Halloysite nanotubes as a novel β-nucleating agent for isotactic polypropylene

The nucleating ability of halloysite nanotubes (HNTs) towards isotactic polypropylene (iPP) was investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD), polarized optical microscopy (POM) and scanning electron microscopy (SEM). HNTs are identified to have dual nucleating ability for α-iPP and β-iPP under appropriate kinetics conditions. The formation of β-iPP is dependent on the HNTs loading in the iPP/HNTs composites. The composite with 20 phr of HNTs is found to have the highest content of β-iPP. Under non-isothermal crystallization the content of β-iPP increases with decreasing of the cooling rate. The maximum β-crystal content is obtained at cooling rate of 2.5 °C/min. The supermolecular structure of the β-iPP is identified as β-hedrites with flower-cup-like and axialite-like arrangements of the lamellae. Under isothermal crystallization the β-crystal can be formed in the temperature range of 115-140 °C. Outside the temperature range, no β-iPP can be observed. The content of β-crystal reaches the maximum value at crystallization temperature of 135 °C. The formation of the β-iPP in the composites is correlated to the unique surface characteristics of the HNTs.     

Fabrication and morphology development of isotactic polypropylene nanofibers from isotactic polypropylene/polylactide blends

The excellent characteristics of polymeric nanofibers with diameters less than 1 μm such as the enormous specific surface result in a dramatic increase in a variety of functional applications. In this article, polymer blends of isotactic polypropylene (iPP) and polylactide (PLA) were fabricated through a twin‐screw extruder. The extrudates were prepared at various processing conditions and the iPP nanofibers were obtained by removal of the PLA matrix from the drawn samples. The influences of drawing ratio, the processing temperature, and the blend ratio of iPP/PLA on the morphology development of iPP phase were investigated by scanning electron microscopy. It was found that the uniformed iPP nanofibers with averaged diameters less than 500 nm were fabricated by the suitable processing parameters. Otherwise, the processing immiscibility and rheological behavior of iPP/PLA blends were studied by means of dynamic mechanical analysis and capillary rheometer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Luminescence emission of isotactic polypropylene

In order to elucidate the origin of luminescent species in unstabilized commercial isotactic polypropylene (IPP), effects of hexane extraction and exposure of the extracted IPP film to the atmosphere on both fluorescence and phosphorescence emissions were examined. Fluorescence emission from the unextracted IPP film disappeared by the extraction, and only a very weak phosphorescence emission was found. During the exposure of the extracted IPP film to the atmosphere, both fluorescence and phosphorescence emissions appeared again. The intensity of the spectra increased with the exposure time and finally almost reached that from the unextracted IPP film. The results indicated that main fluorescent species in IPP are foreign impurities originating from an ambient atmosphere, and that contribution of a very minor amount of phosphorescence species such as carbonyl groups incorporated with the polymer was scarce.     

Yttrium fumaropimarat as a novel heat stabilizer for poly(vinyl chloride)

Yttrium fumaropimarat (YFPA) was synthesized with fumaropimaric acid and yttrium acetate as raw materials. The structure of the product was analyzed and characterized by Fourier transform infrared spectrometer, scanning electron microscope, energy dispersive X‐ray microanalysis, and X‐ray diffraction. The results showed that the product was amorphous state, three‐dimensional reticulation compound by the ionic bond of COO^? and Y³⁺. The effect of YFPA on poly(vinyl chloride) (PVC) thermal stability was researched by means of Congo red method and heat oven aging method. The experimental results showed that YFPA was a good long‐term PVC thermal stabilizer and could greatly improve PVC thermal stability and initial stage stainability mixing calcium stearate, zinc stearate, and pentaerythrite. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45015.     

Influence of β nucleation on the mechanical properties of isotactic polypropylene and rubber modified isotactic polypropylene

The tensile and fracture behaviour of neat α and β nucleated isotactic polypropylene and rubber-modified α and β nucleated isotactic polypropylene has been investigated at test speeds of 0.0001-10 ms⁻¹ in the temperature range −30 to +60 °C. The presence of the β phase had little effect at low temperature. However, at +25 and +60 °C, it increased the speeds corresponding to the ductile-brittle transition in the neat polymer by more than three decades. This behaviour has been linked to changes in microdeformation mechanisms observed at the lamellar and spherulitic level, an increase in cavitational deformation in tensile tests and an increase in the strength of the β relaxation in dynamic mechanical spectra. In the blends, the presence of the β phase led to somewhat higher energy dissipation in regimes of ductile fracture. However, the ductile-brittle transitions were not significantly affected. The modifier phase was therefore inferred to control the initiation and propagation of the plastic zone ahead of the crack tip during fracture.     

聚丙烯复合材料的非等温结晶动力学

采用差示扫描量热仪研究了β成核剂和水滑石(LDH)/β成核剂复配的成核剂对聚丙烯(PP)非等温结晶动力学及熔融行为的影响。结果表明:加入成核剂后,PP中晶体分布不均匀且分散度增大。莫志深方法采用F(θ)表征聚合物在单位时间内达到某一结晶度时所需的冷却(或加热)速率,结晶度达到40%时,纯PP的F(θ)为3.82,加入β成核剂的PP的F(θ)为3.30,加入LDH/β成核剂的PP的F(θ)为2.49。与纯β成核剂相比,LDH/β成核剂能更好地提高PP的结晶温度、结晶速率,增强PP的β晶熔融峰,减弱β晶和α晶共存熔融峰和α晶熔融峰。     

固相氯化法氯化等规聚丙烯结构分析

借助ＤＳＣ,ＩＲ,＾１Ｈ－ＮＭＲ方法对搅拌式固相氯化制备的氯化等规聚丙烯的宏观氯原子分布和微观氯原子分布进行了分析。结果表明,搅拌式固相氯化法能够迅速破坏等规聚丙烯的结晶,从而得到宏观氯原子分布均匀的ＣＩＰＰ。此方法制备的ＣＩＰＰ主要为等丙烯分子链上的仲氢原子被取代的产物。     

Deformation behavior of isotactic polypropylene crystallized via a mesophase

The mechanical behavior of semicrystalline isotactic polypropylene (iPP) of different crystallinity, crystal morphology and superstructure was investigated by standard tensile stress–strain analysis, dynamic-mechanical analysis, and in situ observation of the deformation by atomic force microscopy (AFM). Emphasis is put on the comparison of the mechanical characteristics of specimens containing either non-isometric lamellae, being arranged in spherulites, or nodular isometric domains, which are not organized in a superstructure. The formation of lamellae/spherulites and of nodules was controlled by the conditions of crystallization. The replacement of cross-hatched monoclinic lamellae and a spherulitic superstructure by randomly arranged isometric nodules leads to a distinct increase of the ductility and toughness, even if the crystallinity is identical. The modulus of elasticity and the yield stress increase as expected with increasing crystallinity. Slightly lower values of Young’s modulus and yield strength are detected if samples contained non-lamellar crystals in a non-spherulitic superstructure, proving an effect of the crystal shape on the deformation behavior. For the first time, tensile deformation of semicrystalline iPP which contains nodular ordered domains instead of lamellae has been followed by in situ AFM.     

The physical aging of isotactic polypropylene

The microstructural changes in isotactic polypropylene (PP), subsequent to quench from the melt to around T_g were studied using dynamic mechanical loss, volume dilatometry, small and wide angle X-ray scattering, infrared and NMR spectroscopy. The β-transition loss tangent and the specific volume decreased linearly with logarithm of aging time. Dynamic mechanical loss and NMR spectroscopy results established that amorphous chain mobility reduced during aging. X-ray and IR techniques showed that the crystallinity, the crystalline density, and the average chain conformation do not change during aging. Tensile tests indicated that diffusion of air or moisture into the polymer is not a competitive mechanism for the aging phenomenon. A simple free-volume model is quantitatively consistent with these observations. The fraction of the material which cannot age increased as the quench temperature decreased. Further, at lower temperatures a portion of the nonageable fraction is shown to reside in the amorphous fraction.     

Uniaxial roll-drawing of isotactic polypropylene sheet

The process described as “roll-drawing” has been applied to commercial extruded sheets of isotactic polypropylene (M?_n = 70,900). Preheated billets were drawn into thin, clear, transparent sheets in a single pass, producing uniaxial orientation of the polymer molecules in the draw direction. At the maximum draw ratio of 20, the ultimate tensile strength and Young's modulus in the draw direction were 0.5 GPa and 20 GPa respectively. The mechanical properties transverse to the draw direction were virtually unchanged. The theory of fiber reinforcement for unidirectional anisotropic plates was applied to interpret the orientation dependence of the stress-strain behavior of the drawn sheets. From these results, it was estimated that the mechanical properties of biaxially laminated polypropylene sheets equaled the performance of aramid and carbon fiber composites, The roll-drawing process appears to be economically attractive for the production of ultra-high modulus crystalline thermoplastics in sheet form having excellent uniaxial or biaxial properties.     

Radiation-induced oxidative degradation of isotactic polypropylene

Gas evolution, oxygen consumption, and change of mechanical properties were studied for the γ-ray irradiation of isotactic polypropylene from ⁶⁰Co under various conditions, such as vacuum, air, and oxygen at room temperature. For irradiation under vacuum, G(H₂) = 2.9 and G (CH₄) = 0.09; the G values for other gases were very small. In the presence of oxygen, G(H₂) was the same, and the G values for other hydrocarbons were two times those under vacuum. The G values of oxidative products and oxygen consumption were G(CO₂) = 2.5, G(CO) = 1.1, and G(O₂) = 50 at oxygen pressure of 500 torr and were dependent on oxygen pressure. With irradiation under vacuum at 2–3 Mrad, mechanical properties scarcely changes immediately after irradiation but degrade gradually with storage time in air at room temperature.     

AC breakdown of melt-crystallized isotactic polypropylene

The effect of polymer morphology on the dielectric breakdown of isotactic polypropylene was investigated under the influence of a ramped ac voltage. Samples were prepared by melt-pressing polypropylene beads into plaques and subsequently quenching or isothermally cyrstallizing these plaques. Some of the quenched samples were annealed at different temperatures to induce further crystallinity. The plaques were then characterized by wide-angle X-ray diffraction, density measurements, and differential scanning calorimetry. The 60 Hz, ac breakdown voltages of the samples were determined at 7°C, 23°C, and 45°C in a specially designed test cell. There was a lack of any significant effect on the ac breakdown strength of isotactic polypropylene of either the overall crystallinity or the crystallite thickness. This result can be understood in light of previous studies relating the electrical breakdown of polymers to morphology. It is postulated that the degree of crystallinity would influence the breakdown characteristics only when the amorphous regions constitute a small fraction of the total volume, that is, at very high crystallinity values—values beyond the range of the present study.     

Photostabilization of commercial polypropylene by a hindered amine stabilizer

The photostabilization of commercial polypropylene by a hindered amine stabilizer is examined by luminescence and ESR spectroscopy. The presence of the amine stabilizer inhibits the photolysis of the α,β unsaturated carbonyl impurity groups present in the polymer. Examination by ESR, of the stabilized polymer before and after irradiation shows the development of a highly stabilized free radical indicating that the stabilizer can act as an ultraviolet stable antioxidant. Possible mechanisms whereby the hindered amine inhibits the photolysis of the α,β unsaturated carbonyl groups are discussed.     

Thermal stability of additivated isotactic polypropylene

Summary Isotactic polypropylene stabilised with fullerene [C60], its adduct with methyl levopimarate, carbon black, p-t-butylcalix[4]arene, p-t-butylcalix[6]arene, Irganox 1076 or Topanol OC was investigated by means of oxygen uptake method under isothermal (165^°C) and isobaric (normal pressure) conditions. Oxidation investigations were performed in air as degradation environment. Additive concentration was 0.25 % (w/w). Kinetic parameters, oxidation induction and oxidation rate are compared with similar characteristics of additive-free i-PP. Effect of γ-irradiation on thermal oxidation is also presented. Three γ-exposure doses (50, 100 and 150 kGy) were selected. The influence of radiation treatment on the efficiency of studied compounds and some mechanistic aspects are also presented. Received: 5 June 2002/Revised version: 10 August 2002/ Accepted: 12 September 2002 Correspondence to Traian Zaharescu     

The morphology of irradiated isotactic polypropylene

The research in this article explores the response of semicrystalline isotactic polypropylene to gamma radiation in air, and relates the morphological changes of the polymer to corresponding changes in mechanical properties. The effect of the initial morphology of the polymer on its response to irradiation is considered using infrared spectroscopy (FTIR), small‐ and wide‐angle X‐ray scattering, dynamic mechanical thermal analysis (DMTA), and mechanical testing. The extent of chain scission and crosslinking is dependent on the dose but not the initial starting morphology. These chemical changes cause the crystallinity to increase slightly, and the glass transition temperature to rise by a few degrees in all samples, but the overall morphology is only subtly changed. In contrast, a major deterioration in mechanical properties is caused. The effects of the irradiation observed under these conditions are similar in each material and the ultimate properties determined by the properties seen in the original material. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2234–2242, 1999     

Some crystallization kinetics of isotactic polypropylene

Infra-red evidence is presented that the building of helices in the crystallization process from the glassy (or smectic) phase or from the melt are second order or zero-th order respectively. The observation coupled with data from density and X-ray diffraction measurements is interpreted in molecular structural terms.     

Crystallization features of oxidized isotactic polypropylene

The effect of the initial molecular weight parameters of polypropylene on the kinetics of isothermal polymerization is shown. It is found that the feed polymer with a wider molecular weight distribution (P-1) is characterized by lower values of the half-crystallization time as compared to the polymer with a narrower molecular weight distribution (P-2). Comparison between the crystallization parameters and the kinetics of accumulation of oxidation products showed that as the degree of oxidation of the polypropylene increases, the crystallization rate for both samples decreases and the concentration of the oxidation products increases. In this case, the degradation of tie chains accelerates the formation of crystallites. It is shown that P-1 has a higher nucleation energy as compared with P-2 and that this parameter increases during the oxidation of both polymers.