1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS ISO 15063:2011Plastics Polyols for use in theproduction of polyurethanes Determination of hydroxylnumber by NIR spectroscopyBS ISO 15063:2011 BRITISH STANDARDNational foreword
2、This British Standard is the UK implementation of ISO 15063:2011.The UK participation in its preparation was entrusted to TechnicalCommittee PRI/42, Fibre reinforced thermosetting plastics andprepregs.A list of organizations represented on this committee can beobtained on request to its secretary.Th
3、is publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. BSI 2011ISBN 978 0 580 53942 8ICS 83.080.10Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under
4、 the authority of theStandards Policy and Strategy Committee on 30 November 2011.Amendments issued since publicationDate Text affectedBS ISO 15063:2011Plastics Polyols for use in the production of polyurethanes Determination of hydroxyl number by NIR spectroscopyPlastiques Polyols pour la production
5、 de polyurthannes Dtermination de lindice dhydroxyle par spectroscopie dans le proche infrarouge ISO 2011Reference numberISO 15063:2011(E)Second edition2011-09-15ISO15063INTERNATIONAL STANDARDBS ISO 15063:2011ISO 15063:2011(E)COPYRIGHT PROTECTED DOCUMENT ISO 2011All rights reserved. Unless otherwise
6、 specified, no part of this publication may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or ISOs member body in the country of the requester.ISO copyright offi
7、ceCase postale 56 CH-1211 Geneva 20Tel. + 41 22 749 01 11Fax + 41 22 749 09 47E-mail copyrightiso.orgWeb www.iso.orgPublished in Switzerlandii ISO 2011 All rights reservedBS ISO 15063:2011ISO 15063:2011(E)Contents PageForeword ivIntroduction v1 Scope 12 Normative references .13 Terms and definitions
8、 .14 Principle .14.1 General .14.2 Procedure employed 24.3 Limitations .25 Instrumentation 25.1 General .25.2 Light source and detector .35.3 Spectrometer 35.4 Sampling system .35.5 Software .36 Developing a calibration model .36.1 Selection of calibration materials .36.2 Reference method and refere
9、nce values 46.3 Determining wavelength regions and pathlength 46.4 Reduction of sources of spectral variation 46.5 Multivariate mathematical treatments .56.6 Evaluating calibration models .57 Validation of a multivariate calibration model .58 Calibration transfer .69 Calibration quality control 610
10、Procedure 610.1 General .610.2 Calibration curve .610.3 Measurement 710.4 Illustrative results 711 Precision of NIR estimated values 712 Test report .7Annex A (informative) Illustrative results .8Annex B (informative) NIR spectral measurements 15Annex C (informative) Spectrometers .16Annex D (inform
11、ative) Sampling systems 17Annex E (informative) Selection of calibration materials 18Annex F (informative) Multivariate analysis 20Annex G (informative) Statistical tools used to optimize calibration models 22Annex H (informative) Sources of calibration and analysis error .25Annex I (informative) Mo
12、nitoring the performance of the instrument and calibration model .26Bibliography .27 ISO 2011 All rights reserved iiiBS ISO 15063:2011ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing Int
13、ernational Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison w
14、ith ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.The main task of technica
15、l committees is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote.Attention is drawn to
16、the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights.ISO 15063 was prepared by Technical Committee ISO/TC 61, Plastics, Subcommittee SC 12, Thermosetting materials.This second e
17、dition cancels and replaces the first edition (ISO 15063:2004), which has been technically revised so that the document is no longer a guidance document (as it was in the first edition) but specifies the precise requirements which have to be met when determining the hydroxyl number of a polyol. Subj
18、ect matter which has remained informative in nature has been transferred to informative annexes.ISO 15063:2011(E)iv ISO 2011 All rights reservedBS ISO 15063:2011IntroductionInternational Standards have been published which deal with the determination of hydroxyl values of polyols and surface-active
19、agents using conventional chemistry based on esterification reactions (ISO 14900, ISO 4326, ISO 4327, ISO 4629, ISO 2554 and ISO 6796). This International Standard provides a method for the determination of hydroxyl numbers of polyols using NIR spectroscopy. It is based on ASTM D6342 and on work con
20、ducted by laboratories associated with the Japan Urethane Raw Materials Association.ISO 15063:2011(E) ISO 2011 All rights reserved vBS ISO 15063:2011BS ISO 15063:2011INTERNATIONAL STANDARD ISO 15063:2011(E)Plastics Polyols for use in the production of polyurethanes Determination of hydroxyl number b
21、y NIR spectroscopySAFETY STATEMENT Persons using this document should be familiar with normal laboratory practice. This document does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user to establish appropriate safety and health pr
22、actices and to ensure compliance with any regulatory requirements.1 ScopeThis International Standard specifies a method for the determination of hydroxyl numbers of polyols using NIR (near-infrared) spectroscopy. Definitions and calibration techniques are given. Procedures for selecting calibration
23、materials and for collecting and processing data to develop NIR calibrations are outlined. Criteria for building, evaluating and validating the NIR calibration model are also described. Procedures for sample handling, data gathering and evaluation are included.It is necessary to know the hydroxyl nu
24、mber of polyols in order to properly formulate polyurethane systems. This International Standard is suitable for use in research, quality control, specification testing and process control.2 Normative referencesThe following referenced documents are indispensable for the application of this document
25、. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.ISO 14900, Plastics Polyols for use in the production of polyurethane Determination of hydroxyl numberASTM E1655-05, Standard Practices for
26、 Infrared Multivariate Quantitative Analysis3 Terms and definitionsFor the purposes of this document, the following terms and definitions apply.3.1hydroxyl numberOH#hydroxyl valueHVnumber of milligrams of potassium hydroxide equivalent to the hydroxyl content of 1 g of sample3.2polyurethanepolymer p
27、repared by the reaction of an organic di- or polyisocyanate with compounds containing two or more hydroxyl groups4 Principle4.1 GeneralMultivariate mathematics is applied to correlate the NIR absorbance values for a set of calibration materials to the respective reference hydroxyl number for each ma
28、terial. The resultant multivariate calibration model is then applied to the analysis of unknown materials to provide an estimate of their hydroxyl numbers. ISO 2011 All rights reserved 1BS ISO 15063:2011Methods of optimizing the performance of calibration models are described in Annex G.When there i
29、s any doubt, the hydroxyl value determined by the standard method specified in ISO 14900 shall be used.4.2 Procedure employed4.2.1 Multilinear regression (MLR) analysis, principal-component regression (PCR) and partial least-squares (PLS) regression are the mathematical techniques used for the devel
30、opment of the calibration model.4.2.2 Statistical tests are used to detect outliers during the development of the calibration model. Outliers can include high-leverage samples and materials whose hydroxyl numbers are inconsistent with the model.4.2.3 Validation of the calibration model is performed
31、by using the model to analyse a set of validation materials. The hydroxyl number estimates for the validation set are statistically compared to the reference hydroxyl number for this set to test for agreement of the model with the reference model.4.2.4 Statistical expressions are given for calculati
32、ng the precision and bias of the NIR method relative to the reference method.4.3 Limitations4.3.1 Factors affecting the NIR spectra of the analyte polyols need to be determined before a calibration procedure is started. Chemical structure, interferences, any non-linearities, the effect of temperatur
33、e, and the interactions of the analyte with other test sample components, such as catalyst, water and other polyols, need to be understood in order to properly select calibration material that will model those effects which cannot be adequately controlled.4.3.2 Calibrations are generally considered
34、valid only for the specific NIR instrument used to generate the calibration. Using different instruments (even when made by the same manufacturer) for calibration and analysis can seriously affect the accuracy and precision of the measured hydroxyl number. Procedures used for transferring calibratio
35、ns between instruments are problematic and shall be utilized with caution when using Clause 8. These procedures generally require a completely new validation and a statistical analysis of errors on the new instrument.4.3.3 The analytical results are statistically valid only for the range of hydroxyl
36、 numbers used in the calibration. Extrapolation to lower or higher hydroxyl values can increase the errors and degrade the precision. Likewise, the analytical results are only valid for the same chemical composition as used for the calibration set. A significant change in composition or contaminants
37、 can also affect the results. Outlier detection, as discussed in ASTM E1655, is a tool that can be used to detect the possibility of problems such as those mentioned above.NOTE Refer to Annex B for NIR spectral measurements.5 Instrumentation5.1 GeneralA complete description of all applicable types o
38、f NIR instrument is beyond the scope of this International Standard. Only a general outline of key factors is given here. Consult the instrument manufacturers literature for details of a specific instrument. The implementation of this International Standard requires that the NIR spectrometer has bee
39、n installed in compliance with the manufacturers specifications.ISO 15063:2011(E)2 ISO 2011 All rights reservedBS ISO 15063:20115.2 Light source and detectorTungsten-halogen lamps with quartz envelopes usually serve as the energy sources for NIR instruments. Most of the detectors used for NIR are so
40、lid-state semiconductors. PbS, PbSe, InGaAs and TGS detectors are most commonly used.5.3 SpectrometerMonochromator instruments, filter-wheel instruments, acousto-optic tuneable filter (AOTF) instruments, light-emitting diode (LED) instruments and Fourier transform (FT) instruments are used.NOTE Refe
41、r to Annex C for further details of such instruments.5.4 Sampling systemCuvettes, flow-through cells, transmission probes, immersion probes and attenuated total reflection (ATR) probes can be used in the laboratory or for online instruments, or both.NOTE Refer to Annex D for further details of suita
42、ble sampling systems.5.5 SoftwareThe software used shall have the following capabilities:a) the ability to record all sample identification and spectral data accurately and to access the reference data;b) the ability to record the date and time of day that all spectra and files were recorded or crea
43、ted;c) the ability to move or copy spectra, or both, from file to file;d) the ability to add or subtract spectral data, and to average spectra;e) the ability to perform transformations of log(1/null) optical data (where null is the reflectance) into derivatives or other forms of mathematical treatme
44、nt, and to reverse the transformation;f) the ability to compute multilinear regressions (MLRs), principal-component regressions (PCRs) or partial least-squares (PLS) regressions;g) the ability to store PCR or PLS regression loadings, weights, scores and other desirable data, and to display these dat
45、a for subsequent examination and interpretation;h) the ability to enable the operator to evaluate the calibration model by computing the standard error of validation (SEV), the coefficient of regression and the root mean square deviation (RMSD), and to display various plots;i) the ability to perform
46、 cross-validation automatically;j) the ability to identify outliers;k) the ability to develop and save regression equations and analyse a test sample to calculate a hydroxyl number.NOTE Most NIR instruments provide necessary software for collecting and modelling data. Several non-instrumental compan
47、ies also supply chemometric software packages that can be used to analyse NIR data.6 Developing a calibration model6.1 Selection of calibration materialsMaterials selected for the calibration set shall comply with the following requirements.NOTE Refer to Annex E for guidance on the selection of cali
48、bration materials.ISO 15063:2011(E) ISO 2011 All rights reserved 3BS ISO 15063:2011a) The materials chosen shall include all components which are expected to be present in the samples of interest.b) The materials chosen shall include, and ideally exceed, the expected hydroxyl number range.c) The cal
49、ibration material hydroxyl numbers shall be evenly distributed throughout the calibration range so as to provide a “boxcar” distribution (evenly distributed throughout the range of interest).d) The number of materials chosen shall be large enough to define statistically the relationship between the spectral variables and the hydroxyl numbers to be modelled.Since the appropriate number of materials might vary, depending on the properties of samples, it shall be verified by means of a statistical method.e) The spectra of all materials sh
