Polypropylene Random Copolymer Research Articles

Impacts of Photooxidation on Commercially Available Homo and Copolymers of Polypropylene on Their Microstructure and Mechanics: A Cross‐Sectional Analysis

ABSTRACTPolyolefin degradation is widely studied to assess the lifetime of packaging materials. In this work, a combination of bulk (DSC, GPC, 13C‐NMR, XRD), surface (FTIR) and cross‐sectional characterization (Raman spectroscopy and nanoindentation) was used to examine changes in the mechanical properties and microstructure of two different commercially‐available polyolefins, with similar crystallinities, produced by injection molding—a polypropylene homopolymer (PPH) and a polypropylene random copolymer (PPRC)—aged under accelerated UV‐A conditions. The aim was to characterize the variations in the crystallinity and microstructure across the cross‐section of these materials. Our results suggest that the presence of ethylene comonomer units in PPRC results, on average, in smaller crystal dimensions, leads to improved packing, and a more homogeneous microstructure and hardness across the cross‐section of the sample. The ethylene monomers stabilize PPRC from oxidation during the first 14 days of accelerated aging, but eventually the rate of degradation matches the PPH at 28 days of aging, probably because of the higher surface area to volume ratio of the smaller crystals. The work emphasizes the importance of incorporating ethylene comonomers into polyolefins to limit variation of the microstructure across the core to the skin layer, for improved future design of packaging that degrades fully.

Crystallization‐correlated phase separation of polypropylene random copolymers

AbstractEthylene segments are incorporated into stereoregular propylene‐propylene‐propylene (PPP) homo‐sequences to create locally disordered ethylene‐propylene (EP) segments in polypropylene random copolymer (PPR) through a phase separation process, resulting in large quantities of spherical EP rubbery particles for improving impact toughness. However, the manipulation on size and distribution of these spherical EP rubbery phases remains insufficiently understood. In this study, the phase separation of PPR and the influence of crystallization on phase separation were investigated using rheological measurements and small‐angle x‐ray scattering (SAXS) methods. Combined with the isothermal crystallization method, phase separation was differentiated by the crystallization rate. The molecular chain states corresponding to different crystallization conditions were studied to interpret the varying rubbery particle sizes resulting from phase separation. The results showed that phase separation of EP segments from PPP is highly related to crystallization. Isothermal crystallization at temperatures ranging from 110 to 130°C leads to a high degree of phase separation due to the fast crystallization rate, as evidenced by the presence of small quantities of large pores in microscopic observations. This work provides insights into the phase separation of random copolymers and establishes correlations for manipulating the low‐temperature toughness of PPR.

Collaboration of β-crystals and rubbery phases in polypropylene random copolymer for toughening

Polypropylene random copolymer (PPR) is in high demand for pipelines due to its comprehensively brittle-ductile balance. It is a multiphase polymer composed of crystalline phases and rubbery phases in which improving the quantities of ductile β-crystals can effectively toughen PPR. However, the influence of β-crystallization on the aggregation of rubbery phases and their collaboration for toughening are still not well elucidated. In this work, the toughening mechanism of PPR/iPP/β-NA composites were illustrated by manipulating the crystallization and phase separation behaviors using different molecular weight of isotactic polypropylene (iPP) and β-nucleating agent (β-NA). A high relative β-crystal content (Kβ) was obtained in PPR/iPP/β-NA composites and the influence of molecular weight of iPP on crystal structures of PPR/iPP/β-NA composites was investigated via differential scanning calorimetry (DSC) and x-ray diffraction (XRD). The phase separation behaviors were then studied using rheological measurements and scanning electron microscope (SEM). The impact behaviors of PPR/iPP/β-NA composites with similar crystal structures but different size of rubbery particles were demonstrated. It was found that crystallization of PPR into β-crystal promoted the phase separation process and the resulting rubbery particle size. The deformation of large rubbery particles induced small wavy cracks at the fracture surface other than layered cracks for small rubbery particles. This work basically introduces the toughening mechanism from collaboration of β-crystals and rubbery phases in polypropylene random copolymers and provides a new method for fabricating high toughness PPR pipe.

Insight into the less β-phase induction by calcium pimelate in polypropylene random copolymer

Although calcium pimelate (CaPim) is recognized as an efficient β-nucleating agent for polypropylene with nucleating ability solely for the β-phase, it was found to induce less β-phase in polypropylene random copolymer (PPR) compared to polypropylene homopolymer (PPH). Generally, this reduction is attributed to unfavorable β-growth. Besides growth, here, nucleation behavior was also investigated in detail. With nucleation barrier determined through fractionated crystallization, the relative β-nuclei proportion induced by CaPim was calculated to be 96.6 % for PPH and 79.1 % for PPR with 7.3 mol% ethylene inserted. This fewer β-nuclei induction may be linked to a decreased proportion of isometric sequences exceeding the critical length required for β-nucleation. As expected, the relative growth rate of the β- to α-phase (Gβ/Gα) is lower in PPR indicating unfavorable β-growth. These results indicate that diminished β-nuclei induction and subsequent unfavorable β-growth jointly result in less β-phase induction in PPR.

Comparative Analysis of Water Hammer Performance in Different Pipe Parameters with FSI

Water hammer (WH) is a critical phenomenon in fluid-filled piping systems that can lead to severe pressure surges and structural damage. The characteristics of the pipe material, geometry, and support conditions play a crucial role in the fluid–structure interaction (FSI) during WH events. This study investigates the impact of various pipe parameters, including material, length, thickness, and diameter, on the WH behavior using an FSI-based numerical approach. A comprehensive computational model was developed based on the algorithm presented in Delft Hydraulics Benchmark Problem (A) to simulate the WH phenomenon in pipes made of different materials, such as steel, copper, ductile iron, PPR (polypropylene random copolymer), and GRP (glass-reinforced plastic). This study examines the influence of pipe parameters on WH performance in pipelines, utilizing FSI to analyze the phenomenon. The results show that the pipe material has a significant influence on the pressure wave speed, stress wave propagation, and the overall system response during WH. Pipes with lower modulus of elasticity, such as PPR and GRP, exhibit lower pressure wave speeds but higher stress wave speeds compared with steel pipes. Increasing the elastic modulus, pipe wall thickness, length, and diameter enhances the pipe’s stiffness and impacts the timing, magnitude of pressure surges, and the likelihood of cavitation. The findings of this study provide valuable insights into the design and mitigation of WH in piping systems.

Ternary Blends of Polypropylene Copolymer, Polyethylene and Thermoplastic Polyurethane for Fused Deposition Modeling Three-Dimensional Printing Technology: Preparation, Printing and Properties.

A set of filaments for fused deposition modeling (FDM) three-dimensional (3D) printing was developed from the ternary blends of polypropylene random copolymer (PPR or P), high density polyethylene (HDPE or E), and thermoplastic polyurethane (TPU or T), formulated with different weight ratios of polymers, i.e., 80:20:0, 70:20:10, 60:20:20, and 50:20:30, respectively, and coded as P80E20T0, P70E20T10, P60E20T20, and P50E20T30, respectively. The blend composition was optimized to obtain both high-quality filaments with low ovality and FDM-fabricated objects with minimized warpage and good interlayer bonding. The crystallization and crystalline morphologies of individual polymers in the blend filaments were comprehensively analyzed by differential scanning calorimetry (DSC), X-ray diffraction (XRD), and polarized light optical microscopy (PLOM). It was found that HDPE acted as crystalline nuclei for PPR crystallization; PPR appeared to crystallize more readily at a slightly higher T c with somewhat greater crystallinity. Meanwhile, TPU explicitly restricted the crystallization of both polyolefins; decreases in both the size and growth rate of their spherulites were observed. The PLOM and SEM results indicated that the surface morphology of the ternary blends was not absolutely phase-separated; an increasing number of TPU droplets inherently imbedded at the boundary of the polyolefin aggregate phase when a higher TPU quantity was integrated. Consequently, the warpage deformation and layer interfusion of the as-printed articles were most remarkably improved when P50E20T30 was used. Nonetheless, the incorporation of relatively flexible TPU material into the PPR-based filaments inevitably reduced their mechanical performance; the flexural strength and modulus of the highest-quality 3D-printed P50E20T30 object were fairly decreased by approximately 25% and 12%, respectively.

Phase Separation Behaviors and Correlated Crystallization of β-Nucleated Polypropylene Random Copolymer Composites for Regulating Impact Toughness

Phase Separation Behaviors and Correlated Crystallization of β-Nucleated Polypropylene Random Copolymer Composites for Regulating Impact Toughness

Stepwise crystallization method combining isotactic polypropylene-based plastic waste film to prepare high-performance polypropylene random copolymer

Upcycling of waste plastic film is increasingly important at the background of energy shortage and environmental crisis. However, direct reuse of the waste plastics as reworked material inevitably downgrades the mechanical properties. Herein, a stepwise crystallization method was used to enable the recycling of waste isotactic polypropylene (iPP) film value-added in iPP-based homocomposites. In detail, the effect of β-nucleating agent (β-NA) and iPP on crystallization behaviors of polypropylene random copolymer (PPR) was investigated at first. The stepwise crystallization procedure was further introduced to promote the β-crystallization of PPR/iPP/β-NA composites in which the crystal structures, polymorph compositions and phase morphologies were systematically researched. At last, impact behaviors of PPR/iPP/β-NA composites were characterized and a penitential toughening mechanism was proposed. It was found that the stepwise crystallization boosted β-crystallization and growth of rubbery phase during the isothermal procedure, resulting in an increase of relative β-crystal content and low temperature impact toughness from 0 % and 2.02 kJ/m2 of neat PPR to 33.4 % and 3.06 kJ/m2 of PPR/iPP/β-NA composites. This work provides a simple, implementable, and effective method for the recycling of waste iPP films and the low-temperature toughening of PPR.

Toughening mechanism of α/β core-shell structure for high toughness polypropylene random copolymer

Weak interfaces can impede crack propagation in rigid natural materials containing small amounts of organic compounds. Inspired from this, we start from the core-shell structured isotactic propylene (iPP)/polypropylene random copolymers (PPR) homocomposites and construct serval kinds of interfaces to study the toughening mechanisms by applying the crystallization epitaxies of PPR on iPP. Through molecular chain diffusion and crystallization epitaxy, derived models from microscopic core-shell structured crystals in the homocomposites to macroscopic layer-by-layer assemblies with different interfaces are established to magnify the role that each layer plays during crack initiation and propagation. As a result, the ductile β-PP interface can decrease crack tip strength so that a further step of crack initiation is triggered in the composite laminates with a fold of fracture energy consumption compared to the laminates with weak or rigid interfaces. At last, we come back to the core-shell structured homocomposites and toughen them with an improve in impact toughness from ∼10.8 to ∼18.2 kJ/m2 by manipulating the content of ductile interfaces. This work provides a novel research routine and a new toughening mechanism toward the toughening of PP and can be extended to study the fracture mechanisms of other toughening systems with core-shell structures.

The Crystallization Morphology and Conformational Changes of Polypropylene Random Copolymer Induced by a Novel β-Nucleating Agent.

The crystal morphology and conformational changes during crystallization of a polypropylene random copolymer (PPR) are the basis for understanding its crystallization process. In this work, novel rare-earth β-nucleating agent WBN-28 was directly added into PPR to induce β-crystallization. The results of differential scanning calorimetry (DSC) showed that it has an excellent β-crystal-induced effect. The β-crystal content could surpass 85%, calculated from wide-angle X-ray diffraction (WAXD) data. The morphology of the β-crystal and α-crystal was intuitively observed via a polarizing optical microscope (POM). The β-crystallites were interconnected to naturally develop plate-like crystalline regions possessing a certain size, and the α-crystallites with sufficient thicknesses possessed a cross-hatched phenomenon. The bundle-like supramolecular structure of the β-crystal induced by WBN-28 was further observed via a scanning electron microscope (SEM). The conformational changes in the crystallization process of PPR were resolved via high-resolution infrared spectroscopy to understand its β-crystallization in depth. The conformational changes during the crystallization of PPR were found to be different from those of the isotactic polypropylene homopolymer (PPH); they had their own characteristics. This will provide guidance for understanding the β-crystallization of PPR in depth.

Design and analysis of serviceable cantilever fit snap in automotive plastic parts

Purpose Snap fits are crucial in automotive applications for rapid assembly and disassembly of mating components, eliminating the need for fasteners. This study aims to focus on designing and analyzing serviceable cantilever fit snap connections used in automobile plastic components. Snap fits are classified into permanent and semi-permanent fittings, with permanent fittings having a snap clipping angle between 0° and 5° and semi-permanent fittings having a clipping angle between 15° and 45°. Polypropylene random copolymer is chosen for its exceptional fatigue resistance and elasticity. Design/methodology/approach The design process includes determining dimensions, computing assembly, disassembly pressures and creating three-dimensional computer-aided design models. Finite element analysis (FEA) is used to evaluate the snap-fit mechanism’s stress, deformation and general functionality in operational scenarios. Findings The study develops a modified snap-fit mechanism with decreased bending stress and enhanced mating force optimization. The maximum bending stress during assembly is 16.80 MPa, requiring a mating force of 7.58 N, while during disassembly, it is 37.3 MPa, requiring a mating force of 16.85 N. The optimized parameters significantly improve the performance and dependability of the snap-fit mechanism. The results emphasize the need of taking into account both the assembly and disassembly processes in snap-fit design, because the research demonstrates greater forces during disassembly. The approach developed integrates FEA and design for assembly (DFA) concepts to provide a solution for improving the efficiency and reliability of snap-fit connectors in automotive applications. Originality/value The research paper’s distinctiveness comes from the fact that it presents a thorough and realistic viewpoint on snap-fit design, emphasizes material selection, incorporates DFA principles and emphasizes the specific requirements of both assembly and disassembly operations. These discoveries may enhance the efficiency, reliability and sustainability of snap-fit connections in plastic automobile parts and beyond. In conclusion, the idea that disassembly needs to be done with a lot more force than installation in a snap-fit design can have a good effect on buzz, squeak and rattle and noise, vibration and harshness characteristics in automobiles.

Effect of silver particles on the crystal structure and the mechanical, optical and antibacterial properties of various polypropylene based plastomers and elastomers

In composite materials consisting of silver particles and a polypropylene matrix, the silver must migrate to the surface of the materials in order to exert on antibacterial effect. Substrates with various crystal structures may have different interactions with the silver particles, which can significantly impact the antibacterial performance. The research described in this paper investigates the influence of silver particles on the crystallization behavior of materials with varying crystallinity capabilities by selecting various polypropylene-based plastics and elastomers (Homopolymer polypropylene (PPH-T03), random poly(propylene/ethylene) copolymers (PPR-YPR503 and PPR-P340R), polyolefin elastomers (VERSIFY3000 (POE-1) and VERSIFY3401 (POE-2)), and ethylene propylene diene monomer for polymers (EPDM4725 and EPDM4770)). The research results indicated that the silver only entered the amorphous regions of the PP rather than entering the crystal regions, where they can more easily migrate to the material surface, resulting in a higher antibacterial effect. Therefore, the antibacterial degree of PP-Ag was as high as 99.9%. Silver can enter the micro-crystals of both the random copolymer polypropylene, (PPR-YPR503, PPR-1) and the random copolymer polypropylene, (PPR-P340R, PPR-2,) with a stronger effect on PPR-2. More silver entered the micro-crystals of PPR-2, and it was difficult for the silver ions to migrate out of the crystalline regions to exhibit antibacterial properties. The antibacterial degree of PPR-1-Ag was higher than that of PPR-2-Ag (77.8% vs. 66.7%). Similarly, silver had a greater impact on the lamellar structure of the polyolefin elastomer (VERSIFY3401, POE-2) compared to the polyolefin elastomer (VERSIFY3000, POE-1). In comparison with POE-2-Ag, POE-1-Ag exhibited a higher antibacterial degree (79.6% vs. 57.4%). Research on the two types of ethylene propylene diene monomer (EPDM) composite materials indicated that EPDM-1 exhibited a lower Mooney viscosity and poorer flowability. The EPDM-1 tended to encapsulate the silver within its molecular chains, thereby impeding the migration of silver to the surface. The optical performance analysis indicated that silver antibacterial agents had little impact on the optical properties of PP-Ag, PPR-1, PPR-2, POE-1, POE-2 and the EPDMs. We suggest that this research provides theoretical guidance for selecting highly antibacterial polypropylene materials.

An efficient β-nucleating agent with high lattice matching rate for plate-like crystallization of polypropylene random copolymer.

It is challenging to naturally produce large amounts of β-crystals by directly adding a commercial β-nucleating agent (β-NA) into polypropylene random copolymer (PPR) at present. In this work, a novel rare earth β-NA WBN-28 was directly introduced into PPR to prepare β-PPR with high β-crystal conversion. The results of differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) indicated that it is an efficient β-NA for PPR. The β-conversion rate (β-CR) could surpass 85% when the nucleating agent content was mere 0.05%. With the further increment of nucleating agent, the β-CR increased gradually, which could reach 89.5% and 86.9% respectively calculated by DSC and WAXD when the addition amount was 0.4%. The incredible high β-CR delayed the βα-recrystallization in isothermal crystallization. The fusion peak of α-crystal was unobserved below the isothermal crystallization temperature of 122 °C when the addition amount was more than 0.2%. Furthermore, there was a highly ordered structure in WBN-28 with the periodicity of 12.89 Å, which was approximately twice of the unit cell parameter in the c direction of β-PP, indicating a high lattice matching rate between them. Intuitively observed by polarizing optical microscope (POM), the crystal grains of the blends with β-NA were more refined and finally crystallized in a plate-like shape. The forming process of the plate-like β crystalline regions were proposed by scanning electron microscope (SEM) and POM.

Mechanochemical synthesis and properties of basalto-plastics based on polypropylene random copolymer

Mechanochemical synthesis and properties of basalto-plastics based on polypropylene random copolymer

Lignocellulosic fiber reinforcement in PPRC composites: An analysis of structural and thermal enhancements.

This study investigates the fabrication process of biocomposites and their resultant mechanical and thermal properties, essential for evaluating the performance of finished products. Polypropylene random copolymer (PPRC) was employed as the matrix phase, while rice husk (RH), a biowaste filler, was incorporated in varying concentrations. The rice husk fiber was treated with alkali (RHT) to enhance its lignocellulosic content. To improve interfacial bonding, maleic anhydride and NaOH treatment were utilized. Glass fiber grafted on polypropylene (PPGF) and talc powder functioned as additives. Both raw and treated rice husk fibers were characterized using Fourier-transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), and analytical methods to quantify the composition of lignin, cellulose, hemicellulose, and ash. Significant structural changes were observed, with cellulose content increasing from 26% to 53%. Wood polymer composites (WPC) produced from raw and treated rice husk were evaluated based on morphological studies, Izod impact testing, water absorption, heat distortion temperature (HDT), and VICAT softening temperature (VST). The results demonstrated that the HDT and VST of WPC improved by 24% and 7%, respectively, compared to PPRC, indicating enhanced structural and thermal properties. Additionally, impact strength and water absorption were found to be dependent on cellulose concentrations in the biocomposite. This study underscores the environmental benefits of utilizing biowaste rice husk in biocomposites, promoting sustainability by converting agricultural waste into valuable materials with enhanced properties for various industrial applications.

Exploitation of a New Nucleating Agent by Molecular Structure Modification of Aryl Phosphate and Its Effect on Application Properties of the Polypropylene.

In this work, a novel α-nucleating agent (NA) for polypropylene (PP) termed APAl-3C-12Li was prepared and evaluated compared with the commercially available type NA-21. For the synthesis of the organophosphate-type NA (APAl-3C), the -OH group of the acid part of NA-21 was substituted by the isopropoxy group. The structure of APAl-3C was analyzed by spectroscopy and element analysis, the results of which were consistent with the theoretical molecular formula. APAl-3C's thermal stability was studied by differential scanning calorimetry (DSC) and thermogravimetry (TG), which showed only weak mass loss below 230 °C, meaning that it would not decompose during the processing of PP. The APAl-3C-12Li was used as a novel nucleating agent, studying its effects on crystallization, microstructure, mechanical and optical properties. Tests were performed in a PP random copolymer at different contents, in comparison to the commercial NA-21. The composite with 0.5 wt% APAl-3C-12Li has a similar crystallization temperature of 118.8 °C as with the addition of 0.5 wt% NA-21. An advantage is that the composite with the APAl-3C-12Li has a lower haze value of 9.3% than the counterpart with NA-21. This is due to the weaker polarity of APAl-3C-12Li after the introduction of methyl and better uniform dispersion in the PP matrix, resulting in stronger improvement of optical and mechanical properties.

Investigation of tribo-mechanical performance of alkali treated rice-husk and polypropylene-random-copolymer based biocomposites

This study was based on the experimental performance evaluation of a wood polymer composite (WPC) that was synthesized by incorporating untreated and treated rice husk (RH) fibers into a polypropylene random copolymer matrix. The submicron-scale RH fibers were alkali-treated to modify the surface and introduce new functional groups in the WPC. A compatibilizer (maleic anhydride) and a thermos-mechanical properties modifier (polypropylene grafted with 30 % glass fiber) were used in the WPC. The effects of untreated and treated RH on the WPC panels were studied using FESEM, FTIR, and microscope images. A pin-on-disk setup was used to investigate the bulk tribological properties of PPRC and WPC. The complex relationship between the friction coefficient of different loading of RH fibers in the WPC, as a function of sliding distance, was analyzed along with the temperature and morphology of the surface. It was observed that untreated RH acted as a friction modifier, while treated RH acted as a solid lubricant. Microhardness was calculated using the QCSM module on nanoindentation. It was found that untreated RH led to an increase in microhardness, while treated RH caused a decrease in hardness compared to PPRC.

Effect of hydrophobic nano‐silica/β‐nucleating agent on the crystallization behavior and mechanical properties of polypropylene random copolymers

AbstractIn this work, hydrophobic nano‐silica (SiO2) and β‐nucleating agent are incorporated into polypropylene random copolymer (PP‐R) matrix by melt blending. The effect of the content of nano‐SiO2/β‐nucleating agent on the crystallization and mechanical behaviors of PP‐R was investigated in detail. For a nano‐SiO2 content of 0.5 wt% and a β‐nucleating agent content of 0.5 wt%, the tensile strength and impact strength of the composite were in a more balanced position. Regarding isothermal and non‐isothermal crystallization experiments, nano‐SiO2/β‐nucleating agent significantly accelerated the nucleation and growth of crystallites with a synergistic nucleation effect. Also, the crystallization kinetics of PP‐R/nano‐SiO2/β‐nucleating agent, PP‐R/nano‐SiO2 and PP‐R/β‐nucleating agent composites were analyzed and compared using the Avrami equation. The results showed that the PP‐R/nano‐SiO2/β‐nucleating agent composites have better crystallization rate and shorter semi‐crystallization time. This study shows far‐reaching theoretical and practical implications for accelerating the development of new high‐performance PP‐R materials. © 2023 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.

Toward a Further Understanding of the Decreased β-Phase Content in β-Nucleated Polypropylene Random Copolymer: From Nucleation and Growth Kinetics

Toward a Further Understanding of the Decreased β-Phase Content in β-Nucleated Polypropylene Random Copolymer: From Nucleation and Growth Kinetics

Factors affecting the leaching of micro and nanoplastics in the water distribution system

The role of the water distribution system (WDS) requires that it supply water of sufficient quality to households. Unregulated leaching of micro and nanoplastics from plastic pipes of the distribution system is therefore a cause for concern, particularly with the rise in research associating these plastic particles to adverse health impacts in living organisms. Within this study, four parameters (pH, free chlorine concentration, pipe material, and time) were varied in a pipe loop network to observe their effect on microplastic (MP) and nanoplastic (NP) leaching into the simulated distribution network. Results indicated an abundance of MPs/NPs in different shapes and sizes throughout the samples. Graphical trends illustrated that basic pH values contributed to a higher number of particles. Statistical analysis via analysis of variance (ANOVA) confirmed this observation and further showed interaction of chlorine dose and pH concentration (p-value = 0.000), and chlorine dose and pipe material (p-value = 0.038) was also significant to leaching. Numerically, polyethylene (PE) particles were the most abundant with a total of 15194 particles, followed by 12920 polypropylene random copolymer (PPR) particles and 12317 polyvinyl chloride (PVC) particles. It was also noticed that the number of particles decreased with time.© 2023 Elsevier Inc. All rights reserved.