Improvements in the Use of Attenuated Total Reflection Fourier Transform Infrared Dichroism for Measuring Surface Orientation in Polymers

Author:

Everall Neil J.1,Bibby Arran1

Affiliation:

1. ICI Research and Technology Centre, P.O. Box 90, Wilton, Middlesbrough, Cleveland, TS90 8JE, U.K. (N.J.E.); and Graseby-Specac Ltd., River House, 97 Cray Avenue, St. Mary Cray, Orpington, Kent, BR5 4HE, U.K. (A.B.)

Abstract

Improvements in the use of attenuated total reflection (ATR) Fourier transform infrared (FT-IR) dichroism for measuring surface orientation in polymer films are described, with poly(ethylene terephthalate) (PET) as an example material. It is shown that normalizing band intensities relative to a nondichroic band, prior to calculating dichroic ratios, eliminates the need to maintain identical contact areas/pressures when removing, rotating, and reclamping samples to the ATR element, which has been a major historical drawback to this technique. The normalization is vital; it makes the calculated dichroic ratios largely insensitive to variations in sample/prism contact area, and less sensitive to uncertainties in the refractive indices and birefringence of the polymer. For PET, it is shown that the birefringence can be neglected in the analysis, and a single approximate refractive index used. This is a significant benefit since the birefringence will vary as a function of orientation and crystallinity. Polymers that are much more birefringent than PET can also be analyzed by using the formalism described in this paper, provided that the three independent indices are known. This paper is presented in two parts; first, equations are derived which allow the calculation of all second-order orientation parameters ( P200, P220, P202, and P222), and the averaged squared direction cosines, from the normalized ATR dichroic ratios. Second, we show how a single-reflection diamond ATR unit is an ideal tool for this work, since it allows small, hard, or irregularly shaped samples to be examined without fear of damaging the ATR element. We illustrate the technique using data obtained from a series of uniaxially drawn films, and one biaxially drawn film, using a commercially available accessory. From these data, orientation parameters were calculated as a function of draw ratio and compared with those obtained from specular-reflectance FT-IR and birefringence analysis of the same samples. The method should be applicable to any polymer provided that (1) a suitable nondichroic band is available for normalization and (2) the largest polymer refractive index lies well below that of the ATR element (2.4 in the case of diamond). It must be realized that condition 1 is not trivial; careful investigation is required to identify truly nondichroic bands (if any exist for the polymer of interest).

Publisher

SAGE Publications

Subject

Spectroscopy,Instrumentation

同舟云学术

1.学者识别学者识别

2.学术分析学术分析

3.人才评估人才评估

"同舟云学术"是以全球学者为主线,采集、加工和组织学术论文而形成的新型学术文献查询和分析系统,可以对全球学者进行文献检索和人才价值评估。用户可以通过关注某些学科领域的顶尖人物而持续追踪该领域的学科进展和研究前沿。经过近期的数据扩容,当前同舟云学术共收录了国内外主流学术期刊6万余种,收集的期刊论文及会议论文总量共计约1.5亿篇,并以每天添加12000余篇中外论文的速度递增。我们也可以为用户提供个性化、定制化的学者数据。欢迎来电咨询!咨询电话:010-8811{复制后删除}0370

www.globalauthorid.com

TOP

Copyright © 2019-2024 北京同舟云网络信息技术有限公司
京公网安备11010802033243号  京ICP备18003416号-3