How the morphology of poly (vinyl chloride) compounds affects toughness and weatherability

Suspension polymerized poly (vinyl chloride) (PVC) is made up of 150 μm grains. Within these grains are 2 μm primary particles which apparently become the flow units under low melt temperature (175°C) extrusion conditions. The 2 μm particles are visible by light transmission microscopy by shearing the extruded product between glass slides after swelling in acetone or by electron transmission microscopy of ultrathin microtomed samples. This product, made up of 2 μm flow units, is brittle and has poor toughness retention upon weathering. At higher melt temperatures (185–190°C), agglomeration of the 2 μm particles occurs, giving a rough surface but tougher product. At higher melt temperatures, a continuous melt occurs, leading to a smooth surface and tough product with excellent toughness retention upon weathering.     

Plasticization of PVC with ethylene copolymer resins

Ethylene copolymer resin (ECR) modifiers, designed to be soluble in all proportions in PVC, form a wide variety of plasticized PVC blends. These solid, high molecular weight (Mw > 250,000) resin modifiers, unlike conventional liquid plasticizer, exhibit outstanding permanence in PVC. Compounding procedures, used for liquid plasticized PVC, are sometimes inadequate to produce homogeneous blends of PVC/ECR. A number of effective melt compounding techniques and a new family of ECR modifiers have been developed to produce homogeneous blends exhibiting many outstanding properties, including fluids/chemical resistance, high/low-temperature service, and weatherability.     

The effect of crystallites on the rheological properties of microphase‐separated PVC‐PBA‐PVC triblock copolymers obtained by single electron transfer‐degenerative chain transfer living radical polymerization

Linear and nonlinear rheological properties of poly(vinyl chloride) (PVC)‐poly(n‐butyl acrylate)‐PVC triblocks of different compositions, obtained by single electron transfer‐degenerative chain transfer living radical polymerization, are investigated, focusing on the effect of crystallites. Dynamic mechanical thermal analysis results show the existence of two glass transition temperatures, denoting microphase segregation. However, rather than phase separation, it is the presence of two types of crystals that melt at T_m1 = 127 ± 0.8°C and T_m2 = 185 ± 2°C, respectively, the factor that determines the rheological response of the copolymers. To the difference with PVC homopolymers, extrusion flow measurements at very low temperatures (T = 100°C) are possible with the copolymers. A change in the viscosity‐temperature dependence is observed below and above the lowest melting temperature. Notwithstanding the microphase separation and the presence of crystallites, experiments carried out in conditions similar to industrial processing reveal a remarkable viscosity reduction for our copolymers with respect to PVC obtained by single electron transfer‐degenerative chain transfer living radical polymerization, conventional PVC, and PVC/[diethyl‐(2‐ethylhexyl) phthalate] compounds. Extrudates free of surface instabilities are obtained at low extrusion temperatures, such as 90–100°C. J. VINYL ADDIT. TECHNOL., 21:24–32, 2015. © 2014 Society of Plastics Engineers     

Preparation and characterization of double‐MF shell microPCMs used in building materials

A kind of double‐shell heat energy storage microcapsule was prepared used melamine formaldehyde (MF) resin as shell material, and the properties of the microcapsules were investigated. A phase change material, with melt point of 24°C and phase transition heat of 225.5J/g, was used as core. The microcapsules would be used in indoor walls to regulate the temperature and save energy. The surface morphological structure was examined by means of scanning electron microscopy. The strength of the shell was evaluated through observing the surface change after pressure by means of scanning electron microscopy. The average diameter of the microcapsules was 5 μm ～ 10 μm. Diameter of 1 μm ～ 5 μm could also be obtained by using different stirring speeds. The globular surface was smooth and compact. The thickness was 0.5 μm ～ 1 μm. Also, the melting point of the microcapsules was 24.7°C, nearly equal to the pure phase change material. The DSC results make clear that the polymer shell of the microcapsules does not influence the properties of the phase change material. It was also found that the avoiding penetration property of the double‐shell microcapsules was better than that of single shell, and the average diameter of 5 μm was better than 1 μm. With the increase of ratio of the core material, the compactability decreased, and the shell thickness decreased. The mass ratio of core and shell was 3 : 1 to ensure that the microcapsules had good heat storage function. The measuring test showed that the microcapsules did not rupture at a pressure of 1.96 × 10⁵ Pa. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1755–1762, 2005     

Poly (vinyl chloride) processing morphology

This paper describes how morphology of PVC changes in the Brabender mixing head. At the range of temperatures used for PVC processing, the Brabender torque-time curve shows minimum torque and maximum torque. The minimum torque is associated with a breakdown of 150 μm PVC grains and 10 μm agglomerates resulting in the release of the 1μm primary particles. The torque increases from minimal interaction between primary particles to the point where primary particles agglomerate at maximum torque so that fibriles can be formed when PVC samples are swollen in acetone and sheard. Further heating reduces the viscosity resulting in lower torque even though residual primary particles still exist with much particle to particle interaction. Primary particle structure disappears at about 215° C with complete melting.     

Development and characterization of reactively extruded PVC/polystyrene blends

PVC/PS blends are obtained through a reactive extrusion–polymerization method by the absorption of a solution of styrene monomer, initiator, and a crosslinking agent in commercial suspension‐type porous polyvinyl chloride (PVC) particles, forming a dry‐blend with a relatively high monomer content. These PVC/styrene dry‐blends are reactively polymerized in a twin‐screw extruder in the melt state. They do not contain monomer residues as detected by GC. The transparency, fracture surface morphology, thermal stability, rheology and static and dynamic mechanical properties of these blends are compared to physical PVC/PS blends at similar compositions. Owing to the high polymerization temperature (180°C), short PS chains are formed in the reactive extrusion process. These short chains are dispersed both as a separate phase of ～2 μm particles (recognized by SEM) and also as molecularly dispersed chains enhancing plasticization and compatibilization. The molecularly dispersed short PS chains tend to plasticize the PVC phase, reducing its melt viscosity and glass transition temperature. The content of the short PS chains forming the dispersed separate PS particles is too low for DMTA to detect a separate T_g. Thus, reactively extruded PVC/PS blends exhibit single T_g transitions at lower temperatures compared with the neat PVC. Migration of the PVC's low‐molecular‐weight additives (lubricants and thermal stabilizer) to the PS phase is observed in the physical PVC/PS blends, causing antiplasticization of the PS phase. This results in both reduction of the T_g and an increase in the thermal stability of the PS phase in the physical PVC/PS blends. Comparing TGA thermograms of reactively extruded and physical PVC/PS indicates that the PS formed in the extruder is different from the commercial PS. This can stem from various chemical reactions that can take place in the studied reactive polymerization process. Polym. Eng. Sci. 44:1473–1483, 2004. © 2004 Society of Plastics Engineers.     

Microstructural evolution in bone china

Abstract

Phase and microstructural evolution in model bone china bodies was determined by XRD and electron microscopy of quenched samples fired for 3 h at 600–1500°C. Unfired but shaped bone china comprised bone ash and clay agglomerates (≤70 μm) in a matrix of smaller (from submicron to 10 μm) mixed clay, feldspar, and bone ash particles. The unfired microstructure and subsequent phase evolution is believed to be strongly dependent on the extent of prior mixing. On firing, the clay component dehydroxylated to metakaolin at ～550°C. Metastable sanidine formed from decomposition of the feldspar component above 600°C and dissolved at 1100°C. The bone ash com ponent decomposed into β-TCP and lime (and/or Ca²⁺ and O^2- ions) beginning at ～800°C. CaO from the bone ash reacts with the clay decomposition products forming liquid and anorthite at ～900°C. Liquid formation is due to reaction of CaO with feldspar and clay relict grains and is discussed in terms of the CaO–P₂O₅–Al₂O₃ ternary phase diagram. Above 1200°C pure bone ash relicts contained small (5–10 μm) β-TCP crystals, CaO penetrated clay relicts contained anorthite, and mixed clay–bone–feldspar regions contained both anorthite and larger (>50 μm) β-TCP crystals in calcium aluminosilicate glass. The major phase in the clay relicts was anorthite although a few elongated (～100 nm) needles resembling mullite in composition and morphology also crystallised in samples fired to 1100°C and grew to ～30 μm in length at 1300°C.     

Crystallization and melting behavior of polyester/clay nanocomposites

Polyester/clay nanocomposites were prepared by melt compounding with different clay loadings. Comparing against neat polyester resins, the crystallization and multiple melting behavior of the nanocomposites was investigated by differential scanning calorimetry (DSC) and X‐ray diffraction (XRD). Nanoclay filler is an effective heterogeneous nucleating agent, as evidenced by a decrease and an increase in the crystallization temperature for both cold and melt crystallization of polyesters, respectively. The degree of crystallinity was found to increase with increasing clay content, due to heterogeneous nucleation effects by the addition of a nanofiller. For the annealed samples, multiple melting peaks were always observed for both neat polyester and its nanocomposites. The origins of the multiple melting behavior are discussed, based on the DSC and XRD results. Interestingly, an ‘abnormal’ high‐temperature endothermic peak (T_{m, 3}) at about 260 °C was observed when the nanocomposite samples were annealed at higher temperatures (eg ≥240 °C). The constrained polyester crystals formed within intercalated clay platelets due to confinement effects were probably responsible for this melting event at these higher temperatures. Copyright © 2004 Society of Chemical Industry     

Thermal stability of epoxidized soybean oil and its absorption and migration in poly(vinylchloride)

Thermal analyses of epoxidized soybean oil (ESO) were conducted and showed that it was stable up to temperatures as high as 240–260°C in air‐free environment. The solubility and transport characteristics of ESO in poly(vinylchloride) (PVC) were also investigated under various conditions. The absorption study showed that the resin had a void volume of ～0.3 cm³/g. Furthermore, ESO was found to be sufficiently soluble in the PVC matrix to function as an effective plasticizer, with equilibrium solubility of 72 g/100 g PVC at 80°C and 163 g/100 g PVC at 120°C. The absorption of ESO in PVC grains was a three step process comprising “induction,” “swelling,” and “saturation” periods. Torque rheometer studies showed that higher mixer temperature and/or speed facilitated uptake of plasticizer in PVC and ultimate fusion. Migration studies of plasticized and stabilized PVC compositions showed no change in mass at 40°C, but increasingly greater mass loss as the temperature was raised up to 120°C. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Viscosity ratio effects in the compounding of low viscosity,immiscible fluids into polymeric matrices

Many low viscosity, immiscible fluids are difficult to incorporate into polymer matrices because of thermodynamic immiscibility and a large mismatch of melt viscosities. In this investigation, a model system was used to determine the mechanisms and kinetics of mixing in such formulations. The model systems consisted of a series of different molecular weight polyethylenes in polystyrene. The viscosity ratio, η(polyethylene)/η(polystyrene), at 180°C and 100 s⁻¹ was varied from 0.7 to 0.003. Phase inversion was observed during the compounding of these formulations. The phase inversion was associated with a transition from low to high mixing torque during compounding. This change was primarily due to an increase in the blend viscosity caused by the morphological transformation. The melting behavior during compounding depended on the melt viscosity of the polyethylene. A critical viscosity ratio of ≈ 0.1 exists below which softening of the polystyrene, and thus mixing of the two components, was greatly retarded. Even at very low concentrations, low viscosity polyethylene can have a significant effect on the processing behavior. Effects of mixer set temperature, degree of fill, and polyethylene particle size were explored. The roles of thermal conduction and mechanical energy input were evaluated in the melting regime of the process.     

Synthesis and properties of ultralow dielectric constant porous polyimide films containing trifluoromethyl groups

In this research, a series of porous copolyimide (co‐PI) films containing trifluoromethyl group (CF₃) were facilely prepared via a phase separation process. The co‐PI were synthesized by the reaction of benzophenone‐3,3′,4,4′‐tetracarboxylic dianhydride (BTDA) with two diamines of 4,4′‐diaminodiphenyl ether (ODA) and 3‐trifluoromethyl‐4,4'‐diaminodiphenyl ether (FODA) with various molar ratios. The flexible and tough porous co‐PI films with about 300 μm thickness and 8～10 μm average diameter could be obtained by solution casting conveniently. The thermal properties of the obtained porous co‐PI films were excellent with a glass transition temperature at 270 °C ～ 280 °C and only 5% weight loss in temperature from 530 °C to 560 °C under nitrogen atmosphere. In addition, the dielectric and hydrophobic properties of porous co‐PI films were remarkably improved owing to the presence of trifluoromethyl groups (CF₃) in the polymer chains. Moreover, our synthesized porous co‐PI films also showed good mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44494.     

Cooling and annealing properties of copolymer-type polyacetals and its crystallization behavior

Copolymer-type polyacetals (POMs) that have been cooled at seven different rates from the melt at 180°C to the solid at 23°C show average spherulite diameters from 10 to 25 μm on an etched fracture surface using scanning electron microscopy (SEM). The wide-angle X-ray diffraction (WAXD) of POM displays a degree of crystallinity ranging from 60 to 66% by applying the two-phase model. From studies of mechanical properties, physical properties, and dielectric dissipation factor (tan δ), we found that POM with a faster cooling rate shows looser packing and smaller spherulites on the fracture surface than that with a slower cooling rate. This conclusion is in agreement with the observations made on SEM and WAXD. DSC measurements were used to measure the heat of fusion, melting point, and crystallization temperature of POMs. An equilibrium melting temperature was estimated from the Hoffman–Weeks plot. The overall crystallization kinetics of POMs were analyzed by the Avrami equation. Results for the Avrami exponent n, between 2 and 3, indicate small disklike spherulites following nucleation growth kinetics. Annealing the cooled POM at 150°C results in recrystallization featuring a significant increase in the average diameter of spherulites in SEM.     

Photonic Sintering of Aerosol Jet Printed Lead Zirconate Titanate (PZT) Thick Films

Lead Zirconate Titanate (PZT) is a commonly used piezoelectric material due to its high piezoelectric response. We demonstrate a new method of printing and sintering micro‐scale PZT films with low substrate temperature increase. Self‐prepared PZT ink was Aerosol‐Jet printed on stainless steel substrates. After drying for 2 h in vacuum at 200°C, the printed PZT films were divided into two groups. The first group was traditionally sintered, using a thermal process at 1000°C for 1 h in an Argon environment. The second group was photonically sintered using repetitive sub‐msec pulses of high intensity broad spectrum light in an atmospheric environment. The highest measured substrate temperature during photonic sintering was 170.7°C, enabling processing on low melting point substrates. Ferroelectric measurements were performed with a low‐frequency sinusoidal signal. The remanent polarization (P_r) and coercive field (E_c) for thermally sintered PZT film were 17.1 μC/cm² and 6.3 kV/cm, respectively. The photonically sintered film had 32.4 μC/cm² P_r and 6.7 kV/cm E_c. After poling the samples with 20 kV/cm electric field for 2 h at 150°C, the piezoelectric voltage constant (g₃₃) was measured for the two film groups yielding ?16.9 × 10^?3 (V·m)·N^?1 (thermally sintered) and ?17.9 × 10^?3 (V·m)·N^?1 (photonically sintered). Both factors indicate the PZT films were successfully sintered using both methods, with the photonically sintered material exhibiting superior electrical properties. To further validate photonic sintering of PZT on low melting point substrates, the process and measurements were repeated using a polyethylene terephthalate (PET) substrate. The measured P_r and E_c were 23.1 μC/cm² and 5.1 kV/cm, respectively. The g₃₃ was ?17.3 × 10^?3 (V·m)·N^?1. Photonic sintering of thick film PZT directly on low melting point substrates eliminates the need for complex layer transfer processes often associated with flexible PZT transducers.     

Processing and formulation effects on gel levels in flexible PVC extrusions

Gels, or fisheyes, in flexible PVC extruded or calendered products are the ～ 150 μm PVC grains which, for one reason or another, survive the compounding and processing steps to appear as defects on the surface of the profile, sheet, or film. In most applications they are aesthetically objectionable. In other applications, such as medical tubing or blood bags, they are functionally intolerable. Gels are a function of resin and plasticizer selection, processing temperature, residence time at temperature, and shear history. In flexible PVC extrusion, process parameters include cube or pellet versus powder processing, barrel L/D, screw compression ratio, screw RPM, and temperature profile. Choice of resin is, of course critical. Resin morphological parameters of importance include friability, porosity, and absence of glassy particles. Plasticizers vary greatly in their ability to solvate the PVC grain. Various types of dry blend and resin contamination result in large increases in gels.     

Effect of Dispersion Condition of Calcium Carbonate on the Crystallization and Melting Behavior of Polypropylene/CaCO3 Nanocomposites

Polypropylene/calcium carbonate (PP/CaCO₃) nanocomposites were prepared by melt compounding (C-1) and novel compounding process (C-2), respectively. Scanning electronic microscope (SEM) results illustrated that CaCO₃ nanoparticles were well dispersed at nanoscale in C-2, whereas the nanoparticles were mostly aggregate in C-1. Differential scanning calorimetry (DSC) measurements indicated the onset crystallization temperature was increased by 11.4°C and the supercooling wasdecreased by 13.68°C in C-2. A faster crystallization rate, a higher melting point, and a higher degree of crystallization in C-2 were also detected. Polarization light microscope (PLM) photographs showed the spherulites sizes of C-2 were 60 mm, whereas common spherulites with an average size of about 200 mm were observed in both pure PP and C-1. These phenomena demonstrated that the well-dispersed CaCO₃ nanoparticles could result in heterogeneous nucleation effect on PP even at quite low loading Q2 (1.5% wt.).     

Preparation and structural characterization of nanocrystalline poly(vinyl chloride)

This article describes the development of novel nanocrystalline poly(vinyl chloride) (PVC) for potential applications in PVC processes and reports improvements in the mechanical properties and thermal resistance. Before the preparation of nanocrystalline PVC via jet milling, PVC was spray‐treated and heat‐treated to improve its crystallinity. The pulverization and degradation, morphology, crystalline structure, and melting‐point changes of postmodified PVC during jet milling and the relationship between the distributions of the particle size and processing temperature were investigated. X‐ray analysis and density testing indicated increased density and improved crystallinity. The crystalline region of nanocrystalline PVC was less than 80 nm, with a particle size distribution of 5–20 μm and a melting point of less than 128°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 563–569, 2004     

Change of phase composition and morphology of sonochemically synthesised hydroxyapatite nanoparticles with glycosaminoglycans during thermal treatment

Abstract

Based on the preparation of glycosaminoglycans (GAGs) stabilised hydroxyapatite (HAP) nanoparticle suspension via sonochemical synthesis, the change of phase composition and morphology of freeze dried HAP nanoparticles with GAGs was investigated from 500 to 1200°C by TEM, X-ray diffraction, Fourier transform infrared spectroscopy and SEM. Results show that thermal treatment brought the phase transformation and the morphology change of HAP nanoparticles. In the low temperature stage (～650°C), the samples were mainly composed of HAP as main crystalline phase and β-NaCaPO₄ as minor crystalline phase. This phase transformation was mainly attributed to the residues containing sodium derived from combustion of GAGs. The particles were near spherical, and the nanocrystalline nature was retained. In the high temperature stage (650–1200°C), the samples were glass ceramic powders composed of HAP, β-tricalcium phosphate, Na₃Ca₆(PO₄)₅, β-NaCaPO₄ and Na–Ca–P–O glass phase. The grains rapidly grew into larger particles with morphology transformation from rodlike shape to irregular shape and the size increase from (0·1–0·15) × (0·3–0·5) μm to 1·5–10 μm.     

Nylon 66 nanofibers prepared by CO2 laser supersonic drawing

Nylon 66 nanofibers were prepared by irradiating as‐spun nylon 66 fibers with radiation from a carbon dioxide (CO₂) laser while drawing them at supersonic velocities. A supersonic jet was generated by blowing air into a vacuum chamber through the fiber injection orifice. The fiber diameter depended on the drawing conditions used, such as laser power, chamber pressure, laser irradiation point, and fiber supply speed. A nanofiber obtained at a laser power of 20 W and a chamber pressure of 20 kPa had an average diameter of 0.337 μm and a draw ratio of 291,664, and the drawing speed in the CO₂ laser supersonic drawing was 486 m s^?1. The nanofibers showed two melting peaks at about 257 and 272°C. The lower melting peak is observed at the same temperature as that of the as‐spun fiber, whereas the higher melting peak is about 15°C higher than the lower one. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40015.     

Melt‐electrospun fibers obtained from polypropylene/poly(ethylene‐co‐vinyl alcohol)/polypropylene three‐layer films

Production of polypropylene (PP) nanofibers below 1 μm in average diameter is difficult with conventional melt‐spinning. A nozzle‐free melt‐type electrospinning (M‐ESP) system with a line‐like CO₂ laser beam melting device were used to produce PP nanofibers. To achieve the purpose, core [poly(ethylene‐co‐vinyl alcohol) (EVOH)]–clad (PP) nanofibers (average diameter, 0.88 μm) were fabricated from PP/EVOH/PP three‐layer films using the M‐ESP. The core–clad structure was formed by a wrapping phenomenon caused by the difference in the melt flow rates (MFRs) of PP and EVOH melts. Hollow PP nanofibers were obtained from the core–clad nanofibers by extraction of EVOH. Nanofiber diameter and hollow wall thickness could be altered by changing the MFR of the PP melt. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46393.     

Structure and transformation of low‐temperature phases of 1,3‐distearoyl‐2‐oleoyl glycerol

Polymorphic transformations of 1,3‐distearoyl‐2‐oleoyl glycerol (SOS) at low temperatures (10 °C–30 °C) have been studied by time‐resolved synchrotron X‐ray diffraction (XRD) measurements at small and wide angles. Three structures have been identified: α‐phase structure forms by quenching to 10 °C from the liquid state, a metastable structure formed simultaneously with α‐phase and γ‐phase formed at 30 °C during α‐melt‐mediated crystallisation as well as at the pre‐melting temperature (22.5 °C) of the α‐phase when the coexistence of two phases (α and γ) is observed. The metastable structure produces three broad peaks in XRD patterns at small angles (one strong and two weak peaks corresponding to d‐spacings of ～4 nm, ～12 nm and ～1.5 nm respectively) and a peak in X‐ray diffraction patterns at wide angles (0.42 nm). A model is proposed for the metastable structure based on a combination of double‐ and triple‐chain packing of SOS molecules due to the similar length of alkyl chains (stearoyl and oleoyl) in the molecules.