Application of Lamellar Clustering Theory to Isotactic Polypropylene and Direct Observation of Lamellar Cluster Morphology by Electron Microscopy

In this work the lamellar cluster model was found to be applicable to the explanation of the mechanical yield behavior in polypropylene materials. According to the lamellar clustering theory, a spherulite is composed of radiating arms, each arm is composed of lamellar clusters, and each lamellar cluster is an aggregate of structural units of the cluster, including several crystalline lamellae and amorphous layers. The intercluster links capable of supporting external force play a role in the destruction of lamellar clusters at the yield point. These morphological features were directly confirmed from TEM observation on two-dimensional polypropylene spherulites that were crystallized from mixtures of isotactic polypropylene and atactic polypropylene, with the latter being removed later by a solvent. In addition, the structural parameters, such as the distance between intercrystalline links and the lamellar cluster thickness, which were determined by applying the mechanical yielding data to the lamellar cluster theory, were confirmed to be in agreement with the quantitative estimations from the TEM images of the polypropylene spherulites.     

Quantitative structural characterization of the deformation and shrinkage of isotactic polypropylene fibers and films

A quantitative determination has been made of the structural elements which control deformation and shrinkage processes in isotactic polypropylene fibers and films. It is found that strain processes such as fabrication draw and shrinkage are controlled by the noncrystalline region of this highly crystalline polymer. Quantitative structure-property correlations are obtained for the polymer, which reveal the interactions between temperature, strain, and orientation. The thermal activation energy of the noncrystalline chains is also determined from these solid-state structure measurements.     

Influence of structure on the dynamic mechanical properties of crystalline polymers

A dynamk mechanical theory is presented whose structural elements correspond to such physically measurable material parameters as the compliance of the phases, the percent crystallinity, and the orientation of the crystalline and noncrystalline regions. The theory is tested by using both structural and dynamk mechanical data from samples of isotactic polyproylene films of varying crystallinity and orientation. For the specific case of isotactic polypropylene the general theory is shown to reduce to a simple two-parameter model. It is further shown that the two-parameter model not only identifies the unique properties of each of the phases separately, but also predicts the dynamic mechanical properties of the polymer over a temperature range of—130°C to 120°C, for samples ranging from unoriented to highly oriented, and varying in crystallinity from 40 to 70%. The model can also predict the dynamic mechanical properties over the same temperature range for strips of these samples cut at varying angles to the machine direction.     

Correlation Between Structural and Dynamic‐Mechanical Transitions of Different Syndiotactic Polypropylene Polymorphs

Abstract

We prepared several well‐characterized syndiotactic polypropylene (sPP) polymorphs so as to correlate their thermal and dynamic‐mechanical behaviors. A sample was crystallized in pure form I at 100°C; a second sample containing only the trans‐planar mesophase was prepared by directly drawing a quenched sample at 0°C; a third sample, drawn at room temperature, contained both the trans‐planar mesophase and a fraction of the helical form II. By annealing this sample at increasing temperatures, we obtained a series of samples containing either trans‐planar mesophase, or form II and form I crystallinities.

In the dynamic‐mechanical analysis, the sample containing form I crystallinity showed only the amorphous glass transition, at 19°C, before melting at a high temperature. The trans‐planar mesophase transformed, at temperatures higher than 50°C, into the helical forms, and this transition was completed at 80°C. The dynamic mechanical curve of the sample containing only the mesophase showed a peak, centered at 50°C, which could be clearly associated to this transition. The sample containing the trans‐planar mesophase and the helical form II, showed in the dynamic‐mechanical curve a third peak that can be associated with the melting recrystallization of form II into the most stable form I. These results are important, because it was possible to directly correlate the structural transitions of the sPP polymorphs to the dynamic‐mechanical behavior. Moreover, a dynamic‐mechanical analysis could help recognize the presence of the trans‐planar mesophase or of the helical form II in more complex structural organizations.     

Structural Interpretation of Eyring Activation Parameters for Tensile Yielding Behavior of Isotactic Polypropylene Solids

The temperature and strain rate dependence of the stress-strain curves of isotactic polypropylene were analyzed on the basis of Eyring kinetic theory. The molecular and structural basis underlying the parameters, such as activation volume and activation energy, used by the Eyring analysis were studied using the lamellar cluster theory, where a stacked lamella acts as a basic structural unit under yielding and necking deformation. It was suggested that, at lower temperatures, the activation volume corresponds to chain slippage within crystalline lamellae in the lamellar clusters whereas at higher temperature the increase in activation volume results in intralamellar slip corresponding to the α₂ relaxation.     

Shape-memorizable styrene-butadiene block copolymer. I. Thermal and mechanical behaviors and structural change with deformation

Thermal properties in the range from room temperature to 150°C, mechanical properties from room temperature to 80°C, and structural changes by drawing and contraction at 80°C followed by crystallization have been studied in a crystalline styrene-butadiene block copolymer, which has the property of shape memory, using differential scanning calorimetry (DSC), mechanical analysis, wide-angle x-ray diffraction (WAXD), and smallangle x-ray scattering (SAXS). This copolymer has the crystal transformation temperature, the melting temperature of the trans- 1,4-polybutadiene domains, and the higher glass transition temperature of the polystyrene domains. When a high strain is adopted for the deformation at 80°C (i.e., between the melting temperature of the polybutadiene [PB] domains and the glass transition temperature of the polystyrene regions) and crystallization conditions with fixed ends are employed, a fibrillar structure with a better regularity of long spacings and a high orientation of crystals forms. When the drawn sample is allowed to contract at 80°C, the high contraction or the shape recovery appears. Nevertheless, crystallization after contraction presents essentially the same supermolecular structure as that before contraction. It is suggested that the molecular chains of polybutadiene were inhibited from flowing freely by the glassy polystyrene molecules and that there must be some structural units separated by amorphous domains that contribute to the elongation and contraction at the high temperature.     

Structure and mechanical properties of nylon 6.12 prepared by temperature slope crystallization. II. Rolling deformation and microhardness of the oriented negative spherulite

Oriented negative spherulites of nylon 6.12 were crystallized by the temperature slope method. Rolling deformation of the negative texture was performed in three directions. The deformation mechanism of the negative spherulites was investigated by x-ray diffraction and microhardness measurements. Slip deformation between crystalline lamellae (interlamellar slip) was observed in the first stage of deformation. The results are compared with the rolling deformation of other polymer textures such as the positive spherulites of nylon 6.12 and β-phase isotactic polypropylene. In the rolling deformation of nylon 6.12, hydrogen-bonded (010) planes play an important role. For large deformations (λ > 1.5), preferential slip between (010) planes appears, resulting in a lamellar inclination of 60° and a decrease of the lamellar thickness. Microhardness measurements after rolling deformation of the oriented negative texture show good agreement with the structural analysis. The rapid decrease in the microhardness with increasing deformation can be explained by the lamellar thickness decrease brought about by the preferential slip between the (010) planes.     

The Preparation and Study on Ultrahigh Molecular Weight Polypropylene Gel‐spun Fibers

A novel polypropylene (PP) fiber was prepared by using gel spinning/crystallization from dilute solutions of ultrahigh molecular weight isotactic polypropylene (i‐UHMWPP), and subsequently drawing at various temperatures. The influence of drawing temperature on the properties of the resulted fibers was investigated. We found that the draw‐ability and mechanical as well as crystallization properties of the fibers obtained were dramatically improved with increasing drawing temperature. When the drawing temperature is below the α‐crystal relaxation temperature of PP, which was measured by wide‐angle X‐ray diffraction (WAXD) analysis as 100–120°C, the fibers are characterized by lower crystallinity and smaller crystals with less perfection, resulting in brittle fracture and subsequently poor mechanical durability. With drawing at temperatures above the α‐crystal relaxation temperature of PP, a novel UHMWPP fiber with Young's modulus of 27 GPa and tensile strength of 1.3 GPa was obtained. Higher crystallinity and larger crystals with better perfection and orientation were observed in this fiber.     

ESSENTIAL WORK OF FRACTURE AND THE PHASE TRANSFORMATION IN β-iPP

The possibility of phase transformation toughening is demonstrated by the example of the β-modification isotactic polypropylene (β-iPP), which undergoes the β–α transformation (i.e., from hexagonal to monoclinic) during mechanical loading. The β–α recrystallization was examined on essential work of fracture (EWF) specimens with two processing conditions. Differential scanning calorimetry and wide-angle x-ray diffraction demonstrate the occurrence of this β–α transformation. Some structural changes can be identified in EWF specimens by using nano-indentation machine. Toughness of the α- and β-iPP is studied and compared with the EWF concept by using static-loaded deeply double-edge-notched tensile specimens. The main effect of the β–α transformation is a large increase in the specific plastic work consumed in the necked zone.     

A microscopic insight into the deformation behavior of semicrystalline polymers: the role of phase transitions

The deformation behavior of semicrystalline polymers associated with polymorphic transformations under tensile deformation is discussed in the case of syndiotactic polypropylene. We report a phase diagram of this polymer where the regions of stability of the different polymorphic forms are defined as a function of the degree of stereoregularity and deformation. The values of critical strain corresponding to the structural transformations depend on the stereoregularity that affects the relative stability of the involved polymorphic forms and the state of the entangled amorphous phase.     

Investigation of Structural Processes During Indentation of Polymers by Synchrotron Radiation Microdiffraction

Abstract

A Vickers microindentation setup has been integrated into the scanning setup used at the European Synchrotron Radiation Facility (ESRF) microfocus beamline (ID 13). Ex situ wide‐angle x‐ray scattering experiments performed on an isotactic polypropylene (iPP) single fiber show changes in chain orientation and breakup of the monoclinic α‐modification into domains due to plastic deformation in the indented zone. The systematic mapping of the perturbed zone allows spatially dependant structural changes to be determined. Similar experiments for a Vectra single fiber show a partial transformation of the pseudohexagonal phase into the orthorhombic phase. In situ experiments allow following structural changes as a function of time and applied force. During indentation of an iPP fiber, domain doubling during indentation and single domain recovery after the tip has been retracted is observed.     

Thermally Induced Structural and Dynamic‐Mechanical Transition of Form II of Syndiotactic Polypropylene

Abstract

The elusive helical form II of syndiotactic polypropylene (sPP), not yet fully clarified, was recognized in a fiber drawn at 90°C and its thermally induced transitions were followed by x‐ray diffraction and dynamic‐mechanical analysis as a function of temperature. It was found that this form is stable up to 100°C; afterwards a melting and recrystallization phenomenon occurs leading to the ordered form I. In correspondence to this structural change, the dynamic‐mechanical analysis shows a strong dissipation peak that can be unambiguously associated to the transition and, therefore, can be considered distinctive evidence of the presence of form II.     

Crystallization and morphology in blends of isotactic polypropylene and linear polyethylene

Thermooptical, wide-angle x-ray diffraction and morphological investigations of blends of isotactic polypropylene with linear polyethylene revealed an increased crystallization rate of the polyethylene blend component, compared to crystallization of polyethylene alone. Crystallization behavior of the polyethylene component was markedly dependent on the blend thermal history and on the circumstances of the polyethylene phase—whether it was disperse or continuous. The higher crystallization rate of the polyethylene component was related to the presence of various types of heterogeneous crystallization nuclei in the blend and to the stabilizing action of the solid polypropylene matrix on minute polyethylene crystallites which survived above melting temperature.     

A framework for statistical modelling of plastic yielding initiated cleavage fracture of structural steels

The well established consensus that cleavage fracture is preceded by plastic deformation in structural steels implies that plastic yielding is the threshold stress state for a volume element to incur cleavage fracture. An accurate compliance with this consensus underlies the normalisation of cumulative cleavage fracture probability and the justification of constraint effect on cleavage fracture. These understandings lead to the proposal of a framework for statistical modelling of cleavage fracture in structural steels. The framework takes the spatial microcrack distribution into account to formulate the cumulative failure probability model that allows for a pertinent physical interpretation of Weibull statistics, and derives the fracture probability of an elemental volume in conformity with the yielding condition from a set of commonly adopted microcrack size or strength distributions. Alternative approaches to calibrating model parameters are suggested based on frequency analysis of brittle particles as cleavage initiators and on statistical analysis of cleavage fracture stress. The strict adherence to plastic yielding as a prerequisite to cleavage fracture also reveals the probabilistic nature of notch brittleness and ductile-to-brittle transition behaviour.     

多孔脆性材料对高能量密度脉冲的吸收和抵抗能力

作用在脆性结构材料表面的高能量密度脉冲会以冲击波的形式传播进入材料内部, 导致压缩破坏和功能失效. 通过设计并引入微孔洞, 显著增强了脆性材料冲击下的塑性变形能力, 从而使脆性结构材料可以有效地吸收耗散冲击波能量, 并抑制冲击诱导裂纹的扩展贯通. 建立格点-弹簧模型并用于模拟研究致密和多孔脆性材料在高能量密度脉冲加载下的冲击塑性机理、能量吸收耗散过程和裂纹扩展过程. 冲击波压缩下孔洞塌缩, 导致体积收缩变形和滑移以及转动变形, 使得多孔脆性材料表现出显著的冲击塑性. 对致密样品、气孔率5%和10%的多孔样品吸能能力的计算表明, 多孔脆性材料吸收耗散高能量密度脉冲的能力远优于致密脆性材料. 在短脉冲加载下, 相较于遭受整体破坏的致密脆性材料, 多孔脆性材料以增加局部区域的损伤程度为代价, 阻止了严重的冲击破坏扩展贯通整个样品, 避免了材料的整体功能失效.     

Statistical Aspects of Tensile Fracture of Isotactic Polypropylene

The fracture behavior of isotactic polypropylene (iPP) specimen with double-notched shape under a fixed elongation speed at room temperature is described. Over 100 tensile tests were performed, and the statistic fracture data were obtained for the tensile condition. The statistical data of fracture were obtained by examining the time to fracture, the ultimate stress, and the tensile toughness (determined from the area under the nominal stress–strain curve from the origin to the fracture point). The probability density distributions for time to fracture, the ultimate stress, and the tensile toughness approximately followed the normal Gaussian statistics. Using a linear relationship between stress and elongation time near the fracture point, we can apply a static Kalman filter system to the present fracture data to determine a conditional probability density function. As a consequence, this application makes it possible to predict the probability of fracture of iPP under any static condition.     

Effect of Stereodefects Distribution on Rheological Behavior of Isotactic Polypropylene

A series of five isotactic polypropylenes (iPP) used commercially for producing biaxial oriented polypropylene film (BOPP), which had similar average degrees of isotacticity but different stereodefects distribution, was studied. Xylene solubles (XS) at different temperatures and high temperature solution ¹³C NMR were used to characterize the stereodefects distribution of the five samples. These samples gradually became more random following the order of sample A to E. The plateau modulus (G ⁰ _N ≈ 0.2 MPa at 190°C) of these samples was lower than those of metallocene-catalyzed polypropylenes with very narrow molecular weight distributions (MWD) (G ⁰ _N ≈ 0.4 MPa at 190°C), indicating that the influence of MWD on G ⁰ _N cannot be neglected. The storage modulus and complex viscosity of the five samples decreased gradually with the widened stereodefects distribution, due to the formation of a less constrained network that finally caused the reduction of G ⁰ _N and the increase of the flow activation energy. The rheological behavior of the BOPP resin samples could be well related to the results of XS and ¹³C NMR, implying that the rheological measurement can be adopted as a simple and efficient method to characterize the stereodefects distribution of isotactic polypropylene.     

BLENDS OF STYRENE-BUTADIENE-STYRENE TRIBLOCK COPOLYMER AND ISOTACTIC POLYPROPYLENE. REINFORCING EFFECT OF POLYPROPYLENE AT HIGH TEMPERATURES

Blends of styrene-butadiene-styrene (SBS) triblock copolymer with isotactic polypropylene (iPP) or maleic anhydride–grafted polypropylene (MAP) were prepared in a twin-screw extruder. Static and dynamic experiments at room temperature in previous works showed that the added homopolymers have a significant influence in the improvement of the general mechanical properties of the SBS when the homopolymer is the dispersed phase. Our aim was to study the reinforcing effect as a function of temperature. When the glass transition of the polystyrene blocks in the SBS is approached (40°C–50°C in static experiments), there is a significant worsening of the failure properties, as well as a profile change in the stress-strain plot. If a reinforcing hard phase is added, these changes can be decreased. The temperature dependence of the reinforcing effect of the added homopolymer was evaluated with the analysis of tensile experiments in terms of various theoretical models. A modified activation energy model with temperature-dependent parameters was used to describe the nonlinear regime and quantitatively compare the properties of the different blends with those of pure SBS.     

Effect of quenching temperature on the structure of isotactic polypropylene films

Films of isotactic polypropylene (iPP) were quenched at different temperatures. Wide-angle x-ray diffractograms for these samples show the presence of the smectic form of iPP at low quenching temperatures and the appearance of mono-clinic form on increasing the thickness of the substrate and the quenching temperature. A quenching temperature higher than 80°C produces only the monoclinic form of iPP, whereas at intermediate temperatures we obtain three-phase amorphous-smectic-crystalline systems. Except for the two-phase amorphous-crystalline system obtained at high temperatures, density values alone do not allow us to obtain the three-phase fractions. We studied the transport properties, sorption, and diffusion of CH₂Cl₂ vapor in these systems to investigate the thermodynamic state of the amorphous component. The behavior of the amorphous component with respect to the diffusion of CH₂Cl₂, which proved identical in all the samples, led us to conclude that at low penetrant activity the smectic phase is not permeable, and therefore we were able to obtain the amorphous fraction in each sample. This value together with density values allowed the determination of the complete composition in terms of three phases for every sample. The crystalline fraction expressed as % mono-clinic form is very well correlated with the reciprocal of the half-height broadening of the (110) diffraction peak at about 2e = 14°.