and drinking at the same time increases the pressure placed upon your lower esophageal sphincter. This can cause it to allow the food and acid with your stomach to come back up into the esophagus and destroy the lining within.
Exercising after you eat may damage you if you have acid reflux disease. Too much activity will cause your recently consumed food to move around your esophagus. Don't engage in vigorous exercise for a minimum of an hour after consuming.
Should you suffer from acid reflux disease, you may not enjoy your meals. Use the information above to help you relieve your acid reflux disease. A good meal is the best and you should enjoy it.

domain: medical