Séverine A.E. Boyer

The role of nucleating agents in high-pressure-induced gamma crystallization in isotactic polypropylene

Nucleation of the γ-form in isotactic polypropylene (PP) under high pressure was investigated. Three nucleating agents were used to nucleate crystallization of PP under atmospheric pressure: commercial Hyperform HPN-20E from Milliken Chemical, poly(tetrafluoroethylene) particles nucleating the α-form, and calcium pimelate nucleating the β-form. Crystallization of neat PP and PP with addition of 0.2xa0wt% of the nucleating agents was studied. Specimens were either kept at 200xa0°C under pressure of 200xa0MPa for time ranging from 2xa0min to 4xa0h or for 15xa0min under pressure ranging from 1.3 to 300xa0MPa. After cooling to ambient temperature and releasing the pressure, the specimens were analyzed by DSC, WAXD, and PLM to have an insight into the structure andxa0to determine a crystallinity level and contents of crystallographic forms. Both α-nucleating agents strongly nucleated crystallization of PP under high pressure in the γ-form, whereas the β-nucleating agent had only a slight effect. The results show the possibility to use nucleating agents to nucleate the γ-form of PP under high pressure.

CRISTAPRESS: An optical cell for structure development in high-pressure crystallization

An original optical high-pressure cell, named CRISTAPRESS, has been especially designed to investigate phase transitions of complex liquids, i.e., polymers, polymer blends, nano-composites, etc. The design of the cell is based on the optical properties of morphological entities through in situ light depolarizing microscopic observations. Pressure up to 200 MPa with a fine temperature control up to 300u2009°C can be applied. A striking advantage of this cell is the possibility to select the pressure transmitting medium that can be water, silicone oil, a fluid in the supercritical state, etc. The potential of the novel technique was demonstrated by carrying out time-resolved measurements during polymer crystallization induced by water pressure. These preliminary experimental investigations permit to discriminate the role of the barometric and thermal histories on the kinetics of polymer growth, as well as on the subsequent morphologies. It should lead to new reliable crystallization kinetics models.

Thermodynamics and Thermokinetics to Model Phase Transitions of Polymers over Extended Temperature and Pressure Ranges Under Various Hydrostatic Fluids

A scientific understanding of the behaviour of polymers under extreme conditions of temperature and pressure becomes inevitably of the utmost importance when the objective is to produce materials with well-defined final in-use properties and to prevent the damage of materials during on-duty conditions. The proper properties as well as the observed damages are related to the phase transitions together with intimate pattern organization of the materials. Thermodynamic and thermokinetic issues directly result from the thermodynamic independent variables as temperature, pressure and volume that can stay constant or be scanned as a function of time. Concomitantly, these variables can be coupled with a mechanical stress, the diffusion of a solvent, and/or a chemically reactive environment. A mechanical stress can be illustrated in a chemically inert environment by an elongation and/or a shear. Diffusion is typically described by the sorption of a solvent. A chemical environment is illustrated by the presence of a reactive environment as carbon dioxide or hydrogen for example. Challenging aspects are polymer pattern multi scale organizations, from the nanometric to the macrometric scale, and their importance regarding industrial and technological problems, as described in the state of the art in Part 2. New horizons and opportunities are at hands through pertinent approaches, including advanced ad hoc experimental techniques with improved modelling and simulation. Four striking illustrations, from the interactions between a solvent and a polymer to the growth patterns, are illustrated in Part 3.

Crystallization of Polymers in Processing Conditions: An Overview

Abstract In polymer processing, crystallization generally occurs in complex, inhomogeneous and coupled mechanical (flow, pressure), thermal (cooling rate, temperature gradient) and geometrical (surface of processing tools) conditions. A first route to understand crystallization in processing conditions is to design model experiments to isolate the specific influence of a given parameter. The emphasis will be laid here on the influence of: (i) shear flow through rheo-optical measurements using the commercial RheoScope module, (ii) high cooling rates obtained with the modified hot stage Cristaspeed (up to 2 000 °C min−1) and (iii) high pressures in the original Cristapress cell (up to 200 MPa). Numerical simulation is also a useful tool to understand and predict the coupled phenomena involved in crystallization. Based on Avramis ideas and equations, a general differential formulation of overall crystallization kinetics has been proposed by Haudin and Chenot (2004). It is able to treat both isothermal and non-isothermal cases, and has been extended to crystallization in a limited volume without and with surface nucleation inducing transcrystallinity.

Carbon dioxide as a porogen on self-organized nano-structure of amphiphilic side-chain type liquid crystalline di-block copolymers

Liquid and supercritical carbon dioxide (LCO2, SCCO2) have been used as a porogen to swell self-organized nano-structure of an amphiphilic side-chain type liquid crystalline PEO–b-PMA(Az) copolymer. Carbon dioxide interacts with the hydrophilic PEO domain rather than the PMA matrix. The preferential interactions of PEO component with carbon dioxide result in a solvent-induced surface topology changes and the generation of a nano-porous template. The area density of the nano-pores is identical to that of the original copolymer film while keeping the hexagonally packed PEO nano-scale organization. Since the process is based on the gases diffusion on solid surfaces under controlled temperature and since neither polymer block is fundamentally altered by the sorption effect, the process is fully reversible. The supercritical condition of CO2 treatment gives rise to the highest expansion of pre-patterned PEO cylinders and consecutively induces the retardation of PEO crystallization. This versatile thermo-diffuso approach would be applied to a wide variety of pre-patterned copolymers systems for nano-templating applications requiring nano-scale features sizes and/or area feature densities.

Analysis of the No-Flow Criterion Based on Accurate Crystallization Data for the Simulation of Injection Molding of Semi-Crystalline Thermoplastics

Abstract It is well known in practice that the shape and dimensions of injected parts are highly dependent on the packing-holding stage. A major problem in semi-crystalline polymers is the prediction of the solidified layer, whose thickness has an important effect on shrinkage and warpage. We propose a pragmatic approach based on the concept of no-flow temperature. This temperature should be related to crystallization temperature, but the choice is not easy because it depends on cooling rate and pressure which are functions of time and position. The objective of the work is to evaluate the sensitivity of an injection molding computation to the no-flow temperature and to evaluate the relevance of its choice. The crystallization temperature of an isotactic polypropylene is determined as a function of cooling rate and pressure in laboratory experiments. The pressure dependence is measured using the original Cristapress cell. As a case study, we simulate the filling and post-filling of a plate mold using Rem3D, a 3D code for injection molding. Three no-flow temperatures and two sets of parameters for temperature dependence of viscosity are tested. Their respective influences on the pressure evolution are shown, and the crystallization temperature calculated a posteriori using the experimental material data is compared to the “arbitrary” no-flow temperature.

An Original Model Experiment Designed for High-Pressure Crystallization with a Polymer Processing Concern

A comprehensive understanding of the inherent link between in-situ growth kinetics of a polymer spherulite and high-pressure constraints under controlled temperature is concerned. As a matter of fact, while the link with temperature is well illustrated, little comprehensive study has been conducted to quantify the effect of pressure. This is yet required to model ‘extreme’ polymer processing conditions.Mainly, the experimental set-ups developed to reproduce the pressure effect can be classified into four families: “simple” cells, dilatometric set-ups, differential thermal analysis and diamond anvil plus in-situ measurement. In this context, an original model experiment, named CRISTAPRESS, has been constructed. The cell design exploits the optical properties of semi-crystalline spherulites. Time-resolved light depolarizing microscopic observations are conducted concomitantly with a fine PVT control, for high pressure up to 200 MPa and temperature up to 300 °C. The physical analysis of isothermal and isobaric holding of a model polymer shows the influence of temperature and pressure on the key kinetic parameters of crystallization, i.e., the growth rate and the number of activated nuclei, as well as on the subsequent morphologies. Simple modeling dealing with the Avrami equation and the Hoffman & Lauritzen theory is established.