Modelling and parameter estimation of diethyl phthalate partitioning behaviour on glass and aluminum surfaces

The knowledge of the partitioning behaviour of semi-volatile organic compounds (SVOCs), such as phthalates, between different materials and their surrounding air is of extreme importance for quantifying levels of human exposure to these compounds, which have been associated with adverse health effects. Phthalates’ partitioning behaviour also represents a key property for modelling and assessing polymer degradation mechanisms associated with plasticiser loss. However, the characterisation of phthalates partitioning behaviour has been reported only for a limited number of compounds, mainly involving di-2-ethylhexyl phthalate (DEHP), di-isononyl phthalate (DINP) and di-isodecyl phtahalate (DIDP), while the characterisation of diethyl phthalate (DEP) partitioning has been overlooked. As one of the first plasticisers employed in the production of semi-synthetic plastics produced industrially in the late 19th and early 20th century, DEP plays an important role for understanding stability issues associated with historically significant artefacts in museum collections and archives. Here we show that the partitioning behaviour of DEP between borosilicate glass and aluminum surfaces and their surrounding air can be described by an exponential function of temperature, presenting a model to describe this relationship for the first time. Model parameters are estimated using nonlinear regression from experimental measurements acquired using 109 samples which have been equilibrated at different temperatures between 20 and 80 °C in sealed environments. Measured partition coefficients have been predicted accurately by our proposed model. The knowledge of DEP equilibrium distribution between adsorptive surfaces and neighbouring environments will be relevant for developing improved mathematical descriptions of degradation mechanisms related to plasticiser loss

Equilibrium distribution of diethyl phthalate plasticiser in cellulose acetate-based materials: Modelling and parameter estimation of temperature and composition effects

Understanding the transport and fate of semi-volatile organic compounds (SVOCs) such as phthalates in indoor environments is fundamental for quantifying levels of human exposure and preventing adverse health effects. In this context, the partition coefficient of phthalates between indoor built materials and/or consumer goods and the surrounding atmosphere represents a key parameter for determining concentration distributions. Partition coefficients are also of fundamental importance for describing degradation phenomena associated with plasticiser loss from polymeric materials. However, this key parameter has only been determined for a limited number of systems and environmental conditions. Here, we assess the partitioning behaviour of the diethyl phthalate (DEP) plasticiser in cellulose acetate (CA)-based materials for the first time, determining the effects of temperature and plasticiser composition on equilibrium distributions at temperatures between 20 and 80 °C and using CA samples with DEP contents ranging from 6 to 22 wt%. Additionally, we propose a model to describe and quantify the effect of temperature and plasticiser composition, with model parameters being estimated using non-linear regression and measurements from 130 distinct experiments. Finally, we assess the suitability of our developed model to simulate the migration of DEP from CA-based materials

Water sorption and diffusion in cellulose acetate: The effect of plasticisers

The conservation of cellulose acetate plastics in museum collections presents a significant challenge, due to the material's instability. Several studies have led to an understanding of the role of relative humidity (RH) and temperature in the decay process. It is well established that the first decay mechanism in cellulose acetate museum objects is the loss of plasticiser, and that the main decay mechanism of the polymer chain involves hydrolysis reactions. This leads to the loss of sidechain groups and the breakdown of the main polymer backbone. However, interactions between these decay mechanisms, specifically the way in which the loss of plasticiser can modify the interaction between cellulose acetate and water, has not yet been investigated. This research addresses the role of RH, studying the sorption and diffusion of water in cellulose acetate and how this interaction can be affected by plasticiser concentration using Dynamic Vapour Sorption (DVS)

Characterising plasticised cellulose acetate-based historic artefacts by NMR spectroscopy: a new approach for quantifying the degree of substitution and diethyl phthalate contents

As one of the first semi-synthetic plastics produced industrially, cellulose acetate (CA)-based artefacts represent valued items in museum collections and archives which, however, present stability issues. High temperature and relative humidity conditions have long been known to promote changes in CA properties, for instance, due to the deacetylation of CA polymer chains and the loss of plasticiser from the polymer matrix. However, there is a need for improved methods for the quantification of plasticiser loss and CA deacetylation. In this context, this contribution presents a new approach for enabling the investigation of plasticiser loss and deacetylation degradation processes in historic plasticised CA-based artefacts which is based on high-resolution proton nuclear magnetic resonance spectroscopy (1H NMR). The proposed methods allow for simple and fast quantification of diethyl phthalate contents and average degree of substitution (DS), while requiring no need for extractive separation between the plasticiser and the CA polymer matrix prior to analysis. Both methods are demonstrated by their application towards a series of reference samples, historic artefacts and artificially aged plasticised CA materials. Our analysis indicates that plasticiser content and DS can be accurately quantified by using high-resolution 1H NMR and both methods have been compared to analyses performed using infrared spectroscopy

Unveiling the importance of diffusion on the deterioration of cellulose acetate artefacts: The profile of plasticiser loss as assessed by infrared microscopy

Cellulose acetate (CA) artefacts are one of the most valued plastic items in museum collections and are known to present stability issues, with the loss of plasticiser being among the main degradation processes. This study investigates the concentration distribution of diethyl phthalate (DEP) plasticiser throughout the dimensions of CA using infrared microscopy for the first time. Artificial ageing experiments using reference and historic CA plasticised with DEP were performed to assess the change in the concentration profiles as a function of ageing time. Our analysis indicates that the plasticiser loss from CA artefacts is likely controlled by its diffusion, resulting in a concentration gradient in which lower plasticiser contents are observed at the external layers of the material

A comparative evaluation of the effect of internet-based CME delivery format on satisfaction, knowledge and confidence

<p>Abstract</p> <p>Background</p> <p>Internet-based instruction in continuing medical education (CME) has been associated with favorable outcomes. However, more direct comparative studies of different Internet-based interventions, instructional methods, presentation formats, and approaches to implementation are needed. The purpose of this study was to conduct a comparative evaluation of two Internet-based CME delivery formats and the effect on satisfaction, knowledge and confidence outcomes.</p> <p>Methods</p> <p>Evaluative outcomes of two differing formats of an Internet-based CME course with identical subject matter were compared. A Scheduled Group Learning format involved case-based asynchronous discussions with peers and a facilitator over a scheduled 3-week delivery period. An eCME On Demand format did not include facilitated discussion and was not based on a schedule; participants could start and finish at any time. A retrospective, pre-post evaluation study design comparing identical satisfaction, knowledge and confidence outcome measures was conducted.</p> <p>Results</p> <p>Participants in the Scheduled Group Learning format reported significantly higher mean satisfaction ratings in some areas, performed significantly higher on a post-knowledge assessment and reported significantly higher post-confidence scores than participants in the eCME On Demand format that was not scheduled and did not include facilitated discussion activity.</p> <p>Conclusions</p> <p>The findings support the instructional benefits of a scheduled delivery format and facilitated asynchronous discussion in Internet-based CME.</p

Internet-based medical education: a realist review of what works, for whom and in what circumstances

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