Biaxial deformation behavior and mechanical properties of a polypropylene/clay nanocomposite

Polymer nanocomposites offer the potential of enhanced properties such as increased modulus and barrier properties to the end user. Much work has been carried out on the effects of extrusion conditions on melt processed nanocomposites but very little research has been conducted on the use of polymer nanocomposites in semi-solid forming processes such as thermoforming and injection blow molding. These processes are used to make much of today’s packaging, and any improvements in performance such as possible lightweighting due to increased modulus would bring signi?cant bene?ts both economically and environmentally. The work described here looks at the biaxial deformation of polypropylene–clay nanocomposites under industrial forming conditions in order to determine if the presence of clay affects processability, structure and mechanical properties of the stretched material. Melt compounded polypropylene/clay composites in sheet form were biaxially stretched at a variety of processing conditions to examine the effect of high temperature, high strain and high strain rate processing on sheet structure
and properties.

A biaxial test rig was used to carry out the testing which imposed conditions on the sheet that are representative of those applied in injection blow molding and thermoforming. Results show that the presence of clay increases the yield stress relative to the un?lled material at typical processing temperatures and that the sensitivity of the yield stress to temperature is greater for the ?lled material. The stretching process is found to have a signi?cant effect on the delamination and alignment of clay particles (as observed by TEM) and on yield stress and elongation at break of the stretched sheet.

Evolution of Clay Morphology in Polypropylene/Montmorillonite Nanocomposites upon Equi-biaxial Stretching: A Solid-State NMR and TEM Approach

Solid-state NMR and TEM were used to quantitatively examine the evolution of clay morphology upon equibiaxial stretching of polypropylene/montmorillonite (PP-MMT) nanocomposites up to a stretch ratio (?= final length/initial length) of 3.5. 1 H spin-lattice relaxation times were measured by the saturation-recovery sequence. For the nanocomposites, initial portions of the magnetization recovery
curves (e~20 ms) were found to depend on v t, indicative of diffusion-limited relaxation and in agreement with calculations based on estimates of the spin-diffusion barrier radius surrounding the paramagnetic centers in the clay, the electron-nucleus coupling constant, and the spin-diffusion coefficient. Initial slopes of these magnetization recovery curves directly correlated with the fraction of clay/polymer interface. New clay surface was exposed as a near linear function of strain. Long-time portions of the magnetization recovery curves yielded information on the average interparticle separations, which decreased slowly before reaching a plateau at ?=~2.5 as particles aligned. TEM images supported these findings and were used to define and quantify degrees of exfoliation and homogeneity from the NMR data. Exfoliation, defined as (platelets/ stack)-1, increased from 0.38 (unstretched) to 0.80 at ? = 3.5 for PP-MMT nanocomposites stretched at
150 C and 16 s-1. A lower stretch temperature, 145 C, which is slightly below melting onset, led to an exfoliation degree of 0.87 at ?= 2.8, consistent with the ability of higher melt viscosities to allow for higher shear stress transfer. Exposure of new clay surface is attributed to aggregate breakup and orientation at low strains (? e ~2) and to platelets sliding apart at higher strains.

Structure-Property Relationships in Biaxially Deformed Polypropylene Nanocomposites

Semi-solid forming processes such as thermoforming and injection blow moulding are used to make much of today’s packaging. As for most packaging there is a drive to reduce product weight and improve properties such as barrier performance. Polymer nanocomposites offer the possibility of increased modulus
(and hence potential product light weighting) as well as improved barrier properties and are the subject of much research attention. In this particular study, polypropylene–clay nanocomposite sheets produced via biaxial deformation are investigated and the structure of the nanocomposites is quantitatively determined in order to gain a better understanding of the influence of the composite structure on mechanical properties. Compression moulded sheets of polypropylene and polypropylene/Cloisite 15A nanocomposite (5 wt.%) were biaxially stretched to different stretching ratios, and then the structure of
the nanocomposite was examined using XRD and TEM techniques. Different stretching ratios produced different degrees of exfoliation and orientation of the clay tactoids. The sheet properties were then investigated using DSC, DMTA, and tensile tests .It was found that regardless of the degree of exfoliation or
orientation, the addition of clay has no effect on percentage crystallinity or melting temperature, but it has an effect on the crystallization temperature and on the crystal size distribution. DMTA and tensile tests show that both the degree of exfoliation and the degree of orientation positively correlate with the dynamic mechanical properties and the tensile properties of the sheet.

Viscoelastic Material Models of Polypropylene for Thermoforming Applications

Polypropylene (PP), a semi-crystalline material, is typically solid phase thermoformed at temperatures associated with crystalline melting, generally in the 150° to 160°Celsius range. In this very narrow thermoforming window the mechanical properties of the material rapidly decline with increasing temperature and these large changes in properties make Polypropylene one of the more difficult materials to process by thermoforming. Measurement of the deformation behaviour of a material under processing conditions is particularly important for accurate numerical modelling of thermoforming processes. This paper presents the findings of a study into the physical behaviour of industrial thermoforming grades of Polypropylene. Practical tests were performed using custom built materials testing machines and thermoforming equipment at Queen′s University Belfast. Numerical simulations of these processes were constructed to replicate thermoforming conditions using industry standard Finite Element Analysis software, namely ABAQUS and custom built user material model subroutines. Several variant constitutive models were used to represent the behaviour of the Polypropylene materials during processing. This included a range of phenomenological, rheological and blended constitutive models. The paper discusses approaches to modelling industrial plug-assisted thermoforming operations using Finite Element Analysis techniques and the range of material models constructed and investigated. It directly compares practical results to numerical predictions. The paper culminates discussing the learning points from using Finite Element Methods to simulate the plug-assisted thermoforming of Polypropylene, which presents complex contact, thermal, friction and material modelling challenges. The paper makes recommendations as to the relative importance of these inputs in general terms with regard to correlating to experimentally gathered data. The paper also presents recommendations as to the approaches to be taken to secure simulation predictions of improved accuracy.

Influence of molten-state annealing on the phase structure and crystallization behaviour of high impact polypropylene copolymer

The phase structure evolution of high impact polypropylene copolymer (IPC) during molten-state annealing and its influence on crystallization behaviour were studied. An entirely different architecture of the IPC melt was observed after being annealed, and this architecture resulted in variations of the crystallization behaviour. In addition, it was found that the core-shell structure of the dispersed phase was completely destroyed and the sizes of the dispersed domains increased sharply after being annealed at 200 degrees C for 200 min. Through examination of the coarseness of the phase morphology using phase contrast microscopy (PCM), it was found that a co-continuous structure and an abnormal 'sea-island' structure generally appeared with an increase in annealing time. The original matrix PP component appeared as a dispersed phase, whereas the copolymer components formed a continuous 'sea-island' structure. This change is ascribed to the large tension induced by solidification at the phase interface and the great content difference between the components. When the temperature was reduced the structure reverted to its original form. With increasing annealing time, the spherulite profiles became more defined and the spherulite birefringence changed from vague to clear. Overall crystallization rates and nucleation densities decreased, but the spherulite radial growth rates remained almost constant, indicating that molten-state annealing mainly affects the nucleation ability of IPC, due to a coarsened microstructure and decreased interface area. (C) 2011 Elsevier Ltd. All rights reserved.