The effect of nanoclay on the crystallization behavior,microcellular structure,and mechanical properties of thermoplastic polyurethane nanocomposite foams

The effects of nanoclay on the crystallization behavior, microcellular structure, and mechanical properties of thermoplastic polyurethane (TPU)/clay nanocomposite (TPUCN) foams were investigated using differential scanning calorimetry, rheometry, scanning electron microscope, transmission electron microscopy, and X‐ray diffraction. It was found that the nanoclay acted as an effective nucleating agent for both crystal nucleation and cell nucleation. As a result, it significantly enhanced the crystallization behavior of the hard segment (HS) domains in TPU while refining the foamed structure of the microcellular injection molded parts. In particular, the average cell diameter of TPUCN foams decreased from 45 µm for neat TPU to 27 µm for TPUCN5 (5 wt% clay) and 18 µm for TPUCN10 (10 wt% clay). Furthermore, the cell density increased from 0.7 × 10⁷ cell/cm³ for neat TPU to 1.4 × 10⁷ cell/cm³ and 3.1 × 10⁷ cell/cm³ for TPUCN5 and TPUCN10, respectively. In addition, the tensile strength also increased by 56.3% and 89.2% with 5 and 10 wt% clay content, respectively. By controlling the cell nucleation behavior through uniformly dispersed nanoclay, this study demonstrates that it is feasible to produce TPUCN foams via microcellular injection molding with desirable microcellular structures and improved mechanical properties. POLYM. ENG. SCI., 56:319–327, 2016. © 2015 Society of Plastics Engineers     

Rheological study of the influence of branch content on the miscibility of octene m‐LLDPE and ZN‐LLDPE in LDPE

The influences of branch content on the miscibility of octene LLDPE made by metal‐locene catalyst (m‐LLDPE) and by Ziegler‐Natta LLDPE (ZN‐LLDPE) in LDPE were investigated with rheological methods. Dynamic and steady shear measurements were carried out in a Rheometrics Mechanical Spectrometer 800. Here, m‐LLDPEs were used to isolate interaction of molecular parameters. Blends of octene m‐LLDPE and ZN‐LLDPE with LDPE were mixed at 190°C in the presence of an adequate amount of antioxidant. The miscibilities of blends were revealed by the dependence of their measured η_o, η′ and G′ on blend composition as well as on agreement with predictions of different emulsion models. Blends of m‐LLDPE with LDPE were found to be almost miscible in the LLDPE branching range 10–30 branches/1000 C. However, immiscibility was found to develop at lower LLDPE branch contents. For ZN‐LLDPE/LDPE systems, branch content plays a significant role especially at low branch contents. The comparison of m‐LLDPE and ZN‐LLDPE systems suggest the strong influence of branch distribution (uniform and random, respectively). Palierne, Bousmina, and Scholz models fitted the loss and storage moduli data well with a value of α/R in the range 10³?10⁴ N/m². Polym. Eng. Sci. 44:660–672, 2004. © 2004 Society of Plastics Engineers.     

Microcellular foaming of low‐density polyethylene using nano‐CaCo3 as a nucleating agent

In this study, microcellular foaming of low‐density polyethylene (LDPE) using nano‐calcium carbonate (nano‐CaCO₃) were carried out. Nanocomposite samples were prepared in different content in range of 0.5–7 phr nano‐CaCO₃ using a twin screw extruder. X‐ray diffraction and scanning electron microscopy (SEM) were used to characterize of LDPE/nano‐CaCO3 nanocomposites. The foaming was carried out by a batch process in compression molding with azodicarbonamide (ADCA) as a chemical blowing agent. The cell structure of the foams was examined with SEM, density and gel content of different samples were measured to compare difference between nanocomposite microcellular foam and microcellular foam without nanomaterials. The results showed that the samples containing 5 phr nano‐CaCO₃ showed microcellular foam with the lowest mean cell diameter 27 μm and largest cell density 8 × 10⁸ cells/cm³ in compared other samples. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Solid State Rheological Properties of Ultra‐High Molecular Weight Polyethylene Foams

The rheological properties of ultra‐high‐molecular‐weight polyethylene (UHMWPE) foams were studied using solid state rheometry. Frequency and temperature sweeps were performed in the linear viscoelastic regime. For comparison purposes, low‐density polyethylene (LDPE) and high density polyethylene (HDPE) foams were also studied. For the range of densities under consideration (200‐700 kg/m³), several models for prediction of elastic moduli were compared. It was found that none of the models succeeded in representing completely the mechanical behavior of foams. Further refinements must be made in order to take into account parameters relating the morphology of the foam to its mechanical properties.     

Electrical conductivity of carbon black/single-wall carbon nanotube/low-density polyethylene ternary composite foam

In order to obtain high electrical conductive low-density polyethylene (LDPE) foam, carbon black (CB), single-wall carbon nanotube (SWCNT), and LDPE (CB/SWCNT/LDPE) ternary composite foams were successfully fabricated by chemical compression molding method. The electrical conductivity, mechanical properties, microstructure, density, and crystallinity of the foam were studied in detail. It can be found that CB and SWCNT have synergistic effect. For the CB/SWCNT/LDPE composite foam which containing 19 wt % CB and 0.05 wt % SWCNT, its density is only 0.082 g cm⁻¹ and the electrical conductivity can reach at 2.88 × 10⁻⁵ S cm⁻³, which is far more than 15 orders of magnitudes of pure polyethylene and 4 orders of magnitudes times higher than sample which CB content is 19 wt %. It is noteworthy that ultralow concentration of SWCNT could drastically improve the electrical conductivity and reduce the density of LDPE foams. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48382.     

The role of the interface in melt linear viscoelastic properties of LLDPE/LDPE blends: Effect of the molecular architecture of the matrix

The rheological properties of blends consisting of a long chain branched low‐density polyethylene (LDPE) and two linear low‐density polyethylenes (LLDPE) are studied in detail. The weight fractions of the LDPE used in the blends are 5 and 15%. The linear viscoelastic characterization is performed at different temperatures for all the blends to check thermorheological behavior and miscibility in the melt state. Blends containing metallocene LLDPE as the matrix display thermorheologically complex behavior and show evidences of immiscibility in the melt state. The linear viscoelastic response exhibits the typical additional relaxation ascribed to the form deformation mechanism of dispersed phase droplets (LDPE). The Palierne model satisfactorily describes the behavior of these blends in the whole frequency range explored. However, those blends with Ziegler‐Natta LLDPE as the matrix fulfill the time‐temperature superposition, but exhibit a broad linear viscoelastic response, further than the expected for an immiscible system with a sharp interface. The rheological analysis reveals that, in addition to the droplets form relaxation, another mechanism at lower frequencies exists. The broad linear response of the blends with the Ziegler‐Natta LLDPE can be explained by hypothesizing a strong interaction between the high molecular weight linear fraction of the LLDPE and the low molecular weight (almost linear) chains of the LDPE phase, forming a thick interface with its own viscoelastic properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Hot tack of metallocene catalyzed polyethylene and low-density polyethylene blend

Films made of metallocene catalyzed polyethylene (mPE), low-density polyethylene (LDPE), and their blend were prepared to investigate how LDPE influences the hot tack of film. Experimental results showed hot tack is independent of film thickness. The addition of 30 wt % of LDPE can increase the hot tack of mPE film. The thermograms of differential scanning calorimetry (DSC) suggest the respective partial melting and recrystallization of those smaller size crystals at the bond forming and joint fracture stages play very important roles. The large amount of partial melting and high flow may induce a higher degree of molecular diffusion. Higher residual crystallinity and recrystallization at the hot tack testing process may induce higher resistant to bond fracture. Those two positive influences show that the mPE/LDPE film has the higher hot tack. The evidence from optical (higher optical transmission and lower haze) as well as viscoelastic (higher storage modulus and lower melt viscosity) properties further support this hypothesis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1769–1773, 1999     

Investigation of charge transport properties in conducting copolymers of aniline with 3‐aminobenzenesulfonic acid for their applications as antistatic encapsulation materials blended with low‐density polyethylene

The electrostatic charge dissipative (ESD) properties of conducting self‐doped and PTSA-doped copolymers of aniline (AA), o‐methoxyaniline (methoxy AA) and o‐ethoxyaniline (ethoxy AA) with 3‐aminobenzenesulfonic acid (3‐ABSA) blended with low‐density polyethylene (LDPE) were investigated in the presence of external dopant p‐toluenesulfonic acid (PTSA). Blending of copolymers with LDPE was carried out in a twin‐screw extruder by melt blending by loading 1.0 and 2.0 wt% of conducting copolymer in the LDPE matrix. The conductivity of the blown polymers blended with LDPE was in the range 10^?12–10^?6 S cm^?1, showing their potential use as antistatic materials for the encapsulation of electronic equipment. The DC conductivity of all self‐doped homopolymers and PTSA‐doped copolymers was measured in the range 100–373 K. The room temperature conductivity (S cm^?1) of self‐doped copolymers was: poly(3‐ABSA‐co‐AA), 7.73 × 10^?4; poly(3‐ABSA‐co‐methoxy AA), 3.06 × 10^?6; poly(3‐ABSA‐co‐ethoxy AA), 2.99 × 10^?7; and of PTSA‐doped copolymers was: poly(3‐ABSA‐co‐AA), 4.34 × 10^?2; poly(3‐ABSA‐co‐methoxy AA), 9.90 × 10^?5; poly(3‐ABSA‐co‐ethoxy AA), 1.10 × 10^?5. The observed conduction mechanism for all the samples could be explained in terms of Mott's variable range hopping model; however, ESD properties are dependent upon the electrical conductivity. The antistatic decay time is least for the PTSA‐doped poly(3‐ABSA‐co‐AA), which has maximum conductivity among all the samples. © 2013 Society of Chemical Industry     

A conductive foam: Based on novel poly(styrene‐b‐butadiene‐co‐styrene‐b‐styrene) tri‐block copolymer filled by carbon black

In this article, a conductive foam based on a novel styrene‐based thermoplastic elastomer called poly(styrene‐b‐butadiene‐co‐styrene‐b‐styrene) tri‐block copolymer S(BS)S was prepared and introduced. S(BS)S was particularly designed for chemical foaming with uniform fine cells, which overcame the shortcomings of traditional poly(styrene‐b‐butadiene‐b‐styrene) tri‐block copolymer (SBS). The preparation of conductive foams filled by the carbon black was studied. After the detail investigation of cross‐linking and foaming behaviors using moving die rheometer, the optimal foaming temperature was determined at 180°C with a complex accelerator for foaming agent. Scanning electron microscopy (SEM) images shown that the cell bubbles of conductive foam were around 30–50 µm. The conductivity of foams was tested using a megger and a semiconductor performance tester. SEM images also indicated that the conductivity of foams was mainly affected by the distribution of carbon black in the cell walls. The formation of the network of the carbon black aggregates had a contribution to perfect conductive paths. It also found that the conductivity of foams declined obviously with the foaming agent content increasing. The more foaming agent led to a sharp increasing of the number of cells (from 2.93 × 10⁶ to 6.20 × 10⁷ cells/cm³) and a rapid thinning of the cell walls (from 45.3 to 1.4 µm), resulting in an effective conductive path of the carbon black no forming. The conductive soft foams with the density of 0.48–0.09 g/cm³ and the volume resistivity of 3.1 × 10³?2.5 × 10⁵ Ω cm can be easily prepared in this study. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41644.     

Role of the interface in the melt‐rheology properties of linear low‐density polyethylene/low‐density polyethylene blends: Effect of the molecular architecture of the dispersed phase

We studied the melt linear viscoelastic and elongational properties of blends consisting of a Ziegler–Natta linear low‐density polyethylene (LLDPE) and different LDPEs. The weight fraction of the LDPE used in the blends was 15%. The linear viscoelastic characterization was performed at different temperatures for all of the blends to determine the thermorheological behavior in the melt state. The blends fulfilled the time–temperature superposition but exhibited a broad linear viscoelastic response, which was further than that expected for miscible blends and even immiscible systems with a sharp interface. A rheological study of the application of the Palierne model revealed that in addition to the droplet shape relaxation, another mechanism was present at lower frequencies. We discuss the results by hypothesizing a strong interaction between the high‐molecular‐weight linear fraction of the LLDPE matrix and a fraction of molecules of the dispersed phase, which formed a thick interface with its own viscoelastic properties. A clear change in this additional mechanism was observed, depending on the dispersed minor‐phase properties, which produced an impact on the processing of the blends, and more precisely, on the values of the melt strength in the melt‐spinning experiments. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of sintering on processability vis-a-vis microcellular foaming of ultrahigh molecular weight polyethylene

Processing of ultrahigh molecular weight polyethylene (UHMWPE) involves sintering due to its high melt strength and no flowability above melting temperature. Variations in compression molding pressure during sintering lead to chain rearrangement at the sintered interphase and the boundary, affecting foamability. UHMWPE particles are sintered using compression molding; samples are prepared at two different pressures: UHPE-HP (80 bar) and UHPE-LP (40 bar) at 180°C. The sintering phenomenon of UHMWPE particles is observed through an optical microscope, and their effect on foaming was observed. UHPE-HP foams are systematically studied to obtain the foaming window. Increasing foaming pressure (80–120 bar) made UHPE-HP foams softer (0.350–0.219 g/cm³) with varying average cell size (26.37–46.1 μm) and foam cell density (3.98 × 10⁷–1.06 × 10⁸ cells/cm³), and compression modulus decreased from 9 to 5.4 MPa. DMA results showed a strong dependence of stiffness on crystallinity, and foamed samples exhibit higher stiffness than their unfoamed counterpart. The storage modulus for foamed samples decreases with increase in the gas content. The UHPE-LP foam is relatively softer, with a lower foam density (0.233 g/cm³), a higher expansion ratio, bigger average foam cells (35.13 μm), and lower foam cell density (9.33 × 10⁷ cells/cm³). This is due to constrained crystallinity at the interphase and pre-existing cavities, favoring the foaming.     

Effects of clay dispersion on the foam morphology of LDPE/clay nanocomposites

Intercalated and exfoliated low‐density polyethylene (LDPE)/clay nanocomposites were prepared by melt blending with and without a maleated polyethylene (PE‐g‐MAn) as the coupling agent. Their morphology was examined and confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of clay content and dispersion on the cell morphology of nanocomposite foams during extrusion foaming process were also thoroughly investigated, especially with a small amount of clay of 0.05–1.0 wt%. This research shows the optimum clay content for achieving microcellular PE/clay nanocomposite foams blown with supercritical CO₂. It is found that < 0.1 wt% of clay addition can produce the microcellular foam structure with a cell density of > 10⁹ cells/cm³ and a cell size of ～ 5 μm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2129–2134, 2007     

Lightweight investigation of long chain branching polypropylene/cellulose nanofiber composite foams

Long chain branching polypropylene (LCBPP)/cellulose nanofiber (CNF) composite foams were prepared by short shot foam injection molding method and their morphological, mechanical, and thermal properties were also investigated. The cellular structure of LCBPP/CNF composite foams was improved with weight reduction (WR) ratios increasing. The cell densities of LCBPP/CNF composite foams were dramatically increasing with WR ratios rising. More, the fine and uniform cellular structures were obtained due to the incorporation of CNF. The highest cell density, specific flexural strength, and modulus could achieved 20 × 10³ cell/cm², 65 MPa/(g/cm³) and 2.7 GPa/(g/cm³), respectively. Furthermore, the specific Charpy impact strengths were also higher than the ones of solid samples. At last, the thermal insulation properties were discussed accordingly.     

Extrusion of polystyrene nanocomposite foams with supercritical CO2

Intercalated and exfoliated polystyrene/nano‐clay composites were prepared by mechanical blending and in situ polymerization respectively. The composites were then foamed by using CO₂ as the foaming agent in an extrusion foaming process. The resulting foam structure is compared with that of pure polystyrene and polystyrene/talc composite. At a screw rotation speed of 10 rpm and a die temperature of 200°C, the addition of a small amount (i.e., 5 wt%) of intercalated nano‐clay greatly reduces cell size from 25.3 to 11.1 μm and increases cell density from 2.7 × 10⁷ to 2.8 × 10⁸ cells/cm³. Once exfoliated, the nanocomposite exhibits the highest cell density (1.5 × 10⁹ cells/cm³) and smallest cell size (4.9 μm) at the same particle concentration. Compared with polystyrene foams, the nanocomposite foams exhibit higher tensile modulus, improved fire retardance, and better barrier property. Combining nanocomposites and the extrusion foaming process provides a new technique for the design and control of cell structure in microcellular foams.     

Cell structure and dynamic properties of injection molded polypropylene foams

The cell structure and properties of branched and linear polypropylene (PP) foams containing organically modified nanoclay and maleic anhydride grafted polypropylene (PPMA) have been thoroughly investigated. X-ray diffraction (XRD) and melt rheometry were used to identify the structure and linear viscoelastic properties of the nanocomposites, as well as the effectiveness of two different compatibilizers. These nanocomposites were used in injection molding to investigate their foamability and the influence of experimental conditions such as chemical foaming agent concentration, shot size, back pressure, injection speed, as well as melt temperature and different injection methods on the resulting cell structure of the foams. Quite different results were obtained with the linear and the branched PP. While the foamability of the branched PP was intrinsically good, that of the linear one could largely be improved by modifying its rheological properties and favoring nucleation through the addition of nanoclay. The effect of cell structure on the dynamic mechanical properties of the foams was also investigated using dynamic mechanical analysis (DMA). POLYM. ENG. SCI., 47:1070–1081, 2007. © 2007 Society of Plastics Engineers     

Effect of crystalline structure on the cell morphology and mechanical properties of polypropylene foams fabricated by core-back foam injection molding

Foam injection molding (FIM) is an advanced technology for preparing lightweight plastic foams, but its inferior mechanical performance remains a challenge. In this study, microcellular injection-molded β-polypropylene (β-PP) foams with high ductility were successfully prepared by combing the β-nucleating agent with controllable temperature field. Foaming results showed that the microcellular β-PP foams exhibiting a cell size of about 8 μm and cell density over 10⁸ cells/cm³ were prepared with a crystalline diameter approximately 5 μm, while PP foams had a rather large cell size approximately 150 μm and low cell density of 10⁵ cells/cm³ with 30 μm crystalline size. As a result, this significant improvement in cell structure as well as the crystalline size lead to a significant increment of 86% for the ductility of β-PP foams. This work offers a facile strategy to prepare injection-molded foams with desirable mechanical properties for their wide range of applications, such as automotive construction and consumer electronics.     

Development and physico‐mechanical behavior of LDPE–sisal prepreg‐based composites

Low‐density polyethylene (LDPE)‐coated sisal fiber prepreg was prepared by using solution coating process. These coated fiber prepregs were consolidated to make composites having different weight fraction of sisal fibers in a hot compression‐molding machine. This experimental study reveals that higher loading of sisal fiber up to 57wt% in LDPE–sisal composites is possible by this technique. Mechanical and abrasive wear characteristics of these composites were determined. The tensile strength of composites increased with the increase in sisal fiber concentration. Coating thickness of LDPE was varied by changing the viscosity of LDPE–xylene solution that manifested to different weight fraction of fiber in sisal–LDPE composites. Mechanical, dynamic mechanical, and abrasive wear characteristics of these composites were determined. The tensile strength and modulus of sisal composites reached to 17.4 and 265 MPa, respectively, as compared to 7.1 and 33MPa of LDPE. Storage modulus of sisal composites LD57 reached to 2.7 × 10⁹ MPa at 40°C as compared to 8.1 × 10⁸ MPa of LDPE. Abrasive wear properties of LDPE and its composites were determined under multi‐pass mode; pure LDPE showed minimum specific wear rate. The specific wear rate of composites decreased with the sliding distance. Increase of coated sisal fiber content increased the specific wear rate at all the sliding distances, which has been explained on the basis of worn surface microstructures observed by using SEM. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Morphology,rheology, and mechanical properties of dynamically cured EPDM/PP blend: Effect of curing agent dose variation

The structure development, rheological behavior, viscoelastic, and mechanical properties of dynamically cured blend based on the ethylene–propylene–diene terpolymer (EPDM) and polypropylene (PP) with a ratio of 60/40 by weight were studied. The variation of two‐phase morphology was observed and compared as the level of curing agent was increased. Meanwhile, as the level of curing agent increased, viscosity as a function of shear stress always increased at a shear stress range of 2.2 × 10⁴ to 3.4 × 10⁵ Pa at the temperature of 200°C, yet viscosity of the blend approached each other at high shear stress. Dynamic mechanical spectra at different temperatures show that dynamic modulus (E′) of the blend exhibits two drastic transitions corresponding to glass transition temperature (T_g) of EPDM and T_g of PP, respectively. In the blends T_gs of EPDM increase and T_gs of PP almost remain unchangeable with an increase in curing agent level. Tensile strength increased, yet elongation at break decreased as the level of curing agent is increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 357–362, 2004     

Thermal and rheological properties of mLLDPE/LDPE blends

The thermal and rheological properties of two types of metallocene‐catalyzed linear low‐density PEs (mLLDPEs) and two LDPEs, as well as their blends, were studied using differential scanning calorimeter (DSC) measurements and rheometry. The DSC results showed that the mLLDPE‐1 based on the hexene comonomer is immiscible with both LDPEs in crystalline states, whereas the mLLDPE‐2 based on the octene comonomer is miscible with the LDPEs. This suggests that increasing the length of short chains in mLLDPEs can promote the miscibility of mLLDPE/LDPE blends. The linear viscoelastic properties confirmed the immiscibility of the mLLDPE‐1 with the LDPEs in the molten state, and the miscibility of mLLDPE‐2 with LDPEs. In addition, the Palierne [1] emulsion model provided good predictions of the linear viscoelastic data for both miscible and immiscible PE blends. However, as expected, the low‐frequency data showed a clear influence of the interfacial tension on the elastic modulus of the blends for the immiscible blends. POLYM. ENG. SCI., 45:1254–1264, 2005. © 2005 Society of Plastics Engineers     

Melt foamability of reactive extrusion‐modified poly(ethylene terephthalate) with pyromellitic dianhydride using supercritical carbon dioxide as blowing agent

By reactive extrusion with pyromellitic dianhydride (PMDA), foamable poly(ethylene terephthalate) (PET) was obtained, which achieved a maximum intrinsic viscosity of 1.36 dL/g with PMDA content 0.8 wt%. Dynamic shear rheological properties were measured to characterize the structure evolution of modified PET. And the Avrami analysis was extended for the non‐isothermal crystallization process of modified PET, which relates to cell stabilization in the melt foaming process. Based on the batch foaming process with supercritical carbon dioxide as blowing agent, broad foaming temperature windows were obtained for PETs modified with 0.8 and 0.5 wt% PMDA, in which PET foams with the expansion ratio between 10 and 50 times, the cell diameter between 15 and 37 μm, and the cell density between 6.2 × 10⁸ and 1.6 × 10⁹ cells/cm³ were controllably produced. POLYM. ENG. SCI., 55:1528–1535, 2015. © 2014 Society of Plastics Engineers