Heritage PVC objects: Understanding the diffusion-evaporation of plasticizers

IF 7.4 2区 化学 Q1 POLYMER SCIENCE Polymer Degradation and Stability Pub Date : 2025-05-01 Epub Date: 2025-02-15 DOI:10.1016/j.polymdegradstab.2025.111270
Tjaša Rijavec , Sonia Bujok , Sergii Antropov , G. Asher Newsome , Josep Grau-Bové , Irena Kralj Cigić , Krzysztof Kruczała , Łukasz Bratasz , Matija Strlič
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Abstract

The predominance of diffusion-evaporation of plasticizers in heritage collections is investigated and an analytical method of studying surface exudates based on dry swabbing is introduced for an in-situ museum survey. Most plasticized heritage PVC objects exhibit no visible surface exudates, indicating plasticizer loss is governed by the diffusion-evaporation process and not phase-separation. A new approach to analyzing the diffusion-evaporation process based on experimental data is presented to model plasticizer loss at room conditions. Experiments conducted with historical PVC objects exposed to accelerated degradation for up to 8 weeks at moderate temperatures enable the monitoring of plasticizer loss. Evaluation of the mass loss and the chromatographically determined plasticizer content allows us to determine the temperature dependence of the diffusion coefficient and the surface emission coefficient. Three representative groups of heritage PVC are identified and the activation energies for the coupled diffusion-evaporation processes are used to determine the rate-limiting step and introduce a general model for predicting plasticizer loss from the time of storage, temperature, and thickness of an object. The model can be used as part of risk assessment in heritage PVC collections.
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传承PVC物件:了解增塑剂的扩散-蒸发
研究了增塑剂在文物藏品中扩散蒸发的优势,并介绍了一种基于干拭法的表面渗出物分析方法,用于博物馆现场调查。大多数增塑剂遗产PVC物体没有可见的表面渗出物,表明增塑剂损失是由扩散蒸发过程控制的,而不是相分离。提出了一种基于实验数据分析扩散蒸发过程的新方法,以模拟室温条件下增塑剂的损失。对历史上的PVC物体进行的实验在中等温度下暴露于加速降解长达8周,可以监测增塑剂的损失。通过对质量损失和色谱测定增塑剂含量的评估,我们可以确定扩散系数和表面发射系数对温度的依赖关系。识别了三组具有代表性的传统聚氯乙烯,并利用扩散-蒸发耦合过程的活化能来确定限速步长,并引入了从储存时间、温度和物体厚度预测增塑剂损失的通用模型。该模型可作为文物聚氯乙烯收藏品风险评估的一部分。
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来源期刊
Polymer Degradation and Stability
Polymer Degradation and Stability 化学-高分子科学
CiteScore
10.10
自引率
10.20%
发文量
325
审稿时长
23 days
期刊介绍: Polymer Degradation and Stability deals with the degradation reactions and their control which are a major preoccupation of practitioners of the many and diverse aspects of modern polymer technology. Deteriorative reactions occur during processing, when polymers are subjected to heat, oxygen and mechanical stress, and during the useful life of the materials when oxygen and sunlight are the most important degradative agencies. In more specialised applications, degradation may be induced by high energy radiation, ozone, atmospheric pollutants, mechanical stress, biological action, hydrolysis and many other influences. The mechanisms of these reactions and stabilisation processes must be understood if the technology and application of polymers are to continue to advance. The reporting of investigations of this kind is therefore a major function of this journal. However there are also new developments in polymer technology in which degradation processes find positive applications. For example, photodegradable plastics are now available, the recycling of polymeric products will become increasingly important, degradation and combustion studies are involved in the definition of the fire hazards which are associated with polymeric materials and the microelectronics industry is vitally dependent upon polymer degradation in the manufacture of its circuitry. Polymer properties may also be improved by processes like curing and grafting, the chemistry of which can be closely related to that which causes physical deterioration in other circumstances.
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