1、BRITISH STANDARD BS EN 60450:2004 Incorporating amendment no. 1 Measurement of the average viscometric degree of polymerization of new and aged cellulosic electrically insulating materials The European Standard EN 60450:2004, incorporating amendment A1:2007, has the status of a British Standard ICS
2、17.220.99; 29.035.01 BS EN 60450:2004 This British Standard was published under the authority of the Standards Policy and Strategy Committee on 16 August 2004 BSI 2007 ISBN 978 0 580 57762 8 National foreword This British Standard is the UK implementation of EN 60450:2004, incorporating amendment A1
3、:2007. It is identical with IEC 60450:2004, incorporating amendment 1:2007. It supersedes BS 7836:1996 which is withdrawn. The start and finish of text introduced or altered by amendment is indicated in the text by tags !“. Tags indicating changes to IEC text carry the number of the IEC amendment. F
4、or example, text altered by IEC amendment 1 is indicated by !“. The UK participation in its preparation was entrusted by Technical Committee GEL/15, Insulating material, to Subcommittee GEL/15/5, Methods of test. A list of organizations represented on this subcommittee can be obtained on request to
5、its secretary. This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with a British Standard cannot confer immunity from legal obligations. Amendments issued since publication Amd. No. Date Comments 1738
6、8 31 October 2007 See national forewordEUROPEAN STANDARD EN 60450 NORME EUROPENNE EUROPISCHE NORM June 2004 CENELEC European Committee for Electrotechnical Standardization Comit Europen de Normalisation Electrotechnique Europisches Komitee fr Elektrotechnische Normung Central Secretariat: rue de Sta
7、ssart 35, B - 1050 Brussels 2004 CENELEC - All rights of exploitation in any form and by any means reserved worldwide for CENELEC members. Ref. No. EN 60450:2004 E ICS 17.220.99; 29.035.01 English version Measurement of the average viscometric degree of polymerization of new and aged cellulosic elec
8、trically insulating materials (IEC 60450:2004) Mesure du degr de polymrisation moyen viscomtrique des matriaux isolants cellulosiques neufs et vieillis usage lectrique (CEI 60450:2004) Messung des durchschnittlichen viskosimetrischen Polymerisationsgrades von neuen und gealterten cellulosehaltigen E
9、lektroisolierstoffen (IEC 60450:2004) This European Standard was approved by CENELEC on 2004-06-01. CENELEC members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration.
10、 Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the Central Secretariat or to any CENELEC member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translat
11、ion under the responsibility of a CENELEC member into its own language and notified to the Central Secretariat has the same status as the official versions. CENELEC members are the national electrotechnical committees of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Ge
12、rmany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. +A1 June 2007 Foreword The text of document 15E/229/FDIS, future edition 2 of IEC 60450, prepared by SC 15E
13、, Methods of test, of IEC TC 15, Insulating materials, was submitted to the IEC-CENELEC parallel vote and was approved by CENELEC as EN 60450 on 2004-06-01. The following dates were fixed: latest date by which the EN has to be implemented at national level by publication of an identical national sta
14、ndard or by endorsement (dop) 2005-03-01 latest date by which the national standards conflicting with the EN have to be withdrawn (dow) 2007-06-01 Annex ZA has been added by CENELEC. _ Endorsement notice The text of the International Standard IEC 60450:2004 was approved by CENELEC as a European Stan
15、dard without any modification. _ Page2 EN60450:2004 Foreword to amendment A1 The text of document 112/49/CDV, future amendment 1 to IEC 60450:2004, prepared by IEC TC 112, Evaluation and qualification of electrical insulating materials and systems, was submitted to the IEC-CENELEC Parallel Unique Ac
16、ceptance Procedure and was approved by CENELEC as amendment A1 to EN 60450:2004 on 2007-06-01. The following dates were fixed: latest date by which the amendment has to be implemented at national level by publication of an identical national standard or by endorsement (dop) 2008-03-01 latest date by
17、 which the national standards conflicting with the amendment have to be withdrawn (dow) 2010-06-01 _ Endorsement notice The text of amendment 1:2007 to the International Standard IEC 60450:2004 was approved by CENELEC as an amendment to the European Standard without any modification. _ 60450 IEC:200
18、4 3 CONTENTS INTRODUCTION.4 1 Scope.5 2 Normative references .5 3 Terms, definitions and symbols 5 3.1 Terms and definitions5 3.2 Symbols 6 4 Principle.7 5 Apparatus and reagents .7 6 Specimens .8 6.1 Preparation of specimens8 7 Experimental procedure9 7.1 Measurement of water content of paper.9 7.2
19、 Determination of viscosity .9 8 Test report15 Annex A (normative) Cuen solution16 Annex B (normative) Preparation of Cuen solution.17 Annex C (normative) Procedure for the verification of the ratio Cu En c c of the Cuen solution20 Annex D (informative) Numerical values of the product v . c as a fun
20、ction of v s according to Martins formula 21 Bibliorgaphy54 Tlbae 1 Symbols 31 Tabl 2 e v PD valseu fo spcemine .91 Tabl.D e 1 . c sa f aunciton fo s (k 0 =1,4). 6 iFugre 1 hC mecial srtucrutfo e cellulsoe 21 iFugre 2 bU belohde viscmorete tueb72 3egaP 65400 EI2:C400 3 TNOCENTS TNIRODTCUOIN.9 1 cSpo
21、e.11 2 roNmtaive referecnse.11 3 Termsfed ,intiiosn and symslob 11 .31 Terms dna definiitons 11 .32 Symbols31 4 rPinciple.51 5 Apparatus and reagenst.51 6 Scepmisne.71 .61 rPperataion fo spcemines71 7 xErepminetal rpcoerude91 .71 eMsarumetne fo awter cotnent fo paper.91 .72 eDretminatoin fo viscsoti
22、y.91 8 Test report13 Annex A (ronmative) Cune soluiton33 Annex B (ronmative) rPerapaitofo n Cuen soultion.53 Annxe ( Cnromtaiev) rPocderue for htv ereificaitofo n the rtaio uC nE c c fo htC euen solutino14 Annxe ( Difnromtaiv)e Nmureicav laulse fo htrp edocu tv . c sa a fucntino fo v s cacording to
23、Maritns formalu 34 Bibliography22 Table 1 Symbols 6 Table 2 v DP values of specimen .9 Table D.1 . c as a function of s(k = 0,14). 43 Figure 1 Chemical structure of cellulose 5 Figure 2 Ubbelohde viscometer tube13 3egaP 4002:05406NE Annex ZA (normative) Normative references to international publicat
24、ions with their corresponding European publications . 23 Page3 EN 60450:2004 EN 60450:200460450 IEC:2004 9 INTRODUCTION Experience has indicated the need for an improved description of the experimental method for the reproducible determination of the average viscometric degree of polymerization of n
25、ew and aged cellulosic electrically insulating material. The major error appears to arise from oxidative degradation occurring during processing and effluxing. Other significant factors include the need to ensure that all of the material is dissolved and used, as well as the effect of the speed of e
26、ffluxing. 6egaP 4002:05406NE Page4 EN 60450:200460450 IEC:2004 11 MEASUREMENT OF THE AVERAGE VISCOMETRIC DEGREE OF POLYMERIZATION OF NEW AND AGED CELLULOSIC ELECTRICALLY INSULATING MATERIALS 1 Scope This International standard describes a standardized method for the determination of the average visc
27、ometric degree of polymerization ( DP ) of new and aged cellulosic electrically insulating materials. It may be applied to all cellulosic insulating materials such as those used in transformer, cable or capacitor manufacturing. The methods described can also be used for the determination of the intr
28、insic viscosity of solutions of chemically modified kraft papers, provided that these dissolve completely in the selected solvent. Caution should be taken if the method is applied to loaded kraft papers. NOTE Within a sample of material, all the cellulose molecules do not have the same degree of pol
29、ymerization so that the mean value measured by viscometric methods is not necessarily the same as that which may be obtained by, for instance, osmotic or ultra centrifuging methods. 2 Normative references The following referenced documents are indispensable for the application of this document. For
30、dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. IEC 60814, Insulating liquids Oil-impregnated paper and pressboard Determination of water by automatic coulometric Karl Fischer titration ISO 28
31、7, Paper and board Determination of moisture content Oven-drying method ISO 3105, Glass capillary kinematic viscometers Specifications and operating instructions 3 Terms, definitions and symbols For the purposes of this document, the following terms, definitions and symbols apply. 3.1 Terms and defi
32、nitions 3.1.1 degree of polymerization of a cellulose molecule number of anhydrous- -glucose monomers, C 6 H 10 O 5 , in the cellulose molecule NOTE Figure 1 shows the chemical structure of cellulose. CH 2 OH O HO HO OH O HO OH O O O CH 2 OH CH 2 OH HO OH OH n 2 IEC 424/04Figure 1 Chemical structure
33、 of cellulose 7egaP 4002:05406NE Page5 EN 60450:200460450 IEC:2004 13 3.1.2 Cuen 1 mol/l aqueous solution of bis(ethylenediamine)copper(II) hydroxide Cu(H 2 NCH 2 CH 2 NH 2 ) 2 (OH) 2 . CAS 14552-35-3 1NOTE In some countries the abbreviation CED is used for bis(ethylenediamine)copper(II) hydroxide.
34、3.1.3 paper cellulosic electrically insulating material, such as paper, presspaper, pressboard and components made thereof NOTE In the present document such paper is termed “paper”. 3.2 Symbols Symbols used in this standard are shown in Table 1. Table 1 Symbols Symbol Definition Mark Houwink constan
35、t of the cellulose monomer c CuMolarity of copper in Cuen solution c EnMolarity of ethylenediamine in Cuen solution C 0 , C 1and C 2Constants for viscometer tubes 0, 1 and 2 respectively c Concentration of solution DP Average viscometric degree of polymerization Kinematic viscosity of solution v 0Ki
36、nematic viscosity of solvent K Mark Houwink characteristic constant of the polymer/solvent system k Constant in Martins formula m DMass of dry paper m TMass of swollen paper in tared vessel m H 2 OMass of added water H 2 ODensity of water v H 2 OVolume of added water v CuVolume of added Cuen Intrins
37、ic viscosity s vSpecific viscosity t 1A , t 1BEfflux time for tests A and B on dissolved specimen 1 t 2A , t 2BEfflux time for tests A and B on dissolved specimen 2 t 0A , t 0BEfflux time for tests A and B on pure solvent t 0Efflux time for diluted Cuen solvent (50 % Cuen and 50 % water) t SEfflux t
38、ime for Cuen dissolved specimen 1Chemical Abstracts Service (CAS) Registry numbers 8egaP 4002:05406NE Page6 EN 60450:200460450 IEC:2004 15 4 Principle The specific viscosity s of a solution of the paper in Cuen is determined. From this result the intrinsic viscosity of the solution is deduced, and f
39、rom this the degree of polymerization is calculated. NOTE Solutions of cellulose are non-Newtonian fluids. Their viscosity decreases as the flow velocity increases (sometimes known as “structural viscosity”). Although the viscosity of dilute solutions varies only slightly with the gradient of the ve
40、locity modulus, the use of conditions outside those specified in this standard may result in unacceptable errors. Specific viscosity sis defined by solvent of viscosity solvent of viscosity solution paper of viscosity s = (1) Intrinsic viscosity is defined by = c c s 0 lim (2) where c is the concent
41、ration of the solution. The average viscometric degree of polymerization DP (the ratio of the mean molecular mass indicated viscometrically to the molecular mass of the monomeric unit) is related to the intrinsic viscosity by the equation: DP K = (3) K and being characteristic Mark Houwink coefficie
42、nts of the polymer-solvent system (paper/Cuen) and of the monomer respectively. The intrinsic viscosity is calculated from the specific viscosity s vand the concentration c by Martins empirical formula: c = 10 s(4) where k is Martins constant. For kraft papers k = 0,14. 5 Apparatus and reagents NOTE
43、 1 Apparatus and reagents for the preparation of Cuen are given separately in Annexes A and B. During the analysis, unless otherwise specified, use only reagents of recognized analytical grade and only distilled /de-ionized water or equivalent quality. A glass fronted, thermostatically controlled ba
44、th, suitable for the immersion of the viscometer tubes, capable of maintaining a temperature of 20 C to within 0,1 K and fitted with appropriate means for illuminating the tubes. It shall be fitted with a means of displaying the temperature to within an accuracy of 0,05 K. NOTE 2 To obtain the requi
45、red degree of temperature stability, it may be necessary to use a refrigeration unit in addition to the bath heater. 9egaP 4002:05406NE Page7 EN 60450:200460450 IEC:2004 17 Calibrated capillary type viscometer tubes according to ISO 3105 with a capillary constant of 0,005 or 0,01. Non calibrated tub
46、es can be used as long as the viscosities of the Cuen solvent and solution of paper in Cuen are measured in the same tube. A timer/stopwatch capable of measuring to within an accuracy of 0,1 s. Suitable blender or grinder to “activate” the paper sample to allow dissolution. Suitable vials (typically
47、 25 ml to 50 ml) with lids (not paper) that make an effective seal for the preparation of paper/Cuen solution. Alternative glass containers can be used. However, these shall be sealed during dissolution to minimize oxidative degradation of the Cuen. Cuen (see Annex A). Distilled or de-ionized water.
48、 Low oxygen content nitrogen supply (minimum 99,9 % nitrogen). Acetone minimum 99,0 % pure. Pentane or hexane minimum 99,0 % . 20 % aqueous nitric acid. Vented drying oven thermostatically controlled to 105 C 2 K. Analytical balance capable of weighing 20 g to within 0,1 mg. Soxhlet extractor. Pipette to deliver 0,1 ml. Mechanical shaker capable of holding the glass vials used to prepare the paper/Cuen solutions or a magnetic stirrer can be used to dissolve the paper/Cuen solution. 6 Specimens 6.1 Preparation of
