Polypropylene-POSS Nanocomposites: Morphology and Crystallization Behaviour

Nanocomposites of isotactic polypropylene (PP) with polyhedral oligomeric silsesquioxanes (POSS) [RSiO_1,5]₈ having different alkyl substituents (R = methyl, isobutyl, isooctyl) were obtained by melt blending and analysed with electron microscopy, optical microscopy and DSC calorimetry. The influence of POSS structure on the morphological characteristics, the crystallization and melting behaviour of PP/POSS composites was investigated with varying the filler amount. The crystallization kinetics of the composites from the melt, examined both in isothermal and non-isothermal conditions, demonstrated that the nucleation activity of the examined POSS can be related to the length of alkyl substituents which, depending on the loading amount, affect the filler dispersion in the PP matrix and the growth of polymer crystals.     

The Crystallization,Melting Behaviors and Thermal Stability of Cross-linked Poly(3-hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-3-hydroxyvalerate) by Octavinyloctasilasesquioxane

A series of cross-linked poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/octavinyloctasilasesquioxane (PHBV/OVS) composites were obtained by a simple melt reactive processing technique. Dicumyl peroxide (DCP) and OVS were employed as a free radical initiator and a cross-linking agent, respectively. The chemical structure of these produced composites were identified by ¹H/¹³C/²⁹Si-nuclear magnetic resonance spectroscopy (¹H/¹³C/²⁹Si-NMR) and Fourier transform infrared spectroscopy (FTIR). The melting behavior, non-isothermal crystallization, spherulite morphology and thermal stability property of PHBV/OVS composites were also investigated. The nucleation behaviors and crystallization rate of PHBV/OVS were significantly enhanced with the formation of cross-linked networks with different side-chains and cross-linking points. The red shift of crystalline peak temperature with addition of a small amount of OVS content evidenced the higher crystalline ability compared with the neat PHBV. However there was a threshold content, beyond which the crystallization rate weakened again. Additionally, the cross-linked structure of PHBV/OVS composites could be adjusted by changing the amount of OVS.     

Crystallization Behaviors and Regime Kinetics Analysis of Poly(<Emphasis Type="Italic">L</Emphasis>-lactide)-poly(butylene adipate)-poly(<Emphasis Type="Italic">L</Emphasis>-lactide) Based Multiblock Thermoplastic Polyurethanes

Poly(L-lactide)-based (PLLA) poly(ester-urethane)s are particularly relevant and gain significant attention due to their environment-friendly degradability and elastomeric shape memory capability. The tensile properties, resilience and degradation are strongly affected by their crystallization. This work was to investigate crystallization behaviors of the poly(L-lactide)-poly(butylene adipate)-poly(L-lactide) (PLLA-PBAPLLA) based thermoplastic polyurethane elastomers (PLAEUs) we synthesized previously. Dynamic scanning calorimetry (DSC) and polarized optical microscopy (POM) in combination with Avrami, Jezioney and Hoffman-Weeks models were used to analyze the impact of the PLLA block length on the crystallization temperature T_c, degree of crystallinity X_c, nucleation and spherulite growth mode and crystallization regime kinetics of the PLAEUs. The results indicate the low melting point poly(butylene adipate) (PBA) block resides in the amorphous domains while the PLLA block resides in both crystalline and amorphous phases. The X_c of the PLAEUs increase with the increased length of the PLLA block (i.e. higher content of PLLA block). The analyses with Avrami and Jezioney models show the PLAEU copolymers follow a disc-like spherulite growth. The covalently bonded PBA block decreases both nucleation velocity and spherulite growth rate in the isothermal crystallization. Such an impact is lessened as PLLA block length increases. The PLLA homopolymers demonstrate crystallization regime transition from II to III at a certain T_c of isothermal crystallization, while the crystallization regime kinetics of PLLA block in the PLAEUs are explained by a single regime III at low molecular weights of PLLA and the transition is restored as the PLLA block length increases (i.e. regime II to III).     

Curing reaction of <Emphasis Type="Italic">o</Emphasis>-cresol-formaldehyde epoxy/LC epoxy(<Emphasis Type="Italic">p</Emphasis>-PEPB)/anhydride(MeTHPA)

The curing kinetics of a bi-component system about o-cresol-formaldehyde epoxy resin (o-CFER) modified by liquid crystalline p-phenylene di[4-(2,3-epoxypropyl) benzoate] (p-PEPB), with 3-methyl-tetrahydrophthalic anhydride (MeTHPA) as a curing agent, were studied by non-isothermal differential scanning calorimetry (DSC) method. The relationship between apparent activation energy E _a and the conversion α was obtained by the isoconversional method of Ozawa. The reaction molecular mechanism was proposed. The results show that the values of E _a in the initial stage are higher than other time, and E _a tend to decrease slightly with the reaction processing. There is a phase separation in the cure process with LC phase formation. These curing reactions can be described by the Šesták–Berggren (S–B) equation, the kinetic equation of cure reaction as follows: \frac\textda\textdt = Aexp( - \fracE_\texta RT )a^m ( 1 - a )ⁿ {\frac{{{\text{d}}\alpha }}{{{\text{d}}t}}} = A\exp \left( { - {\frac{{E_{\text{a}} }}{RT}}} \right)\alpha^{m} \left( {1 - a} \right)^{n} .     

DSC analysis of isothermally melt-crystallized bacterial poly(3-hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-3-hydroxyhexanoate) films

The multiple melting behavior of isothermally melt-crystallized poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) from its melt was investigated using differential scanning calorimetry (DSC). PHBHHx exhibits a fourfold endothermic melting phenomenon, which were expressed as A, I, II, and III from low to high temperature, and attributed to the melting of secondary lamellae formed at room temperature, the melting of secondary lamellae at crystallization temperature, the melting of primary lamellae, and the melting of the recrystallized lamellae of different stabilities, respectively. Secondary crystallization is much slower than the primary crystallization and needs a relatively long period of time to occur. Furthermore, secondary crystallization at room temperature is heterogeneous, which depends on the presence of the primary lamellae and the secondary lamellae formation.     

Isothermal and nonisothermal cold crystallization kinetics of poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide)/functionalized eggshell powder composites

Functionalized eggshell powder (NES) with nucleating surface of calcium phenylphosphonic acid (PPCa) for poly(l-lactide) (PLLA) was compounded with PLLA via melt blending to improve the cold crystallization process of PLLA. The cold crystallization behavior of the PLLA/NES composites was studied by differential scanning calorimetry. The isothermal cold crystallization rates have been enhanced obviously in the PLLA/NES composites than in the neat PLLA, indicative of the excellent nucleating effects of NES on PLLA. For the nonisothermal cold crystallization, the overall crystallization rate of PLLA increased with both increasing NES loadings and heating rate. It was found that the Avrami equation and the combined Ozawa–Avrami model could describe the experiment data successfully.     

Dielectric classification of <Emphasis Type="Italic">D</Emphasis>-and <Emphasis Type="Italic">L</Emphasis>-amino acids by thermal and analytical methods

Dielectric analysis (DEA), supported by thermogravimetric analysis (TG), differential scanning calorimetry (DSC), powder X-ray diffraction analysis (PXRD) and photomicrography, reveal the chiral difference in the amino acids. The acids are classified as dielectric materials based on their structure, relating chirality to the vector sum of the average dipole moment, composed of the constant optical (electronic) and infra-red (atomic) polarizabilities, as well as dipole orientation. This study encompasses 14 L-and D-amino acid isomers. Physical properties recorded include AC electrical conductivity, charge transfer complexes, melting, recrystallization, amorphous and crystalline phases, and relaxation spectra, activation energies and polarization times for the electrical charging process.     

Morphology and thermomechanical properties of well-defined polyethylene-<Emphasis Type="Italic">graft</Emphasis>-poly(<Emphasis Type="Italic">n</Emphasis>-butyl acrylate) prepared by atom transfer radical polymerization

The morphology and thermomechanical properties of well-defined polyethylene-graft-poly(n-butyl acrylate) (PE-g-PBA) copolymers prepared via atom transfer radical polymerization were investigated. Differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS), wide angle X-ray scattering (WAXS), dynamic mechanical measurement and large deformation tensile tests were performed on the graft copolymers and the results were compared with the behavior of the polyethylene macroinitiator. The existence of both crystalline polyethylene segments and amorphous poly(n-butyl acrylate) segments in the copolymers leads to microphase separation and unique thermomechanical behavior. Strong microphase separation was observed by DSC and X-ray diffraction studies. Correlation of morphology and thermomechanical properties was also studied using dynamic mechanical measurement and large deformation tensile tests.Dedicated to Prof. E. W. Fischer on the occasion of his 75th birthday     

Fluorescence study on the domain formation of <Emphasis Type="Italic">N</Emphasis>-dodecanoyl-<Emphasis Type="SmallCaps">l</Emphasis>-tryptophan within a liposome membrane

The aggregation behavior of N-dodecanoyl-l-tryptophan within a liposome membrane was investigated by fluorescence spectroscopy. Liposomes with a mean diameter of 100 nm, formed from either 1-2-dilauroyl-sn-glycero-3-phosphocholine, 1-2-myristoyl-sn-glycero-3-phosphocholine, or 1-2-palmitoyl-sn-glycero-3-phosphocholine, were used. Fluorescence measurements indicate that the sodium salt of N-dodecanoyl-l-tryptophan forms domains with the liposome membranes below the main phase transition temperature, T _m. Above T _m, the molecules are homogeneously dispersed in the liquid crystalline state of the membranes.     

Thermal behavior of partially hydrogenated polydienes by <Emphasis Type="Italic">p</Emphasis>-toluenesulfonylhydrazide

The hydrogenation of natural rubber (NR), polybutadiene (BR), and styrene-butadiene (SBR) rubbers with different microstructures was performed by a diimide hydrogenation agent generated in situ by a non-catalytic method [1–3]. Many properties of the material depend considerably on variables such as degree of hydrogenation and proportions of vinyl or phenyl units. The mobility of the hydrogenated chain was investigated by differential scanning calorimetry (DSC) and the results confirm the relationship between the degree of hydrogenation and chain flexibility. The flexibility of a high cis-1,4 BR hydrogenated sample, was significantly changed and a melting point (T _m) was detected after a certain degree of hydrogenation. Thermal stability was investigated by thermogravimetric analysis (TG) and an increase was found, but, the thermal resistance was influenced by the presence of the byproduct p-toluenesulfinic acid. Oxidation stability was investigated by chemiluminescence analysis and it improved with hydrogenation.     

Thermochemical study on ternary complex of dysprosium <Emphasis Type="Italic">m</Emphasis>-nitrobenzoic acid with <Emphasis Type="Italic">o</Emphasis>-phenanthroline

A ternary binuclear complex of dysprosium chloride hexahydrate with m-nitrobenzoic acid and 1,10-phenanthroline, [Dy(m-NBA)₃phen]₂·4H₂O (m-NBA: m-nitrobenzoate; phen: 1,10-phenanthroline) was synthesized. The dissolution enthalpies of [2phen·H₂O(s)], [6m-HNBA(s)], [2DyCl₃·6H₂O(s)], and [Dy(m-NBA)₃phen]₂·4H₂O(s) in the calorimetric solvent (V_DMSO:V_MeOH = 3:2) were determined by the solution–reaction isoperibol calorimeter at 298.15 K to be \Updelta_\texts H_\textm^q \Updelta_{\text{s}} H_{\text{m}}^{\theta } [2phen·H₂O(s), 298.15 K] = 21.7367 ± 0.3150 kJ·mol⁻¹, \Updelta_\texts H_\textm^q \Updelta_{\text{s}} H_{\text{m}}^{\theta } [6m-HNBA(s), 298.15 K] = 15.3635 ± 0.2235 kJ·mol⁻¹, \Updelta_\texts H_\textm^q \Updelta_{\text{s}} H_{\text{m}}^{\theta } [2DyCl₃·6H₂O(s), 298.15 K] = −203.5331 ± 0.2200 kJ·mol⁻¹, and \Updelta_\texts H_\textm^q \Updelta_{\text{s}} H_{\text{m}}^{\theta } [[Dy(m-NBA)₃phen]₂·4H₂O(s), 298.15 K] = 53.5965 ± 0.2367 kJ·mol⁻¹, respectively. The enthalpy change of the reaction was determined to be \Updelta_\textr H_\textm^q = 3 6 9. 4 9 ±0. 5 6   \textkJ·\textmol ^{- 1} . \Updelta_{\text{r}} H_{\text{m}}^{\theta } = 3 6 9. 4 9 \pm 0. 5 6 \;{\text{kJ}}\cdot {\text{mol}}^{ - 1} . According to the above results and the relevant data in the literature, through Hess’ law, the standard molar enthalpy of formation of [Dy(m-NBA)₃phen]₂·4H₂O(s) was estimated to be \Updelta_\textf H_\textm^q \Updelta_{\text{f}} H_{\text{m}}^{\theta } [[Dy(m-NBA)₃phen]₂·4H₂O(s), 298.15 K] = −5525 ± 6 kJ·mol⁻¹.     

Heat capacities and thermodynamic properties of (<Emphasis Type="Italic">S</Emphasis>)-<Emphasis Type="Italic">tert</Emphasis>-butyl 1-phenylethylcarbamate

An N-tert-butyloxycarbonylated organic synthesis intermediate, (S)-tert-butyl 1-phenylethylcarbamate, was prepared and investigated by means of differential scanning calorimetry (DSC) and thermogravimetry (TG). The molar heat capacities of (S)-tert-butyl 1-phenylethylcarbamate were precisely determined by means of adiabatic calorimetry over the temperature range of 80-380 K. There was a solid–liquid phase transition exhibited during the heating process with the melting point of 359.53 K. The molar enthalpy and entropy of this transition were determined to be 29.73 kJ mol⁻¹ and 82.68 J K⁻¹ mol⁻¹ based on the experimental C _p–T curve, respectively. The thermodynamic functions, [H_T⁰ - H_298.15⁰ H_{T}^{0} - H_{298.15}^{0} ] and [S_T⁰ - S_298.15⁰ S_{T}^{0} - S_{298.15}^{0} ], were calculated from the heat capacity data in the temperature range of 80–380 K with an interval of 5 K. TG experiment showed that the pyrolysis of the compound was started at the temperature of 385 K and terminated at 510 K within one step.     

Preparation of polypropylene/clay nanocomposites by <Emphasis Type="Italic">in situ</Emphasis> polymerization with TiCl<Subscript>4</Subscript>/MgCl<Subscript>2</Subscript>/clay compound catalyst

TiCl₄/MgCl₂/clay compound catalyst was prepared by chemical reaction.Exfoliated polypropylene（PP）/clay nanocomposites were synthesized by in situ polymerization with this compound catalyst.Effects of polymerization temperature,polymerization time,propylene pressure,solvent consumption and pre-treat time of catalyst on catalyst activity and catalytic stereospecificity were studied.Under optimal conditions,activity of the nano-compound catalyst is about 88.3 kg/（mol Ti·h）.Isotacticity of PP obtained in the nanocomposites is in the range of 89%-99%,and its melting temperature is about 159℃.The weight-average molecular weight of PP can reach 6.7×10⁵ - 7.8×10⁵,and the molecular weight distribution is between 7.7 and 7.9.     

Synthesis of PP-<Emphasis Type="Italic">g</Emphasis>-PIP and properties of PP/PP-<Emphasis Type="Italic">g</Emphasis>-PIP binary blends

The polypropylene-graft-polyisoprene (PP-g-PIP) copolymers with different side chain length were synthesized by the combination of solid phase graft and anionic polymerization. The copolymers were characterized by nuclear magnetic resonance spectrum (¹H-NMR), gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). Five PP/PP-g-PIP blends with PP-g-PIP as a flexibilizer to toughen PP were prepared and characterized by scanning electron microscope (SEM), dynamic mechanical analysis (DMA), DSC, wide-angle X-ray diffraction (WAXD). Their morphologies, glass transition temperatures, crystallinity and mechanical properties were investigated. All the results pointed out that the covalent bonding of PP and PIP increased the compatibility and interfacial adhesion, which led to PIP well dispersed in the system and small size PIP particles in the binary blends. In addition, the toughness of PP was improved while its tensile strength slightly decreased.     

Isothermal Crystallization Kinetics and Crystalline Morphologies of Poly(butylene adipate-<Emphasis Type="Italic">co</Emphasis>-butylene 1,4-cyclohexanedicarboxylate) Copolymers

In this study,the isothermal crystallization kinetics and crystalline morphology of poly(butylene adipate-co-butylene 1,4-cyclohexanedicarboxylate) (PBAC),which refers to a copolyester containing a non-planar ring structure,were investigated by differential scanning calorimetry and polarized optical microscopy,and compared with those of neat poly(butylene 1,4-cyclohexanedicarboxylate) (PBC).The results indicate that the introduction ofbutylene adipate (BA) unit into PBAC did not change the intrinsical crystallization mechanism.But,the crystallization rate and ability,and equilibrium melting temperature of PBAC copolymers were reduced.All PBC and PBAC copolymers could only form high density of nucleation from melt at given supercooling,while no Maltese cross or ring-banded spherulites could be observed.PBAC copolymers with a high amount of BA unit became amorphous after quenching with liquid nitrogen from melt,while PBC and PBAC copolymers with a low amount of BA unit could still form a large amount of nuclei under the same treatment.     

表面接枝改性纳米二氧化硅填充聚丙烯的结晶行为

应用差示扫描量热方法研究了纳米二氧化硅 (SiO2 )及其表面接枝改性对聚丙烯 (PP)结晶过程、等温与非等温结晶动力学的影响 ,并研究了上述等温结晶的熔融行为和平衡熔点 .研究发现纳米SiO2 具有明显的异相成核效应 ,能够提高PP的结晶温度、熔融温度、结晶度和结晶速率 ,但降低聚丙烯结晶的完善程度 .粒子的表面接枝处理 ,因改善了粒子与基体的亲和性而有利于粒子成核效应的提高 ,而且此效应尚与粒子的分散相关     

Crystallization and melting of isotactic polypropylene crystallized from quiescent melt and stress‐induced localized melt

Temperature dependency of crystalline lamellar thickness during crystallization and subsequent melting in isotactic polypropylene crystallized from both quiescent molten state and stress‐induced localized melt was investigated using small angle X‐ray scattering technique. Both cases yield well‐defined crystallization lines where inverse lamellar thickness is linearly dependent on crystallization temperature with the stretching‐induced crystallization line shifted slightly to smaller thickness direction than the isothermal crystallization one indicating both crystallization processes being mediated a mesomorphic phase. However, crystallites obtained via different routes (quiescent melt or stress‐induced localized melt) show different melting behaviors. The one from isothermal crystallization melted directly without significant changing in lamellar thickness yielding well‐defined melting line whereas stress‐induced crystallites followed a recrystallization line. Such results can be associated with the different extent of stabilization of crystallites obtained through different crystallization routes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 957–963     

Synthesis of <Emphasis Type="Italic">o</Emphasis>(<Emphasis Type="Italic">m</Emphasis>)-carborane-containing azomethines

A method of preparative synthesis of o(m)-carborane-containing azomethines via the condensation of o(m)-carboranyl-C-methylene-4-formylbenzoates with aliphatic, cycloaliphatic, and aromatic amines was developed.     

PW based phase change nanocomposites containing <Emphasis Type="Italic">γ</Emphasis>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Phase change nanocomposites were prepared by dispersing γ-Al₂O₃ nanoparticles into melting paraffin wax (PW). Intensive sonication was used to make well dispersed and homogeneous composites. Differential scanning calorimetric (DSC) and transient short-hot-wire (SHW) method were employed to measure the thermal properties of the composites. The composites decreased the latent heat thermal energy storage capacity, L _s, and melting point, T _m, compared with those of the PW. Interestingly, the composites with low mass fraction of the nanoparticles, have higher latent heat capacity than the calculated latent heat capacity value. The thermal conductivity of the nanocomposites was enhanced and increased with the mass fraction of Al₂O₃ in both liquid state and solid state.     

Allotropic transformation of Se<Subscript>8</Subscript> to Se<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

Single crystals of cycloocta-Se, unambiguously characterized by XRD were prepared and used in a study of its allotropic transformation to polycatena-Se by DSC supported by Raman spectroscopy and optical microscopy. It was found that the transformation of a Se₈ single crystal to polycrystalline Se _n proceeds progressively within the volume of the monoclinic single crystal without shape change. All the results of DSC, Raman spectroscopy, and optical microscopy indicate that previous proposals on cycloocta-Se melting during transformation are not realistic.