Relationships between impact performance and structures of rotationally molded crosslinked high-density polyethylene

Crosslinked high-density polyethylene (XL-HDPE) is a preferred material for chemical and fuel tanks due to its superior environmental stress crack resistance and impact strength. The impact performance of rotationally molded specimen is important for final products. In the research the drop weight impact strength (defined as ARM impact strength) of rotationally molded XL-HDPE is tested between −40°C and 25°C. The crosslinking content, crystallization characteristics, and dynamic mechanical properties (DMA) of different thickness gradients are examined to illustrate the relationships between the impact strength, brittle-ductile transition (BDT) and microstructures. The innermost surface layer (about 0.3 mm) has lower gel content, higher crystallinity, and average lamellar thickness compared with the body part. The ARM impact strength is about 1 J/mm at −40°C and −30°C, and about 29 J/mm at −20°C ~ 25°C. There is a BDT between −30°C and − 20°C. After removing the innermost surface layer, the sample breaks in ductile manner in the entire tested temperature range, and the ARM impact strength is about 24 ~ 26 J/mm. The DMA results show that the BDT is consistent with the structure transition of the innermost surface layer. The microstructures of rotationally molded XL-HDPE in the innermost surface layer dominate the low temperature impact performance.     

Rapid crack propagation failures in HDPE pipes: Structure–property investigations

The influence of molecular architecture on the rapid crack propagation (RCP) resistance of a wide variety of high‐density polyethylene pipes was investigated. It was concluded that high molecular weight, high crystallinity and a relatively narrow molecular weight distribution are important architectural attributes for RCP resistance. The ductile‐brittle transition temperature, as measured on compression‐molded specimens using the razor‐notched Charpy impact test, appears to be a reasonably good indicator of the RCP resistance of the resultant pipes. POLYM. ENG. SCI., 46:1358–1362, 2006. © 2006 Society of Plastics Engineers     

Effect of compatibilizer in acrylonitrile‐butadiene‐styrene toughened nylon 6 blends: Ductile–brittle transition temperature

The ductile–brittle transition temperatures were determined for compatibilized nylon 6/acrylonitrile‐butadiene‐styrene (PA6/ABS) copolymer blends. The compatibilizers used for those blends were methyl methacrylate‐co‐maleic anhydride (MMA‐MAH) and MMA‐co‐glycidyl methacrylate (MMA‐GMA). The ductile–brittle transition temperatures were found to be lower for blends compatibilized through maleate modified acrylic polymers. At room temperature, the PA6/ABS binary blend was essentially brittle whereas the ternary blends with MMA‐MAH compatibilizer were supertough and showed a ductile–brittle transition temperature at ?10°C. The blends compatibilized with maleated copolymer exhibited impact strengths of up to 800 J/m. However, the blends compatibilized with MMA‐GMA showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2643–2647, 2003     

Effect of processing parameters on the mechanical properties of in situ compatibilized polybutylene terephthalate/acrylonitrile–butadiene–styrene blends

To evaluate mechanical properties of blends prepared by intermeshing corotating twin‐screw extrusion (ICTSE), it is usually necessary to injection mold specimens after the extrusion mixing process. At this study an alternative method is used to obtain testing specimens from ribbons extruded polybutylene terephthalate/acrylonitrile–butadiene–styrene blends, (PBT/ABS), compatibilized with methyl methacrylate–glycidyl methacrylate‐ethyl acrylate (MGE) by ICTSE, and then to correlate their mechanical properties with the processing parameters. Regarding to the extrusion process parameters, it has been noted that higher feed rates, lower screw speeds and narrower kneading blocks have reduced the ductile‐brittle transition temperature (DBTT) of the compatibilized PBT/ABS blends, thereby suggesting that the molecule integrity of blend polymeric components has been preserved and that a good dispersion of the ABS domains in the PBT matrix has been achieved. Injection molded PBT/ABS blends were obtained to compare to the extruded ribbons. The mechanical tests for both specimens have shown the same trends. The injection molded samples have presented poorer impact strength, tensile strain at break and tensile strength, when compared to the respective extruded samples. That behavior has been attributed to the high level of molecular orientation resulting from the injection molding process and mainly to PBT degradation during process. The PBT degradation could have increased its degree of crystallinity, which has been confirmed by DSC measurements. As result, the blend became more brittle, decreasing its Izod impact strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The calorimetric and mechanical properties of virgin and recycled poly(ethylene terephthalate) from beverage bottles

In the present work, fusion behavior, crystallinity, and mechanical properties of beverage bottle poly(ethylene terephthalate) (PET) was compared with those of the virgin material. Viscosimetry measurements, differential scanning calorimetric studies, impact and tensile determinations were made in both materials. The lower M _v of bottle PET revealed that a thermomechanical degradation occurred during processing. Although bottles possess a considerable degree of crystallinity (≈30 percent), the crystallites are so small that they don't scatter light and, therefore, bottles are transparent. Virgin PET exhibited a brittle behavior while bottle PET exhibited a ductile one. This is a consequence of the difference In crystallinity between both materials (greater for virgin PET because of its original higher crystallinity content), although they were molded under the same conditions. Such difference was attributable to a “crystalline memory” effect having its origin in the orientation of the material during Injection molding at low temperature (250°C). Injection-molded PET specimens showed a strong, crystalline memory, capable of crystallization during very fast quenchings.     

Morphology and physical properties of poly(butylene terephthalate)

Liquid nitrogen-quenched PBT samples produce much larger spherulites of an optic axis orientation different from the of the air-cooled samples. Optical and scanning electron microscopy show that glass fibers in the glass-reinforced PBT sample nucleate the growth of well-defined spherulites along the glass fiber axis. Fracture studies at temperatures below and above the T_g indicate, respectively, brittle and ductile interspherulite boundary fracture. From dynamic mechanical studies, three transitions designated by α (flow transition), β (T_g), and γ (secondary relaxation) are observed. The magnitudes of the β and γ transitions are larger for the more amorphous quenched sample than the air-cooled sample, suggesting their amorphous phase origin. Addition of glass fibers raises the dynamic modulus and flow temperature, but suppresses the γ transition without significantly affecting the melting and glass transition temperatures.     

生物基工程聚酯弹性体对聚（3⁃羟基丁酸酯⁃co⁃3⁃羟基戊酸酯）的增韧改性研究

针对聚（3⁃羟基丁酸酯⁃co⁃3⁃羟基戊酸酯）（PHBV）的晶体尺寸大、结晶度高、呈脆性等问题对其进行增韧改性,通过熔融共混法在PHBV中添加生物基工程聚酯弹性体（BEPE）,制备了PHBV/BEPE共混物,经过测试流变性能、结晶性能、力学性能、热性能及微观形貌,对共混物的结构和性能进行分析和研究。结果表明,PHBV与BEPE之间的氢键作用、链缠结作用以及相似的主链结构使二者有更好的相容性和分散性,还可使PHBV球晶数量增多,球晶尺寸减小;当添加30 %（质量分数,下同）BEPE时共混物的断裂伸长率和冲击强度最高,分别较PHBV提高了589.2 %和149.4 %;BEPE使共混物的结晶度逐渐降低;添加BEPE样品的冲击断面逐渐粗糙,发生了脆韧转变。     

Effect of molecular weight on brittle‐to‐ductile transition temperature of polyetherimide

The fracture and yield strength of polyetherimide was evaluated over a temperature range of 23 to 140°C for materials with number‐average (M_n) and weight‐average molecular weight (M_w) ranging from 15.6 to 22.8 and 36.6 to 52.3 kg/mol, respectively. The brittle‐to‐ductile transition temperature, where an equal probability exists that an impact will result in a brittle or ductile failure, was determined by evaluating the temperature at which fracture and yield strength are equal. The transition temperature decreased from 155 to 60°C with increasing molecular weight and provided a measure of relative ductility between material samples. As a case study, the practical impact strength of an injection‐molded food service tray was determined at 20°C and correlated with fracture strength as a function of molecular weight. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1666–1671, 2004     

Double yield points in poly(tetramethylene terephthalate) and its copolymers under tensile loading

Double yield points before necking were observed in injection molded specimens of poly(tetramethylene terephthalate) (PTMT) and its copolymers under tensile loading. The first yield is associated with deformation of the amorphous region and the second yield is caused by the alpha to beta transition of PTMT crystallites. The first yield point became less apparent with an increase of crystallinity of the specimens. The second yield point became more apparent with an increase of crystallinity. Annealing of injection molded specimens increased the crystallinity and increased the second yield point on stress-strain curves. Copolymerization decreased the crystallinity and made the first yield point more prominent. Effects of annealing on mechanical and thermal properties of the specimens were also measured. The specimens changed their properties from ductile to brittle during annealing. Their change during annealing was mainly attributed to the increase of crystallinity and not to thermal degradation and/or crosslinking.     

Formation mechanism of crystal morphologies in LLDPE/HDPE blends investigated via water‐assisted and conventional injection molding

The LLDPE/HDPE blends with two different weight ratios as well as pure LLDPE were molded by means of water‐assisted and conventional injection molding (WAIM and CIM) in terms of their different thermal fields. The formation of the crystal morphology in the molded parts was investigated by a scanning electron microscope. The results showed that banded spherulites formed in the WAIM and CIM pure LLDPE parts. Banded spherulites of LLDPE coexisted with the randomly oriented lamellae of HDPE for LLDPE/HDPE blend parts with lower HDPE content at higher cooling rates, whereas a banding to nonbanding morphological transition occurred for LLDPE component (particularly for blend with higher HDPE content) at lower cooling rates. The heterogeneous nucleation effect of HDPE component on LLDPE component was responsible for the banding to nonbanding morphological transition by hindering the twist of LLDPE lamellae. It was interesting to find that the thermal effect, rather than the shear effect, was the main factor for the formation of crystal morphologies in both CIM and WAIM blend parts. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Mechanical behavior and optical transparency of polyamide 6 of different morphology formed by variation of the pathway of crystallization

The phase composition and supermolecular structure of polyamide 6 (PA 6) melt-crystallized on cooling at different rates or cold-crystallized at different temperatures were characterized and related to the optical transparency, stiffness and the stress–strain behavior. Cold-crystallization results in non-spherulitic formation of γ-mesophase or α-crystals, depending on the maximum annealing temperature. Both mesophase and crystals are of nodular shape. Melt-crystallization at low supercooling leads to formation of lamellar α-crystals and spherulites, while at high supercooling the nodular mesophase is forming. The absence of spherulites in cold-crystallized PA 6 films leads to high see-through clarity which is in contrast to the slowly melt-crystallized samples with opaque appearance. While Young’s modulus and the glass transition temperature increase with increasing crystallinity, for samples of identical crystallinity stiffness is considerably higher if the crystals are of lamellar rather than of nodular shape. The higher glass transition temperature of cold-crystallized PA 6 is related to a higher rigid amorphous fraction than in melt-crystallized samples pointing to a stronger coupling of the amorphous phase to ordered domains.     

The role of crystallinity and reinforcement in the mechanical behavior of polyamide‐6/clay nanocomposites

The mechanical behavior of compression‐molded polyamide‐6 (PA6) reinforced with 2 wt% of organo‐nanoclay (montmorillonite intercalated with ω‐amino dodecanoic acid) has been studied and compared to that of PA6. The tensile strength and the Young's modulus of the PA6/clay were 15% higher than those of PA6. Differential scanning calorimetry, Fourier transform infrared spectroscopy, and X‐ray diffraction showed that the crystalline structures of PA6 and PA6/clay differed considerably. A crystallinity of 25% with a dual structure composed of the γ and α forms was obtained in PA6/clay, while a crystallinity of 31% with the α form as the dominant crystalline structure was obtained in PA6. To understand the role of the crystalline structure of PA6, the molding process was modified to obtain PA6 specimens with different levels of crystallinity and different crystalline forms. Quenching molten PA6 at a cooling rate sufficiently high to prevent crystallization gave a material that was predominantly amorphous (crystallinity of 7%) with traces of the mesomorphic β or γ* form. Annealing this material at 80°C considerably increased crystallinity to 21%, which was also of the mesomorphic β or γ* form. PA6 with a predominant crystalline γ form could not be generated. Comparisons with PA6/clay in terms of crystallinity and mechanical behavior lead to the conclusion that the improvements in rigidity and strength observed when montmorillonite is added to PA6 are related to the reinforcing filler and not to a modification of the crystalline structure.     

An investigation into the relationship between the impact performance of rotationally molded polyethylene products and their dynamic mechanical properties

In this paper, a study of the relationship between the impact performance of rotationally molded polyethylenes and their dynamic mechanical properties is carried out. A wide range of conventional linear low density polyethylene powders and met‐allocene catalyzed linear low density polyethylene powders were rotationally molded and tested. Instrumented falling weight impact tests were carried out over a temperature range of ?60°C to 20°C. Dynamic Mechanical Thermal Analysis (DMTA) tests were also carried out between ?100°C and 90°C, at a frequency of 100 Hz. Comparisons between the impact performance of metallocene catalyzed LLDPEs and Ziegler‐Natta LLDPEs are made. The transitions evident in the DMTA results are related to changes in impact performance with temperature. The beta transition is found to fall in the transition region between high impact performance at low temperatures and lower impact performance at ambient temperatures.     

Optimizing the impact strength of rotationally molded parts

Rotational molding of thermoplastics has become an important process in industry. However, the optimization of this technique has been essentially based on a trial‐and‐error process. In this report, an L'16 experimental matrix design based on the Taguchi method was conducted to optimize the impact strength of rotationally molded parts. Oven temperature and oven time were found to be the principal factors affecting the impact property of rotationally molded thermoplastics. Density and melt flow index measurements were also employed to identify the material and structural parameters. The part density increased with increasing total energy transmitted into the molding system. The melt flow index provides an easy indication of the mechanical properties of rotationally molded parts.     

Use of a nanoindentation fatigue test to characterize the ductile–brittle transition

When considering grinding of minerals, scaling effect induces competition between plastic deformation and fracture in brittle solids. The competition can be sketched by a critical size of the material, which characterizes the ductile–brittle transition. A first approach using Vickers indentation gives a good approximation of the critical size through an extrapolation from the macroscopic to the microscopic scales. Nanoindentation tests confirm this experimental value. According to the grain size compared to the indent size, it can reasonably be said that the mode of damage is deformation-induced intragranular microfracture. This technique also enables to perform cyclic indentations to examine calcite fatigue resistance. Repeated loadings with a nanoindenter on CaCO₃ polycrystalline samples produce cumulative mechanical damage. It is also shown that the transition between ductile and brittle behaviour depends on the number of indentation cycles. The ductile domain can be reduced when the material is exposed to a fatigue process.     

Application of the essential work of fracture concept to high temperature deformation in polyoxymethylene

Essential Work of Fracture (EWF) tests have been carried out on double edge notched samples machined from injection molded sheets of commercial grades of polyoxymethylene homopolymer with different molecular weight averages. Most of the measurements were made at 100⁰C and over a range of test speeds in which polyoxymethylene is anticipated to undergo a macroscopic ductile‐brittle transition with decreasing strain rate. The results reflect both the existence and the molecular weight dependence of this transition, and are argued to be valid in terms of the European Structural Integrity Society's EWF draft test protocol under certain test conditions. However, it is shown that the applicability of the test method used here becomes highly questionable for test speeds in the immediate vicinity of the transition, owing to the influence of the initial ligament length on the crack tip deformation mechanisms.     

Crazing,yielding, and fracture of polymers. I. Ductile brittle transition in polycarbonate

Most thermoplastics far below their glass transition give a brittle fracture when de-formed in uniaxial tension. Bisphenol-A polycarbonates are an exception and deform in a ductile manner. However, it has been observed in Izod impact studies of notched samples that the mode of failure changes from a ductile to a brittle fracture on annealing samples below T_g. It has been found that, when notched samples are stressed, a Griffith type flaw is formed under the notch. The criterion for the ductile brittle transition is evaluated in terms of σG (the stress required to propagate the Griffith flaw), and σ_y, the yield stress for the polymer. It has been found that the density and yield stress for the samples annealed at various temperatures are dependent upon previous thermal history and in particular on the molecular weíAght. On the basis of these measurements, it is concluded that many of the so-called anomalous effects observed with polycarbonate can be explained.     

Structure modification of isotactic polypropylene through chemical crosslinking: Toughening mechanism

Reversibly crosslinked isotactic polypropylene (iPP) was prepared in the presence of dicumyl peroxide. The effects of the peroxide oxy‐radicals in the melt were investigated in relation to the modification of the polymer. The dynamic rheology analysis of the crosslinking process was carried out by using a plastograph. The crosslinking reaction was evaluated by the Monsanto method. The resulting structure of the modified samples was studied by means of differential scanning calorimetry (DSC), wide‐angle X‐ray scattering (WAXS), microhardness, and mechanical properties. The degree of crystallinity of the modified iPP, derived from DSC and WAXS, remains almost unchanged, i.e., the crystalline structure is unaffected, though the lamellar thickness slightly decreases. The impact strength of the crosslinked iPP is greatly improved with reference to that of the unmodified material. A transition from brittle to ductile behavior appears in the modified iPP for all the crosslinking agents studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2968–2976, 2007     

Co‐injection molding: Effect of processing on material distribution and mechanical properties of a sandwich molded plate

The effect of molding parameters on material distribution and mechanical properties of co‐injection molded plates has been studied using experimental design. The plates were molded with a polyamide 6 (PA 6) as skin and a 20% glass fiber‐reinforced polybutyleneterephtalate (PBTP) as core. Five molding parameters—injection velocity, mold temperature, skin and core temperature, and core content—were varied in two levels. The statistical analysis of the results showed that three parameters—Injection velocity, core temperature, and core content—were the most significant in affecting skin/core distribution. A high core temperature was the most significant variable promoting a constant core thickness, while core content was the most significant factor influencing a breakthrough of the core. Mechanical properties, such as flexural and impact strength showed a high correlation with the skin/core distribution. The slight increase in falling weight impact strength of the sandwich molded plates, compared to similar plates molded from PBTP only, could be explained from the failure process, which initiates in the brittle core and propagates through the ductile skins.     

Effect of an acrylic modifier on the brittle to ductile transition in poly(vinyl chloride)

Instrumented notched Izod measurements were made on test specimens cut from milled compression molded plaques of modified and unmodified poly(vinyl chloride) (PVC). The experimental variables were notch radius (from 0.025 to 6.35 mm in 8 steps) and two temperatures (23 and 12.5°C). Load-time and energy-time curves were determined under each set of experimental conditions, and each condition was replicated five times. The brittle to ductile transition is readily observed in this experimental range. The transition always occurs at shorter notch radii at each temperature for the modified PVC. In the transition region, the total energy drops from the 1,000 to 2,000 J/m range to less than 150 J/m. In this region, maximum loads remain the same while the times to break becomes much shorter for the brittle materials. These results suggest that the underlying molecular mechanism for brittle failure is the inability of the system to respond to the applied deformation. The oscillations observed in the printed output of the instrumented impact test were identified as having instrument rather than test specimen origins.