Annealing of commercial block polypropylene. II. Behavior of poly(ethylene-co-propylene) component

Moldings of ethylene–propylene block copolymer (block PP) are improved by annealing in their tensile impact strength (TIS) and brittle temperature (Tb). To elucidate the mechanism, the role of the poly(ethylene-co-propylene) (PEP) component was studied, and the component extracted with n-heptane from annealed test pieces was subjected to characterization by a fractionation technique. It is found that recrystallization takes place by annealing in the PP matrix and results in segregation of atactic PP and high molecular weight amorphous PEP from the crystal region to the amorphous region. Furthermore, crystalline PEP also undergoes recrystallization by annealing, increasing the miscibility in the interface of PP and PEP. These phenomena in the solid phase are discussed in connection with the annealing effect related to impact strength. © 1992 John Wiley & Sons, Inc.     

Physical aging and thermal aging resistance of polycarbonate/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) blends

The effect of thermal annealing on the mechanical properties of polycarbonate (PC) was investigated by tensile testing, Izod impact testing, and differential scanning calorimetry (DSC). An endothermic peak appeared in the DSC curve by annealing at various temperatures below T_g. The peak area, as a measure of the degree of physical aging, increased with annealing time. The Izod impact strength decreased suddenly just before an endothermic peak became detectable. The results imply that at the very early stage of physical aging, a trigger for the ductile‐to‐brittle transition may be initiated. By blending hydrogenated styrene‐butadiene‐styrene block copolymer (SEBS), the embrittlement by annealing was prevented. That is, in the PC/SEBS blends, the physical aging of PC matrix proceeded in the same way as in neat PC; however, the Izod impact strength did not decrease. This thermal aging resistance seems to originate from the negative pressure effect of SEBS particles that provides dilational stress fields for PC matrix to enhance the local segment motions. POLYM. ENG. SCI., 52:1958–1963, 2012. © 2012 Society of Plastics Engineers     

Annealing of polypropylene–poly(ethylene-co-propylene) blends. I. Thermal and physical properties of blends

Annealing of polypropylene and blends of polypropylene and poly(ethylene-co-propylene) was studied. The structural and physical properties were determined from thermal, mechanical, physicochemical, and spectral investigations. The particular emphasis was on the characteristics of structure and thermal properties of relatively amorphous components segregated from the crystalline region by annealing. Annealing of polypropylene induced an increase in crystallinity resulting in a decrease in impact strength. In contrast, by annealing a blend of polypropylene and poly(ethylene-co-propylene), the impact strength and rigidity were significantly improved with an increase in annealing temperature. The effect of annealing in a binary system was ascribed to the formation of a thicker transitional layer at the interface of the two polymers owing to the increased mobility of amorphous polymer segments. The results of tensile impact strength and brittle temperature were correlated with a deformational mechanism involving the crazing of the matrix.     

Effect of graphite nanoplatelets on fracture behavior of HDPE/PA66 microfibrillar composites

Effect of in situ formation of PA66 fibrils and modification with graphite nanoplatelets (GNP) on fracture behavior of the high‐density polyethylene (HDPE)‐matrix microfibrillar composites (MFC) has been evaluated using tensile impact strength (TIS) and J‐integral methods. According to J‐integral, the main mechanism of failure is unstable crack growth; dissimilar layout of both methods causes different contribution of reinforcement with GNP and PA66 fibrils to fracture process evaluated. More marked orientation and parallel loading lead to increase in impact energy by both GNP and fibrils in TIS; on the other hand, much lower contribution of fibres and even negative effect of GNP pre‐blended in HDPE was found for J‐integral as a consequence of load acting in perpendicular direction. The fact that lower addition of GNP pre‐blended in PA66 does not deteriorate impact behavior indicates that such modification of MFC is an efficient way to get materials with enhanced, well‐balanced parameters. POLYM. ENG. SCI., 59:382–388, 2019. © 2018 Society of Plastics Engineers     

Synergistic Toughening Effect of Nucleating Agent and Annealing Treatment and Morphological Research on Block Copolymerization Polypropylene

The toughening effects of α and β nucleating agents (α-NA and β-NA) and annealing treatment on block copolymerization polypropylene (PPB) were ascertained. The synergistic effect of β-NA and the annealing treatment at 130°C for 3 h impacted the toughness greatly for all test temperatures (?15, 0 and 23°C), specifically, the notched Izod impact strength tested at ?15°C increased from 7.3 kJ/m² to 30.1 kJ/m². Moreover, the addition of α-NA or the annealing treatment also improved the toughness of PPB. The changes of the crystallite morphology and multiphase structure play an important role on the toughening.     

Effect of high‐temperature annealing on the microstructure and mechanical properties of polypropylene with shish kebab or spherulite structure

Various annealing temperatures below, near, or above the melting temperature were used to anneal polypropylene with oriented shish kebab and isolated spherulite structures in this work. The results showed that a high annealing temperature decreases the time needed to achieve the ideal material property. When the annealing temperature is near or above the melting temperature, the impact strength would be 1.6 times improved by partial melting and recrystallization. The crystal structure of the oriented shish kebab or isolated spherulite structures was improved when annealed at 150 °C, whereas annealing at 165 or 170 °C recombined the crystal lamellae of the structure. Moreover, the high crystallinity and thick lamellae improved the impact and yield strength values of the spherulite structure. However, excessively high crystallinity and thick lamellae in the oriented shish kebab structure did not result in good mechanical performance. Therefore, the prediction of mechanical properties for the shish kebab structure based on crystallinity and lamellar thickness is not feasible. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46465.     

Annealing of polypropylene/poly(ethylene-co-propylene) blend. II. Influence of the structure and properties of poly(ethylene-co-propylene) and blended polyethylene on impact strength

The effect of annealing on the impact strength of PP/poly(ethylene-co-propylene) (PEP) and PP/PEP/PE blends was studied with regard to the structure of PEP and the polyethylene crystallinity. The tensile impact strength of annealed blends was remarkably affected by the PEP structure such as molecular weight and comonomer composition and the annealing temperature, while the brittle temperature was scarcely affected. For the PP/PEP/PE blends, annealing at temperatures above the melting point of PE lowers the tensile impact strength in a similar manner as the PP/crystalline PEP blend. These phenomena were explained on the basis of the deformation mechanism presented in the previous article, that is, a thicker interfacial layer of PP and PEP forms by means of annealing to increase the energy needed to deform the interface. By using a scanning electron microscope, the transition layer was observed at the interface between amorphous PEP and PE in the PP/amorphous PEP/PE blend after etching with nitric acid. The formation of a thicker transition layer between amorphous PEP and PE and a sizeable increase in PE particle size by annealing was observed. The phenomena should be correlated with the impact sensitivity, especially tensile impact strength, in the PP/crystalline PEP and PP/amorphous PEP/PE blends. A reasonable explanation of the microstructure in PP/PEP blends has been developed in terms of comonomer composition and melting property of PEP.     

DIELECTRIC BEHAVIOR OF ANNEALED POLY(VINYLIDENE FLUORIDE)

This study deals with the effect of annealing temperature of Polyvinylidene Fluoride quenched from melt into ice-water on the dielectric behavior. Measurements were carried out in the temperature range 25°C to 130°C and in the frequency range 1 kHz to 10 MHz. It was found that the dielectric permittivity and dielectric strength decreases with increasing annealing temperature. This is a result of morphological changes including defects creation, recrystallization and additional crystallization at expense of the amorphous phases.     

Studies on impact modification and fractography of solution cast blends of PVC and NR/PU block copolymers

Segmented polyurethanes based on toluene diisocyanate (TDI) with three different chain extender diols, viz., propylene glycol (PG), 1,4-butanediol (1,4-BDO), and 1,3-butanediol (1,3-BDO) were synthesized by a two-step, solution polymerization method. These different NR-b-PU block copolymers were incorporated into PVC at various compositions by the solution blending method. These blend systems were subjected to FTIR analysis, DSC, tensile testing, tensile impact measurements, and tensile impact fracture studies by SEM. It was observed that systems showed modification in tensile impact properties. Optimum impact properties were shown at concentrations 6–8% of the block copolymer. At higher compositions there is deterioration in impact properties. High impact properties showed by these blends are attributed to the optimum level of compatibility achieved between the blend components. Tensile impact fracture studies revealed that failure pattern for these blend system transitioned from brittle to ductile fracture. Blends up to 10 wt% of block copolymer showed partially compatible heterogeneous nature exhibiting domain morphology. Blends with higher block copolymer content showed deterioration in tensile strength, modulus, yield strength, and tensile impact strength due to higher particle size of the agglomerated rubber soft segments of the block copolymer.     

Morphology and mechanical properties of polypropylene/polystyrene blends compatibilized with styrene–butadiene block copolymers

The effect of molecular structure of styrene–butadiene block (SB) copolymers on the morphology, tensile properties, impact strength, and microhardness of polypropylene/polystyrene (PP/PS) (80/20) blends was studied. The addition of SB copolymers substantially reduces the size of dispersed PS particles formed at mixing. The distribution of SB copolymers between the interface and bulk phases is controlled by the length of styrene blocks in SB, but a decrease in the size of PS particles at mixing correlates with total molecular weight of SB copolymers. For a substantial part of compatibilized blends, PS particles aggregate rapidly during compression molding and form honeycomb‐like particles split by SB partitions, which persist at further annealing. Aggregation of PS particles continues slowly at further annealing. Blends containing PS particles with well‐developed honeycomb structure show lower yield stress, higher plasticity, and lower tensile impact strength than the blends having PS particles with simple or undeveloped honeycomb structure. Microhardness of PP/PS blends is additive and of PP/PS/SB blends is lower than the additive due to the effect of SB copolymers on crystalline structure of PP matrix. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Impact strength of polymers: 1. The effect of thermal treatment and residual stress

The effect of thermal annealing and quenching on the notched Izod impact strength of several polymers has been studied. Primary emphasis was placed on polycarbonate, but ABS, PVC, polysulfone, and polymethylmethacrylate were also studied. It was determined that residual stresses created by thermal quenching from above the glass transition temperature can have a great effect on impact strength for the polycarbonate, PVC, and polysulfone polymers studied. In fact, it is shown that the thickness transition observed in impact strength for polycarbonates is governed by the residual stresses and not by thickness. In polycarbonates, quenched sheets up to 3/8 in. in thickness have shown impact strengths of 18 ft-lb/in. whereas sheets 1/8 in. in thickness can be embrittled by annealing, showing an impact strength of 2 ft-lb/in. However, it has been shown that this embrittlement results from the absence of residual stress. Residual stresses having maximum values up to 3000 psi (in Compression) have been determined at the polycarbonate sheet surface using birefringence measurement techniques. The existence of these compressive stresses is postulated to restrict the extent of craze growth at the notch tip, and the impact specimen can yield rather than fail in a brittle manner if the stress state is sufficient.     

Compatibilizers for recycling of the plastic mixture wastes. II. The effect of a compatibilizer for binary blends on the properties of ternary blends

In this article, we discuss the effect of a compatibilizer for binary blends on the properties of ternary blends composed of high‐density polyethylene (HDPE), polypropylene (PP), or polystyrene (PS) and poly(vinyl chloride) (PVC) virgin polymers with a simulated waste plastics fraction. Chlorinated polyethylene (CPE), ethylene–propylene rubber (EPR), and their 1/1 (w/w) mixture were tested as compatibilizers for the HDPE/PP/PVC ternary blend. CPE, styrene‐ethylene‐propylene block copolymer (SEP), or their 1/1 (w/w) mixture were tested as compatibilizers for the HDPE/PS/PVC ternary blend. The composition of the ternary blends were fixed at 8/1/1 by weight ratio. The amount of the compatibilizer was 3 phr. Rheological, mechanical, and thermal properties were measured. For the 8/1/1 HDPE/PP/PVC ternary blends, the tensile strength was slightly decreased, but the impact strength was significantly increased by adding EPR, CPE, or their mixture. EPR exhibited the most significant impact modification effect for the ternary blends. In a similar way, for 8/1/1 HDPE/PS/PVC ternary blends, on adding SEP, CPE, or their mixture, the tensile strength was slightly decreased, but the impact strength was noticeably increased. It was found that the SEP worked much better as an impact modifier for the ternary blends than CPE or the SEP/CPE mixture did. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1048–1053, 2000     

Effect of annealing on morphologies and performances of hydroxypropyl methylcellulose/hydroxypropyl starch blends

The morphologies and performances of the blends of hydroxypropyl methylcellulose (HPMC), which is a thermal gel, and hydroxypropyl starch (HPS), which is a cooling gel, provides a scientific model to understand the relationship between the microstructure and performance of the unique thermal/cooling gel system. The films based on these blends have been developed for various applications, such as food packaging and medicine capsules, mainly for improving processibility. The morphologies and performance of the blends strongly depend on annealing or storage conditions and time since they are neither miscible nor compatible. This work focuses on the effects of storage conditions and time on the morphologies and performance of the blend films. It was found that the morphologies of the blend system depend on temperature, moisture, and annealing time. Correspondently, the gas permeability and mechanical properties of the film were also environmentally and time dependent. When HPS is continuous phase, the annealing results in starch recrystallization, which increases rigidity. When HPMC is the continuous phase, the materials showed less moisture sensitivity. Starch recrystallization and phase separation, which resulted in microcracks on the surface of the films, are the main reasons for the reduction in gas barrier and elongation. This work will study these issues using scanning electron microscope, X-ray diffraction, mechanical testing and establish their relationship.     

Contour mapping 2D and 3D-photoluminescence of Au-doped one-dimensional Eu(III) and Tb(III) hydroxide and oxide nanostructures

Au nanoparticles were embedded in one-dimensional Eu(III) and Tb(III) hydroxide and oxide nanostructures, and the Au doping effect was understood by contour mapping 2D and 3D-photoluminscecne profiles. Photoluminescence intensity was commonly quenched by dipole–dipole coupling between Au NPs and luminescent centers. The ⁵D₀→⁷F_J emission of Eu(III) was observed by a direct excitation of Eu(III), while the emission was further quenched upon annealing, and only observed by an indirect excitation. The ⁵D₄→⁷F_J emission of Tb(III) was seen before annealing. Upon annealing, the emission was totally quenched, and a broad emission peak was observed at 550 nm.     

Changes in properties of rigid PVC during weathering

Changes in properties of PVC compounds upon weathering are categorized as due to physical aging or due to chemical change. PVC's tensile strength, flexural strength, tensile modulus, and flexural modulus generally rise slightly with weathering. DSC data on weathered samples show an annealing effect identical to physical aging. The impact strength of weathered PVC is substantially lower than expected from physical aging. Molecular weight of PVC on the weathered surface is lowered upon weathering. Thus the loss of impact strength of PVC upon weathering is mainly due to chemical change.     

Effect of calcium carbonate on the mechanical and thermal properties of isotactic polypropylene/ethylene vinyl acetate blends

The effect of calcium carbonate (CaCO₃) on the mechanical properties (with heat treatment) and thermal properties of polypropylene and isotactic polypropylene (i‐PP)/ethylene vinyl acetate (EVA) blends was investigated. CaCO₃, in five different concentrations (3, 6, 9, 12l, and 15 wt %), was added to i‐PP/EVA (88/12) to produce ternary composites. The mechanical properties, including the yield and tensile strengths, elastic modulus, Izod impact strength for notch radii of 0.25 and 1 mm, and hardness with and without an annealing heat treatment, and the thermal properties, such as the melting point and melt‐flow index, of the composites were investigated. The annealing heat treatment was carried out at 100°C for three different holding times: 75, 100, and 150 h. On the basis of the results, attempts were made to establish a relationship between the CaCO₃ content, the annealing holding time, and the mechanical and thermal properties to obtain the best results. The tensile test results showed that the heat treatment was not effective for the ultimate tensile strength, and the yield strength and tensile strength decreased gradually as the CaCO₃ content increased. However, CaCO₃ was effective for higher elastic modulus, impact strength, and hardness values. A considerable increase in the elastic modulus was found with a 3% CaCO₃ concentration for a holding time of 100 h. The maximum impact strength for a notch radius of 1 mm was obtained with 3% CaCO₃ with annealing for a holding time of 100 h, whereas a 9% CaCO₃ concentration produced higher toughness values for a notch radius of 0.25 mm. The fracture surfaces also supported the results from the Izod impact tests. Similarly, hardness values increased with the annealing heat treatment and increasing CaCO₃ content. However, different holding times showed similar effects on the hardness values. The increased CaCO₃ content caused the melting point to increase 5°C, whereas the melt‐flow index showed a sharp decrease as the CaCO₃ content increased to 3%. Taking into consideration the mechanical and thermal properties and the annealing holding time, we recommend a CaCO₃ concentration of 3% with an annealing heat treatment for 100 h for optimum properties of such ternary composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1126–1137, 2005     

Annealing effects of polymers and their underlying molecular mechanisms

This paper indicates that changes in chain mobility, heat capacity, WAXS crystallinity, SAXS long period, SAXS peak intensity, specific volume and morphology as a function of increasing temperature, occur in three fairly distinct annealing ranges (I, II and III) that are more or less the same for all crystallized polymers with a lamellar morphology. It is shown that none of the proposed molecular models to date, including the well-known fold surface premelting model, can satisfactorily account for all the experimental data. However, a new molecular interpretation, based primarily on electron microscopy and SAXS studies of changes such as lateral ‘melting’ from edges of microparacrystallites (mPC) within the lamellae seen at the annealing temperatures can account for the data. With our new molecular interpretation, the effect of temperature increase is established to result in a slight breakup of the laterally aligned mPC within the lamellae at low annealing temperatures in range I, and selective lateral ‘melting’ of the exposed mPC and recrystallization at higher annealing temperatures in ranges II and III, with the recrystallization being very limited in range III. Annealing effects seen in cold- or hot-drawn polymers with a fibrillar morphology can also be readily accounted for by this very general molecular mechanism occurring in the same annealing temperature ranges.     

Effect of a diamine additive on the structure-property relationships of rim polyurethane elastomers

Structural and mechanical data have been compared for reaction injection molding (RIM) polyurethanes prepared from uretonimine-modified diphenylmethane 4,4′-diisocyanate (MDI), ethylene glycol (EG), and a polyol (a polyether; M_n ? 5000), in order to investigate the effect of addition of a small amount of a polyetherdiamine (PEDA; M_n ? 400) to the reaction mixture, A series of specimens containing 18 parts and 30 parts EG, with and without the diamine additive, were examined both as-prepared and after thermal annealing. The specimens were compared in terms of their x-ray crystallinity, elongation, flexural modulus, impact strength, and heat-sag behavior. All of the specimens showed evidence for crystalline hard segments, which are more abundant in the series containing 30 parts EG. The crystallinity is lowest in the as-prepared specimens without the PEDA additive, and is increased by annealing for 1 hour at 120°C. The as-prepared specimen with additive has a hard segment crystallinity similar to that of the annealed specimen without additive. These results correlate with the mechanical property data, which improve as a result of annealing and/or the use of a PEDA additive. It is argued that the use of the polyetherdiamine enhances the phase separation and facilitates hard segment crystallization, leading to better heat-sag behavior. It is significant that the unannealed/with PEDA and annealed/without PEDA specimens have similar properties. Use of PEDA additive improves the green strength and impact strength of molded parts.     

Mechanical properties and morphology of polypropylene composites. Talc-filled,elastomer-modified polypropylene

The balance of impact strength and rigidity of polypropylene can be significantly improved by physical blending of the polypropylene with a talc filler and a variety of elastomer types. Unsaturated elastomers were found to be effective impact strength improvers in 70/15/15 percent PP/elastomer/talc composites, whereas saturated elastomers gave rise to a high stiffness of such compounds. This is attributed primarily to different tendencies of the elastomers to coat the filler surface. Studies on a wider range of compositions, using a butadienestyrene-butadiene (SBS) block copolymer and a ethylene-propylene-diene (EPDM) terpolymer as representatives of the two elastomer classes, indicated that at high stiffness levels (flexural modulus > 1.6 GN/m²), the composites with SBS show the best balance of properties, whereas at higher impact levels EPDM leads to a higher rigidity and impact strength. On the basis of morphological studies such differences can be explained qualitatively, in spite of the complex structure of these composites.     

Studies on mechanical properties of polyethylene–organic fiber composites. I. Nut shell flour

Composites were made from polyethylene and an organic fiber (pecan shell and peanut hull flour) using a compression-molding technique. Studies of variations in molding temperature (145–180°C), fiber concentration (0–40% by weight), and fiber mesh size (100, 200, and 325) were correlated to the mechanical properties of the composites (tensile strength, elongation, fracture energy, modulus, and impact strength). In untreated nut shell composites, tensile strength decreased steadily as the fiber concentration increased. This was due to poor bonding between the untreated fiber and polymer. Polyisocyanate was used as a coupling agent and its effect on mechanical properties of the composites was studied. Significant improvement in tensile strength was achieved with an isocyanate coupling agent, but it had no effect on modulus of the composites. Both untreated and isocyanate-treated composites had lower impact strength values; further composite matrix modifications would be necessary to maintain or improve impact strength.