IEC 60450:2004
(Main)Measurement of the average viscometric degree of polymerization of new and aged cellulosic electrically insulating materials
Measurement of the average viscometric degree of polymerization of new and aged cellulosic electrically insulating materials
Describes a standardized method for the determination of the average viscometric degree of polymerization (DPv) 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 intrinsic 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 polymerization 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. Experience has indicated the need for improved description of the experimental method. It describes a revised procedure that overcomes the limitations of the first edition.
Mesure du degré de polymérisation moyen viscosimétrique des matériaux isolants cellulosiques neufs et vieillis à usage électrique
Décrit une méthode normalisée pour déterminer le degré de polymérisation moyen viscosimétrique (DPv) des matériaux isolants cellulosiques neufs et vieillis, à usage électrique. Elle peut s'appliquer à tous les matériaux isolants cellulosiques comme ceux utilisés dans la fabrication des transformateurs, des câbles et des condensateurs. Les méthodes décrites peuvent également être utilisées pour déterminer la viscosité intrinsèque des solutions de papiers kraft modifiés chimiquement, pourvu que ceux-ci se dissolvent totalement dans le solvant choisi. Il convient de prendre des précautions si la méthode s'applique à des papiers kraft chargés. Note: Dans un échantillon de matériau, toutes les molécules de cellulose n'ont pas le même degré de polymérisation de sorte que la valeur moyenne mesurée par les méthodes viscosimétriques n'est pas nécessairement la même que celle obtenue, par exemple, par les méthodes par osmose ou par ultra-centrifugation. L'expérience a mis en évidence le besoin d'améliorer la description de la méthode expérimentale. La procédure ainsi revue permet de surmonter les limitations de la première édition.
General Information
Relations
Standards Content (Sample)
NORME CEI
INTERNATIONALE
IEC
INTERNATIONAL
Deuxième édition
STANDARD
Second edition
2004-04
Mesure du degré de polymérisation moyen
viscosimétrique des matériaux isolants
cellulosiques neufs et vieillis à usage électrique
Measurement of the average viscometric degree
of polymerization of new and aged cellulosic
electrically insulating materials
Numéro de référence
Reference number
CEI/IEC 60450:2004
Numérotation des publications Publication numbering
Depuis le 1er janvier 1997, les publications de la CEI As from 1 January 1997 all IEC publications are
sont numérotées à partir de 60000. Ainsi, la CEI 34-1 issued with a designation in the 60000 series. For
devient la CEI 60034-1. example, IEC 34-1 is now referred to as IEC 60034-1.
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NORME CEI
INTERNATIONALE
IEC
INTERNATIONAL
Deuxième édition
STANDARD
Second edition
2004-04
Mesure du degré de polymérisation moyen
viscosimétrique des matériaux isolants
cellulosiques neufs et vieillis à usage électrique
Measurement of the average viscometric degree
of polymerization of new and aged cellulosic
electrically insulating materials
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CODE PRIX
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PRICE CODE
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Международная Электротехническая Комиссия
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– 2 – 60450 CEI:2004
SOMMAIRE
AVANT-PROPOS.4
INTRODUCTION.8
1 Domaine d’application.10
2 Références normatives.10
3 Termes, définitions et symboles .10
3.1 Termes et définitions .10
3.2 Symboles.12
4 Principe.14
5 Appareil et réactifs.14
6 Eprouvettes.16
6.1 Préparation des éprouvettes.16
7 Procédure expérimentale.18
7.1 Mesure de la teneur en eau du papier .18
7.2 Détermination de la viscosité.18
8 Rapport d’essai.30
Annexe A (normative) Solution d’hydroxyde de Cuen.32
Annexe B (normative) Préparation de la solution d’hydroxyde de Cuen.34
c
En
Annexe C (normative) Procédure de vérification du rapport de la solution
c
Cu
d’hydroxyde de Cuen .40
.
Annexe D (informative) Valeurs numériques du produit [v] c en fonction de v ,
s
calculées d’après la formule de Martin .42
Bibliographie.44
Tableau 1 – Symboles .12
Tableau 2 – Valeurs DP de l'éprouvette .18
ν
.
Tableau D.1 – [ν] c en fonction de ν (k = 0,14) .42
s
Figure 1 – Structure chimique d’une molécule de cellulose .10
Figure 2 – Tube de viscosimètre de Ubbelohde.26
60450 IEC:2004 – 3 –
CONTENTS
FOREWORD.5
INTRODUCTION.9
1 Scope.11
2 Normative references.11
3 Terms, definitions and symbols .11
3.1 Terms and definitions .11
3.2 Symbols.13
4 Principle.15
5 Apparatus and reagents.15
6 Specimens.17
6.1 Preparation of specimens.17
7 Experimental procedure.19
7.1 Measurement of water content of paper.19
7.2 Determination of viscosity.19
8 Test report.31
Annex A (normative) Cuen solution.33
Annex B (normative) Preparation of Cuen solution.35
c
En
Annex C (normative) Procedure for the verification of the ratio of the Cuen solution.41
c
Cu
.
Annex D (informative) Numerical values of the product [v] c as a function of v
s
according to Martin's formula .43
Bibliography.45
Table 1 – Symbols .13
Table 2 – DP values of specimen .19
v
.
Table D.1 – [ν] c as a function of ν (k = 0,14). .43
s
Figure 1 – Chemical structure of cellulose .11
Figure 2 – Ubbelohde viscometer tube.27
– 4 – 60450 CEI:2004
COMMISSION ÉLECTROTECHNIQUE INTERNATIONALE
____________
MESURE DU DEGRÉ DE POLYMÉRISATION MOYEN VISCOSIMÉTRIQUE
DES MATÉRIAUX ISOLANTS CELLULOSIQUES NEUFS ET VIEILLIS
À USAGE ÉLECTRIQUE
AVANT-PROPOS
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La Norme internationale CEI 60450 a été établie par le sous-comité 15E: Méthodes d’essai,
du comité d'études 15 de la CEI: Matériaux isolants.
Cette deuxième édition annule et remplace la première édition, publiée en 1974, et constitue
une révision technique. L’expérience a mis en évidence le besoin d’améliorer la description
de la méthode expérimentale. La procédure ainsi revue permet de surmonter les limitations
de la première édition.
Le texte de cette norme est issu des documents suivants:
FDIS Rapport de vote
15E/229/FDIS 15E/235/RVD
Le rapport de vote indiqué dans le tableau ci-dessus donne toute information sur le vote ayant
abouti à l'approbation de cette norme.
60450 IEC:2004 – 5 –
INTERNATIONAL ELECTROTECHNICAL COMMISSION
–––––––––––
MEASUREMENT OF THE AVERAGE VISCOMETRIC DEGREE OF
POLYMERIZATION OF NEW AND AGED CELLULOSIC ELECTRICALLY
INSULATING MATERIALS
FOREWORD
1) The International Electrotechnical Commission (IEC) is a worldwide organization for standardization comprising
all national electrotechnical committees (IEC National Committees). The object of IEC is to promote
international co-operation on all questions concerning standardization in the electrical and electronic fields. To
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patent rights. IEC shall not be held responsible for identifying any or all such patent rights.
International Standard IEC 60450 has been prepared by subcommittee 15E: Methods of test,
of IEC technical committee 15: Insulating materials.
This second edition cancels and replaces the first edition, published in 1974, and constitutes
a technical revision. Experience has indicated the need for improved description of the
experimental method. It describes a revised procedure that overcomes the limitations of the
first edition.
The text of this standard is based on the following documents:
FDIS Report on voting
15E/229/FDIS 15E/235/RVD
Full information on the voting for the approval of this standard can be found in the report on
voting indicated in the above table.
– 6 – 60450 CEI:2004
Cette publication a été rédigée selon les Directives ISO/CEI, Partie 2.
Le comité a décidé que le contenu de cette publication ne sera pas modifié avant 2008.
A cette date, la publication sera
• reconduite;
• supprimée;
• remplacée par une édition révisée, ou
• amendée.
60450 IEC:2004 – 7 –
This publication has been drafted in accordance with the ISO/IEC Directives, Part 3.
The committee has decided that this publication remains valid until 2008. At this date, in
accordance with the committee’s decision, the publication will be
reconfirmed;
withdrawn;
replaced by a revised edition, or
amended.
– 8 – 60450 CEI:2004
INTRODUCTION
L’expérience a mis en évidence le besoin d’améliorer la description de la méthode
expérimentale destinée à obtenir la détermination reproductible du degré de polymérisation
moyen viscosimétrique des matériaux isolants cellulosiques neufs et vieillis à usage
électrique.
Les erreurs principales prennent naissance lors de la dégradation par oxydation qui se produit
pendant le traitement et l’écoulement. Les autres facteurs importants concernent la nécessité
de s’assurer que tout le matériau a été dissous et utilisé ainsi que les effets de la vitesse de
l’écoulement.
60450 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 new
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 effluxing.
– 10 – 60450 CEI:2004
MESURE DU DEGRÉ DE POLYMÉRISATION MOYEN VISCOSIMÉTRIQUE
DES MATÉRIAUX ISOLANTS CELLULOSIQUES NEUFS ET VIEILLIS
À USAGE ÉLECTRIQUE
1 Domaine d’application
La présente Norme internationale a pour objet de décrire une méthode normalisée pour
déterminer le degré de polymérisation moyen viscosimétrique ( DP ) des matériaux isolants
ν
cellulosiques neufs et vieillis, à usage électrique. Elle peut s’appliquer à tous les matériaux
isolants cellulosiques comme ceux utilisés dans la fabrication des transformateurs, des câbles
et des condensateurs. Les méthodes décrites peuvent également être utilisées pour
déterminer la viscosité intrinsèque des solutions de papiers kraft modifiés chimiquement,
pourvu que ceux-ci se dissolvent totalement dans le solvant choisi.
Il convient de prendre des précautions si la méthode s’applique à des papiers kraft chargés.
NOTE Dans un échantillon de matériau, toutes les molécules de cellulose n’ont pas le même degré de
polymérisation de sorte que la valeur moyenne mesurée par les méthodes viscosimétriques n’est pas
nécessairement la même que celle obtenue, par exemple, par les méthodes par osmose ou par ultra-centrifugation.
2 Références normatives
Les documents de référence suivants sont indispensables pour l'application du présent
document. Pour les références datées, seule l'édition citée s'applique. Pour les références
non datées, la dernière édition du document de référence s'applique (y compris les éventuels
amendements).
CEI 60814, Isolants liquides – Cartons et papiers imprégnés d'huile – Détermination de la
teneur en eau par titrage coulométrique de Karl Fischer automatique
ISO 287, Papier et carton – Détermination de l’humidité – Méthode par séchage à étuve
ISO 3105, Viscosimètres à capillaires en verre pour viscosité cinématique – Spécifications et
instructions
3 Termes, définitions et symboles
Pour les besoins du présent document, les termes, définitions et symboles suivants
s’appliquent.
3.1 Termes et définitions
3.1.1
degré de polymérisation d’une molécule de cellulose élémentaire
nombre de monomères d’anhydride de glucose β, C H O , dans une molécule de cellulose
6 10 5
NOTE La Figure 1 décrit la structure chimique de la cellulose.
CH OH
CH OH
2 2
OH
O
O
HO
HO
O
O
HO
HO
OH
O
OH
OH
CH OH
n – 2
IEC 424/04
Figure 1 – Structure chimique d’une molécule de cellulose
60450 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 viscometric degree of polymerization ( DP ) of new and aged cellulosic electrically
ν
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 intrinsic 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 polymerization 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 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 287, 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 definitions
3.1.1
degree of polymerization of a cellulose molecule
number of anhydrous-β-glucose monomers, C H O , in the cellulose molecule
6 10 5
NOTE Figure 1 shows the chemical structure of cellulose.
CH OH
CH OH
OH
O O
HO
HO
O
O
HO
HO
OH
O
OH
OH
CH OH
n – 2
IEC 424/04
Figure 1 – Chemical structure of cellulose
– 12 – 60450 CEI:2004
3.1.2
Cuen
solution aqueuse d'hydroxyde cupri-éthylène-diamine Cu(H NCH CH NH ) (OH) [CAS
2 2 2 2 2 2
14552-35-3] à 1 mol/l
NOTE Dans certains pays l’abréviation CED est utilisée pour l’expression d'hydroxyde cupri-éthylène-diamine
3.3.
3.1.3
papier
matériau isolant cellulosique à usage électrique tel que le papier, le papier comprimé, le
carton comprimé et les matériaux composés de ceux-ci
NOTE Dans le présent document, un tel matériau est nommé « papier ».
3.2 Symboles
Le Tableau 1 liste les symboles utilisés dans la présente norme.
Tableau 1 – Symboles
Symbole Définition
Constante de Mark Houwink du monomère de cellulose
α
Molarité du cuivre dans une solution de Cuen
c
Cu
Molarité de l’éthylène-diamine dans une solution de Cuen
c
En
Constantes pour tubes de viscosimètres 0, 1 et 2, respectivement
C , C et C
0 1 2
Concentration de la solution
c
Degré de polymérisation moyen viscosimétrique
DP
ν
Viscosité cinématique de la solution
ν
Viscosité cinématique du solvant
v
Constante caractéristique de Mark Houwink du système polymère/solvant
K
Constante dans la formule de Martin
k
Masse du papier sec
m
D
m Masse du papier imbibé dans le récipient taré
T
Masse d’eau ajoutée
m
H O
Densité de l’eau
ρ
H O
Volume d’eau ajoutée
v
H O
Volume de Cuen ajouté
v
Cu
Viscosité intrinsèque
[ν]
Viscosité spécifique
v
s
Durée de l’écoulement pour les essais A et B effectués sur l’échantillon n° 1
t t
,
1A 1B
Durée de l’écoulement pour les essais A et B effectués sur l’échantillon n° 2
t t
,
2A 2B
Durée de l’écoulement pour les essai A et B effectués sur le solvant pur
t t
,
0A 0B
Durée de l’écoulement pour solvant Cuen dilué (50 % Cuen et 50 % eau)
t
t Durée de l’écoulement pour échantillon de Cuen dilué
S
———————
Chemical Abstracts Service (CAS) registry numbers ®.
60450 IEC:2004 – 13 –
3.1.2
Cuen
1 mol/l aqueous solution of bis(ethylenediamine)copper(II) hydroxide
Cu(H NCH CH NH ) (OH) . [CAS 14552-35-3]
2 2 2 2 2 2
NOTE In some countries the abbreviation CED is used for bis(ethylenediamine)copper(II) hydroxide.
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 constant of the cellulose monomer
α
c Molarity of copper in Cuen solution
Cu
Molarity of ethylenediamine in Cuen solution
c
En
Constants for viscometer tubes 0, 1 and 2 respectively
C , C and C
0 1 2
c Concentration of solution
Average viscometric degree of polymerization
DP
ν
Kinematic viscosity of solution
ν
v Kinematic viscosity of solvent
K Mark Houwink characteristic constant of the polymer/solvent system
k Constant in Martin's formula
m Mass of dry paper
D
Mass of swollen paper in tared vessel
m
T
Mass of added water
m
H O
Density of water
ρ
H O
v Volume of added water
H O
Volume of added Cuen
v
Cu
Intrinsic viscosity
[ν]
v Specific viscosity
s
Efflux time for tests A and B on dissolved specimen 1
t t
,
1A 1B
Efflux time for tests A and B on dissolved specimen 2
t , t
2A 2B
t t Efflux time for tests A and B on pure solvent
,
0A 0B
t Efflux time for diluted Cuen solvent (50 % Cuen and 50 % water)
t Efflux time for Cuen dissolved specimen
S
———————
Chemical Abstracts Service (CAS) Registry numbers®
– 14 – 60450 CEI:2004
4 Principe
On détermine la viscosité spécifique ν d’une solution de papier Cuen. A partir de ce résultat,
s
on en déduit la viscosité intrinsèque [ν] de la solution, et on calcule le degré de
polymérisation.
NOTE Les solutions de cellulose sont des fluides non newtoniens. Leur viscosité décroît alors que la vitesse du
flux croît (parfois elle est connue sous le nom de « viscosité structurelle »). Même si la viscosité des solutions
diluées varie très peu avec le gradient du module de la vitesse, l’utilisation de conditions autres que celles
spécifiées dans cette norme peut conduire à des erreurs inacceptables.
La viscosité spécifique ν est définie par
s
viscosité de la solution de papier - viscosité du solvant
ν = (1)
s
viscosité du solvant
La viscosité intrinsèque [ν] est définie par
ν
s
ν = lim (2)
c→0 c
où c est la concentration de la solution.
Le degré de polymérisation moyen viscosimétrique DP (rapport entre la masse moléculaire
ν
moyenne indiquée viscosimétriquement et la masse moléculaire de l’unité monomérique) est
lié à la viscosité intrinsèque [ν] par l’équation
α
[υ] = K ⋅ DP (3)
ν
K et α étant respectivement les coefficients caractéristiques de Mark Houwink du système
polymère-solvant (papier/hydroxyde de Cuen) et du monomère.
v
La viscosité intrinsèque [ν] est calculée à partir de la viscosité spécifique s et de la
concentration c par la formule empirique de Martin:
k[v]⋅c
υ = [ν ] ⋅ c ⋅10 (4)
s
où k est la constante de Martin. Pour les papiers kraft k = 0,14.
5 Appareil et réactifs
NOTE 1 L’appareil et les réactifs destinés à la préparation de l’hydroxyde de Cuen sont indiqués séparément aux
Annexes A et B.
Au cours de l’analyse, sauf spécification contraire, utiliser uniquement des réactifs de degré
connu et uniquement de l’eau distillée/déionisée ou de qualité équivalente.
Un bain contrôlé par thermostat dont la paroi frontale est en verre, adapté pour l’immersion
de tubes de viscosimètre, pouvant maintenir une température à 20 °C à ±0,1 K près, et muni
d'un système permettant d'éclairer les tubes. Celui-ci doit être doté d'un moyen prévu pour
afficher la température avec une précision de ±0,05 K.
NOTE 2 Pour obtenir le niveau de stabilité requis en température, il peut être nécessaire d’utiliser un système de
réfrigération en addition au moyen de réchauffement du bain.
60450 IEC:2004 – 15 –
4 Principle
The specific viscosity ν of a solution of the paper in Cuen is determined. From this result the
s
intrinsic viscosity [ν] of the solution is deduced, and from 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 velocity modulus, the use of conditions outside those specified in this standard may result in
unacceptable errors.
Specific viscosity ν is defined by
s
viscosity of paper solution − viscosity of solvent
ν = (1)
s
viscosity of solvent
Intrinsic viscosity [ν] is defined by
ν
s
νlim (2)
=
c→0 c
where c is the concentration of the solution.
The average viscometric degree of polymerization DP (the ratio of the mean molecular mass
ν
indicated viscometrically to the molecular mass of the monomeric unit) is related to the
intrinsic viscosity [ν] by the equation:
α
[ν] = K ⋅ DP (3)
ν
K and α being characteristic Mark Houwink coefficients of the polymer-solvent system
(paper/Cuen) and of the monomer respectively.
v
The intrinsic viscosity [ν] is calculated from the specific viscosity and the concentration c
s
by Martin’s empirical formula:
� ⋅[]ν�
ν = [ν] ⋅ c ⋅10 (4)
s
where k is Martin’s constant. For kraft papers k = 0,14.
5 Apparatus and reagents
NOTE 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 bath, 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 required degree of temperature stability, it may be necessary to use a refrigeration unit in
addition to the bath heater.
– 16 – 60450 CEI:2004
Viscosimètre à tube capillaire calibré suivant l’ISO 3105, avec une constante capillaire de
0,005 ou 0,01. Des tubes non calibrés peuvent être utilisés si la viscosité du solvant Cuen et
celle de la solution de papier dans le solvant Cuen sont mesurées dans le même tube.
Un chronomètre pouvant faire des mesures avec une précision de ±0,1 s.
Un mélangeur ou broyeur permettant à l'éprouvette papier de se dissoudre plus facilement.
Des fioles adaptées (généralement 25 ml à 50 ml) avec couvercles (à l’exclusion de papier)
réalisant une véritable étanchéité, pour la préparation de la solution papier-hydroxyde de
Cuen. D'autres récipients en verre peuvent être utilisés. Cependant, ceux-ci doivent être
fermés de façon étanche pendant la dissolution pour minimiser la dégradation par oxydation
de la solution Cuen.
Cuen (voir Annexe A).
De l’eau distillée ou déionisée.
Une alimentation en azote à faible teneur en oxygène (99,9 % d’azote au minimum).
De l’acétone pur à 99,0 % au minimum.
Du pentane ou de l’hexane 99,0 % au minimum.
De l’acide nitrique aqueux à 20 %.
Une étuve de séchage ventilée capable de maintenir une température de 105 °C ± 2 K.
Une balance capable de mesurer 20 g à ±0,1 mg près.
Un Soxhlet.
Une pipette de précision ±0,1 ml.
Un agitateur mécanique capable de tenir les fioles en verre utilisées pour préparer la solution
papier/Cuen, ou un agitateur magnétique peuvent être utilisés pour dissoudre la solution
papier/Cuen.
6 Eprouvettes
6.1 Préparation des éprouvettes
Le papier à l’étude doit uniquement être manipulé avec des gants ou avec des pinces. Il ne
doit pas être touché à la main.
Le carton précomprimé d'une épaisseur supérieure à 1 mm doit être clivé en couches
d'épaisseur inférieure à 1 mm.
Les éprouvettes doivent être coupées en morceaux suffisamment petits pour faciliter les
opérations ultérieures. Pour des papiers très fins, les matériaux peuvent être coupés en petits
morceaux à l'aide de ciseaux.
60450 IEC:2004 – 17 –
Calibrated capillary type viscometer tubes according to ISO 3105 with a capillary constant of
0,005 or 0,01. Non calibrated tubes 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 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.
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 specimens
The paper under evaluation shall only be handled with gloves or forceps. It shall not be
touched by hand.
Pressboard with a thickness greater than 1 mm, shall be split into layers of less than 1 mm.
The samples shall be cut into pieces sufficiently small to facilitate the subsequent processes.
For very thin paper, the material may be cut into small pieces using scissors.
– 18 – 60450 CEI:2004
6.1.1 Papiers imprégnés
Les papiers imprégnés doivent être dégraissés avant d’être pesés et mis en solution.
Laver suffisamment de papier pour l’étude afin de disposer d’une masse de papier dégraissé
de 3 g environ, dans un Soxhlet, par utilisation de pentane ou d’hexane pendant au moins
cinq lavages, ou en rinçant dans cinq portions de pentane ou d’hexane neuf dans un récipient
adapté en verre. Laisser sécher le matériau dégraissé en l'exposant à l’air libre jusqu’à
atteindre l’équilibre avec l’humidité atmosphérique. Deux morceaux de papier sont prélevés,
l’un pour une détermination du DP et l’autre pour une détermination de la teneur en eau.
ν
6.1.2 Papiers non imprégnés
Prélever un échantillon ayant approximativement une masse de 3 g, et effectuer les
procédures d’essai. Deux morceaux de papier sont prélevés, l’un pour une utilisation dans
l’essai de détermination du DPν et l’autre pour une détermination de la teneur en eau.
7 Procédure expérimentale
7.1 Mesure de la teneur en eau du papier
Mesurer la teneur en eau du papier conformément à l’ISO 287 ou à la CEI 60814.
La teneur en eau doit être mesurée pendant la préparation de la solution Cuen/papier.
7.2 Détermination de la viscosité
7.2.1 Nombre d’éprouvettes
Une éprouvette doit être utilisée pour un essai préliminaire afin de disposer de données sur
lesquelles fonder un essai valable.
Sauf spécification contraire, une éprouvette doit être utilisée pour chaque essai valable. Si la
valeur [ν]⋅c de l'essai préliminaire est en dehors de la plage 0,5 à 1,5, deux éprouvettes
doivent être utilisées.
7.2.2 Concentration de la solution
La concentration de la solution à utiliser est fonction de la valeur du DP attendue, comme
ν
cela est indiqué dans le tableau suivant.
Tableau 2 – Valeurs DP de l'éprouvette
v
Conditionnement de Concentration résultante
Valeur du DP attendue
v
l’éprouvette approximative
g/dl ou %
Nouvelle 1 000 à 2 000 0,05 à 0,15
Bonne 650 à 1 000 0,08 à 0,25
Moyenne 350 à 650 0,15 à 0,45
Vieillie < 350 0,25 à 0,80
NOTE Le but de cette opération est d'obtenir une valeur déterminée pour la viscosité intrinsèque du produit par
concentration de la solution, située dans la plage 0,5 ≤ [ν]⋅c ≤ 1,5. Plus la valeur du produit [υ] ⋅ c est élevée, plus
grande est la précision.
60450 IEC:2004 – 19 –
6.1.1 Impregnated papers
Impregnated papers shall be degreased before weighing and absorbing solution.
Wash a sufficient amount of the paper under evaluation so as to give a degreased mass of
approximately 3 g in a Soxhlet using pentane or hexane for a minimum of five washings, or by
rinsing in five portions of fresh pentane or hexane in an appropriate glass vessel. Allow the
degreased material to dry and leave it exposed to the atmosphere until equilibrium with the
atmospheric humidity is reached. Two portions of the paper are separated, one for use in the
DP determination and one for use in the moisture determination.
ν
6.1.2 Non-impregnated papers
Take a sample having an approximate mass of 3 g and continue with the test procedures. Two
portions of the paper are separated, one for use in the DP determination and one for use in
ν
the moisture determination.
7 Experimental procedure
7.1 Measurement of water content of paper
Measure the water content according to ISO 287 or IEC 60814.
The water content shall be measured at the same time as the Cuen/paper solution is
prepared.
7.2 Determination of viscosity
7.2.1 Number of test specimens
One specimen shall be used in a preliminary experiment to obtain data on which to base a
valid test.
One specimen shall be used for each valid test, unless otherwise specified. If [ν] ⋅ c of the
preliminary experiment is outside of the range 0,5 to 1,5, two test specimens shall be used.
7.2.2 Concentration of the solution
The concentration of the solution to be used is dependent upon the expected DP value as
ν
given in the following table.
Table 2 – DP values of specimen
v
Specimen condition Approximate resulting
Expected DP
v
concentration
g/dl or %
New 1 000 to 2 000 0,05 to 0,15
Good 650 to 1 000 0,08 to 0,25
Average 350 to 650 0,15 to 0,45
Aged < 350 0,25 to 0,80
NOTE The purpose of this operation is to achieve a fixed value of the product’s intrinsic viscosity and
concentration which is in the range 0,5 ≤ [ν]⋅c ≤ 1,5 . The higher the product of [ν]⋅c the more accurate its
precision.
– 20 – 60450 CEI:2004
7.2.3 Séparation des fibres
Les fibres de cellulose doivent être séparées pour faciliter la dissolution dans la s
...
IEC 60450 ®
Edition 2.1 2007-07
CONSOLIDATED VERSION
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
Measurement of the average viscometric degree of polymerization of new and
aged cellulosic electrically insulating materials
Mesure du degré de polymérisation moyen viscosimétrique des matériaux
isolants cellulosiques neufs et vieillis à usage électrique
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IEC 60450 ®
Edition 2.1 2007-07
CONSOLIDATED VERSION
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
Measurement of the average viscometric degree of polymerization of new and
aged cellulosic electrically insulating materials
Mesure du degré de polymérisation moyen viscosimétrique des matériaux
isolants cellulosiques neufs et vieillis à usage électrique
INTERNATIONAL
ELECTROTECHNICAL
COMMISSION
COMMISSION
ELECTROTECHNIQUE
INTERNATIONALE
ICS 17.220.99; 29.035.01 ISBN 2-8318-9234-1
– 2 – 60450 © IEC:2004+A1:2007
CONTENTS
FOREWORD.3
INTRODUCTION.5
1 Scope.6
2 Normative references .6
3 Terms, definitions and symbols .6
3.1 Terms and definitions .6
3.2 Symbols .7
4 Principle .8
5 Apparatus and reagents .8
6 Specimens .9
6.1 Preparation of specimens .9
7 Experimental procedure.10
7.1 Measurement of water content of paper.10
7.2 Determination of viscosity .10
8 Test report.16
Annex A (normative) Cuen solution.17
Annex B (normative) Preparation of Cuen solution.18
c
En
Annex C (normative) Procedure for the verification of the ratio
c
Cu
of the Cuen solution.21
.
Annex D (informative) Numerical values of the product [ν] c as a function of ν
s
according to Martin's formula .22
Bibliography.23
Table 1 – Symbols .7
Table 2 – DP values of specimen .10
v
.
Table D.1 – [ν] c as a function of ν (k = 0,14).22
s
Figure 1 – Chemical structure of cellulose .6
Figure 2 – Ubbelohde viscometer tube.14
60450 © IEC:2004+A1:2007 – 3 –
INTERNATIONAL ELECTROTECHNICAL COMMISSION
–––––––––––
MEASUREMENT OF THE AVERAGE VISCOMETRIC DEGREE OF
POLYMERIZATION OF NEW AND AGED CELLULOSIC ELECTRICALLY
INSULATING MATERIALS
FOREWORD
1) The International Electrotechnical Commission (IEC) is a worldwide organization for standardization comprising
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2) The formal decisions or agreements of IEC on technical matters express, as nearly as possible, an international
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8) Attention is drawn to the Normative references cited in this publication. Use of the referenced publications is
indispensable for the correct application of this publication.
9) Attention is drawn to the possibility that some of the elements of this IEC Publication may be the subject of
patent rights. IEC shall not be held responsible for identifying any or all such patent rights.
This consolidated version of the official IEC Standard and its amendment has been
prepared for user convenience.
IEC 60450 edition 2.1 contains the second edition (2004) [documents 15E/229/FDIS and
15E/235/RVD] and its amendment 1 (2007) [documents 112/49/CDV and 112/66/RVC].
A vertical line in the margin shows where the base publication has been modified by
amendment 1.
International Standard IEC 60450 has been prepared by subcommittee 15E: Methods of test,
of IEC technical committee 15: Insulating materials.
This second edition cancels and replaces the first edition, published in 1974, and consti-tutes
a technical revision. Experience has indicated the need for improved description of the
experimental method. It describes a revised procedure that overcomes the limitations of the
first edition.
– 4 – 60450 © IEC:2004+A1:2007
This publication has been drafted in accordance with the ISO/IEC Directives, Part 3.
The committee has decided that the contents of the base publication and its amendments will
remain unchanged until the maintenance result date indicated on the IEC web site
under "http://webstore.iec.ch" in the data related to the specific publication. At this
date, the publication will be
• reconfirmed,
• withdrawn,
• replaced by a revised edition, or
• amended.
60450 © IEC:2004+A1:2007 – 5 –
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 new
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 effluxing.
– 6 – 60450 © IEC:2004+A1:2007
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 viscometric degree of polymerization ( DP ) of new and aged cellulosic electrically
ν
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 intrinsic 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 polymerization 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 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 287, 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 definitions
3.1.1
degree of polymerization of a cellulose molecule
number of anhydrous-β-glucose monomers, C H O , in the cellulose molecule
6 10 5
NOTE Figure 1 shows the chemical structure of cellulose.
CH OH
CH OH
OH
O O
HO
HO
O
O
HO
HO OH
O
OH
OH
CH OH
n – 2
IEC 424/04
Figure 1 – Chemical structure of cellulose
60450 © IEC:2004+A1:2007 – 7 –
3.1.2
Cuen
1 mol/l aqueous solution of bis(ethylenediamine)copper(II) hydroxide
Cu(H NCH CH NH ) (OH) . [CAS 14552-35-3]
2 2 2 2 2 2
NOTE In some countries the abbreviation CED is used for bis(ethylenediamine)copper(II) hydroxide.
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 constant of the cellulose monomer
α
c Molarity of copper in Cuen solution
Cu
Molarity of ethylenediamine in Cuen solution
c
En
Constants for viscometer tubes 0, 1 and 2 respectively
C , C and C
0 1 2
c Concentration of solution
Average viscometric degree of polymerization
DP
ν
Kinematic viscosity of solution
ν
v Kinematic viscosity of solvent
K Mark Houwink characteristic constant of the polymer/solvent system
k Constant in Martin's formula
m Mass of dry paper
D
Mass of swollen paper in tared vessel
m
T
Mass of added water
m
H O
Density of water
ρ
H O
v Volume of added water
H O
Volume of added Cuen
v
Cu
Intrinsic viscosity
[ν]
v Specific viscosity
s
t t Efflux time for tests A and B on dissolved specimen 1
,
1A 1B
t t Efflux time for tests A and B on dissolved specimen 2
,
2A 2B
Efflux time for tests A and B on pure solvent
t t
,
0A 0B
Efflux time for diluted Cuen solvent (50 % Cuen and 50 % water)
t
t Efflux time for Cuen dissolved specimen
S
———————
Chemical Abstracts Service (CAS) Registry numbers®
– 8 – 60450 © IEC:2004+A1:2007
4 Principle
The specific viscosity ν of a solution of the paper in Cuen is determined. From this result the
s
intrinsic viscosity [ν] of the solution is deduced, and from 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 velocity modulus, the use of conditions outside those specified in this standard may result in
unacceptable errors.
Specific viscosity ν is defined by
s
viscosity of paper solution − viscosity of solvent
v = (1)
s
viscosity of solvent
Intrinsic viscosity [ν] is defined by
⎡ν ⎤
s
ν =lim (2)
⎢ ⎥
c→0 c
⎣ ⎦
where c is the concentration of the solution.
The average viscometric degree of polymerization DP (the ratio of the mean molecular mass
ν
indicated viscometrically to the molecular mass of the monomeric unit) is related to the
intrinsic viscosity [ν] by the equation:
α
[ (v] = K ⋅ DP 3)
ν
K and α being characteristic Mark Houwink coefficients of the polymer-solvent system
(paper/Cuen) and of the monomer respectively.
v
The intrinsic viscosity [ν] is calculated from the specific viscosity and the concentration c
s
by Martin’s empirical formula:
k[v]⋅c
v = [ν ] ⋅ c ⋅10 (4)
s
where k is Martin’s constant. For kraft papers k = 0,14.
5 Apparatus and reagents
NOTE 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 bath, 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 required degree of temperature stability, it may be necessary to use a refrigeration unit in
addition to the bath heater.
60450 © IEC:2004+A1:2007 – 9 –
Calibrated capillary type viscometer tubes according to ISO 3105 with a capillary constant of
0,005 or 0,01. Non calibrated tubes 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 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.
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 specimens
The paper under evaluation shall only be handled with gloves or forceps. It shall not be
touched by hand.
Pressboard with a thickness greater than 1 mm, shall be split into layers of less than 1 mm.
The samples shall be cut into pieces sufficiently small to facilitate the subsequent processes.
For very thin paper, the material may be cut into small pieces using scissors.
– 10 – 60450 © IEC:2004+A1:2007
6.1.1 Impregnated papers
Impregnated papers shall be degreased before weighing and absorbing solution.
Wash a sufficient amount of the paper under evaluation so as to give a degreased mass of
approximately 3 g in a Soxhlet using pentane or hexane for a minimum of five washings, or by
rinsing in five portions of fresh pentane or hexane in an appropriate glass vessel. Allow the
degreased material to dry and leave it exposed to the atmosphere until equilibrium with the
atmospheric humidity is reached. Two portions of the paper are separated, one for use in the
DP determination and one for use in the moisture determination.
ν
6.1.2 Non-impregnated papers
Take a sample having an approximate mass of 3 g and continue with the test procedures. Two
portions of the paper are separated, one for use in the DP determination and one for use in
ν
the moisture determination.
7 Experimental procedure
7.1 Measurement of water content of paper
Measure the water content according to ISO 287 or IEC 60814.
The water content shall be measured at the same time as the Cuen/paper solution is
prepared.
7.2 Determination of viscosity
7.2.1 Number of test specimens
One specimen shall be used in a preliminary experiment to obtain data on which to base a
valid test.
One specimen shall be used for each valid test, unless otherwise specified. If [ν] ⋅ c of the
preliminary experiment is outside of the range 0,5 to 1,5, two test specimens shall be used.
7.2.2 Concentration of the solution
The concentration of the solution to be used is dependent upon the expected DP value as
ν
given in the following table.
Table 2 – DP values of specimen
v
Specimen condition Approximate resulting
Expected DP
v
concentration
g/dl or %
New 1 000 to 2 000 0,05 to 0,15
Good 650 to 1 000 0,08 to 0,25
Average 350 to 650 0,15 to 0,45
Aged < 350 0,25 to 0,80
NOTE The purpose of this operation is to achieve a fixed value of the product’s intrinsic viscosity and
concentration which is in the range 0,5 ≤ [ν]⋅c ≤ 1,5 . The higher the product of [ν]⋅c the more accurate its
precision.
60450 © IEC:2004+A1:2007 – 11 –
7.2.3 Fibre separation
The cellulose fibres need to be separated in order to facilitate dissolution in Cuen. Two
techniques are described as follows.
7.2.3.1 Dry fluffing
Fluff the material in a suitable blender or grinder. Ensure enough sample remains after fluffing
as some sample may be lost during the process. The temperature rise during fluffing must not
cause any detrimental effect to the specimen.
The fluffed sample is left to acclimatize with the atmospheric humidity before determining the
water content.
Weigh the necessary amount of sample to the nearest 0,1 mg according to Table 2 and place
it in a suitable vessel for dissolution. Calculate the mass of dry paper as m .
D
Add water and allow the fibres to disperse.
7.2.3.2 Wet mulching
Weigh the necessary amount of sample to the nearest 0,1 mg and place in the blender cup
with sufficient distilled/de-ionized water to cover it. Mulch the paper by operating the blender
at approximately 18 000 r/min for about 30 s or until the fibres are well separated. After
mulching, remove the excess water by either centrifuging or using a Grade 3 sintered glass
filter.
Place the swollen paper in a tared vial and weigh it to within ±0,1 mg (m ). Calculate the total
T
mass of water (i.e. original mass of water plus the mass of water remaining after mulching) by
subtracting the dry paper mass (m ) and the tare mass from m .
D T
Calculate the quantity of water required to make the total water content up to 10,000 g.
Selecting this amount to within ±0,5 mg, use a sufficient amount of this water to rinse any
residual paper out of the centrifuge/filter into the vial and then place the remainder of the
water into the vial. Alternatively, make up to 10,000 g, then weigh to within ±0,5 mg and
calculate the concentration.
7.2.4 Dissolution of specimen
Before use, the Cuen solution sample shall be inspected, refurbished and verified as follows:
• ensure that the solution contains no precipitate by filtering or decanting;
c
En
• using the method described in Annex C, verify that the ratio = 2,0 ± 0,1
c
Cu
• in the event of non-conformance, reject the solution and prepare a new sample.
Transfer into the same vial the same volume (±0,1 ml, using a pipette) of Cuen as the quantity
of water already added to the cellulose fibres.
– 12 – 60450 © IEC:2004+A1:2007
If there is some contact between the solution and the atmospheric air in the vial, flush the vial
with nitrogen and shake by hand to ensure good mixing of the components. Flush the vial
again with nitrogen and seal it to ensure a low oxygen environment. Preferably the vial should
be flushed with nitrogen throughout the whole time of dissolution.
NOTE 1 The solution is placed in a nitrogen environment and sealed in the vial because the alkaline solvent is
susceptible to oxidative degradation.
Mechanically shake or stir the specimen until dissolution is complete.
NOTE 2 The time taken is dependent upon the type of paper and the extent of degradation.
a) For heavily aged papers ( DPν < 350) a shaking time of 1h to 2 h is usually adequate.
b) For most papers ( DP > 350) shaking for a period of 16 h (overnight) usually ensures
ν
complete dissolution.
c) Some types of new or nearly new papers do not dissolve easily at room temperature. The
dissolution rate may be increased by using a magnetic stirrer to stir the specimen at 4 °C,
in a refrigerator overnight. The use of a few glass balls can also aid the dispersion of the
cellulose fibres.
When testing heavily degraded papers ( DP < 150) they should be tested immediately after
ν
dissolution.
7.2.5 Determination of the viscosity
7.2.5.1 Selection and filling of the viscometer tube
Select a viscometer tube and support it in a constant temperature bath at 20 °C ± 0,1 K.
Ensure that the viscometer tube is dry, dust free and flushed thoroughly with nitrogen.
Fill the viscometer according to the manufacturer’s instructions. Figure 2 gives an example of
a viscometer.
During the filling and the following measurement procedure, visually observe the solution to
determine the presence of any undissolved matter. In the event of finding undissolved matter,
reject the solution and repeat the experiment.
Wait for 5 min to 10 min before the first measurement of the viscosity, until the solution has
reached its temperature equilibrium.
7.2.5.2 Measurement procedure
An Ubbelohde viscometer is used as an example (see Figure 2). For other viscometers, see
ISO 3105 as well as the manufacturer’s instructions.
Seal the ventilation tube (1) with a finger, a stopper or with plastic film and apply a vacuum to
the capillary tube (2) until the lower reservoir ( 10), the working capillary (6), the timing bulb
( 5), and the upper reservoir ( 4) are filled.
60450 © IEC:2004+A1:2007 – 13 –
Remove the vacuum and seal.
Ensure that the liquid separates at the lower end of the capillary.
Measure and record the time interval (t , efflux time) with an accuracy of ±0,5 s for the upper
1A
meniscus to travel between the two timing marks M and M on the timing bulb ( 5) .
1 2
Repeat the measurement on the same specimen and record as t . Record the percentage
1B
difference between the two results.
Inspect the results to assess whether the efflux time is within the allowable range and whether
the two results lie within 1 % of each other.
Record the details of the tube constant that was used and the efflux times (C t and t ).
1, 1A 1B
Clean the viscometer tube in accordance with 7. 2 . 5. 3.
By taking note of the results of the first experiment, repeat the procedure using a second
specimen selected to give:
• optimum paper mass based on an accurate knowledge of the original water content,
• optimum viscometer tube to give efflux times in the allowable range.
In the event that the two results obtained from the second experiment do not lie within 1 % of
each other, clean the viscometer tube and repeat with a new specimen of the same solution.
In the event that no two results lie within 2 % of each other, the two results that lie closest
together shall be accepted and recorded along with details of the tube constant used as C
2,
t and t . The test report shall indicate the poor agreement between results.
2A 2B
7.2.5.3 Viscometer tube cleaning
Viscometer tubes shall be cleaned in the following manner:
a) dispose of the Cuen/paper sample, as appropriate;
b) rinse the viscometer tube thoroughly with distilled water;
c) if possible, soak in 20 % (aqueous) nitric acid for a minimum of 30 min, between two test,
or alternatively between two tests wash the viscometer first with water and then with
acetone and at the end of the working day soak it in 20 % (aqueous) nitric acid and leave
it overnight;
d) rinse with distilled water;
e) rinse with acetone to help dry the tube;
f) finally either blow dry with clean compressed air or dry in a suitable oven.
7.2.5.4 Solvent measurements
In the same manner measure the efflux time for the diluted solvent alone, 50 % Cuen and
50 % of distilled/de-ionized water. Record the details of the tube constant used and the times
as (C t and t ).
0, 0A 0B
– 14 – 60450 © IEC:2004+A1:2007
2 Key
1 ventilation tube
M 2 capillary tube
3 mounting tube
M 4 upper reservoir
5 timing bulb
6 working capillary
7 dome
8 levelling bulb
9 equalization tube
10 lower resevoir
M timing mark
M timing mark
M
F
M fill up mark for test fluid
F
IEC 425/04
Figure 2 – Ubbelohde viscometer tube
7.2.6 Calculations
Calculate the concentration of the solution:
For dry fluffed materials:
m
D
c = [g/dl] (5)
v + v
H O Cu
For wet mulched materials:
m
D
c = [g/dl] (6)
m − m + m
T D H O
+ v
Cu
ρ
H O
60450 © IEC:2004+A1:2007 – 15 –
Calculate the mean efflux time for the specimen of paper solution from t and t as t.
1A 1B
Calculate the mean efflux time for the diluted solvent from t and t as t .
0A 0B 0
Calculate the kinematic viscosity of the solution ν and of the solvent v from:
ν = C ⋅ t [mm²/s] ν = C ⋅ t [mm²/s] (7)
1 0 0 0
where t and t are the mean efflux times and C and C are tube calibration constants.
0 0 1
v
Calculate the specific viscosity according to Equation (1) as follows:
s
ν −ν
ν = (8)
s
ν
Alternatively, if the same viscometer tube is used to measure the efflux times of the
Cuen/paper solution t and the Cuen solvent t then the specific viscosity can be calculated
S 0
as follows:
t − t
s 0
ν = (9)
s
t
Calculate the intrinsic viscosity using Martin’s empirical formula:
k⋅[]ν ⋅c
ν =[ (ν] ⋅ c ⋅10 10)
s
for kraft papers Martin’s constant k = 0,14.
.
NOTE 1 The value of [ν] c may be calculated using Newton’s approximation method to within 0,0001. Alternatively
.
tables have been reproduced in Annex D giving the product [ν] c as a function of . This allows calculation of [ν]
v
s
from the measured values of and the concentration.
v
s
The DP is related to the intrinsic viscosity [ν] by:
v
α
[ (ν ] = K ⋅ DP 11)
v
where K and α are the Mark Houwink constants: α = 1 and K = 0,0075.
Calculate the individual values and the mean value of DP .
ν
Calculate the difference between the maximum and the minimum of the individual values as a
percentage of the mean DP .
ν
NOTE 2 When estimating the decomposition stage of aged papers, care should always be taken to use, as a
reference, the DP value of a new paper of the very same origin; DP of new papers being a function of their
ν ν
specific gravity and of their manufacturing process.
– 16 – 60450 © IEC:2004+A1:2007
8 Test report
The test report shall include the following information:
a) Information regarding test sample
1) Origin: whether new or aged (taken from service) with a statement, if required, of the
exact location from which the sample was removed.
2) Condition: impregnated or not impregnated, nature of impregnation.
b) Water content of the paper as determined in the course of the tests by the method
described in 7.1 (indicate when this determination could not be made due to lack of a
sufficiently large sample).
c
En
c) Characteristics of the Cuen solution: origin, ratio .
c
Cu
d) Mass of test specimen.
e) Mean efflux times of the solvent and solution through the viscometer tube.
f) Individual values of DP in the two tests and the mean value DP .
ν ν
g) Difference between these two values as a percentage of the mean DP .
ν
h) Temperature at which the viscosity was measured.
i) Whether or not the requirements of 7.2.5.2 have been met.
60450 © IEC:2004+A1:2007 – 17 –
Annex A
(normative)
Cuen solution
Cuen solution:
– may be purchased commercially as an aqueous solution with a molarity of 1,0 mol/l. At
this strength, it may be kept for six months in the refrigerator as long as it is stored under
nitrogen; or alternatively
– it may be made in the laboratory at its working strength of 1,0 mol/l by the method given in
Annex B.
– 18 – 60450 © IEC:2004+A1:2007
Annex B
(normative)
Preparation of Cuen solution
B.1 Reagents
1) Crystallized copper sulphate (CuSO , 5H O); reagent grade
4 2
2) Ammonia, density ρ = 0,925 g/cm (NH )
20°C 3
3) 8 % sodium hydroxide solution (NaOH)
4) Barium chloride solution: dissolve 7 g BaCl , 2H O, per one litre of distilled water
2 2
5) Acetone (CH COCH )
3 3
6) Anhydrous sodium sulphate (Na SO )
2 4
7) 1 mol/l hydrochloric acid (HCl)
8) 10 % potassium iodide solution (KI)
9) Standard 0,05 mol/l solution of sodium thiosulphate (Na S O )
2 2 3
10) Starch indicator: 0,2 % solution
11) Commercial ethylenediamine solution (about 70 %) (NH CH CH NH )
2 2 2 2
12) 0,5 mol/l sulphuric acid (H SO )
2 4
13) Methyl-orange indicator
B.2 Preparation of copper hydroxide
Dissolve 200 g of crystallized copper sulphate ( 1) in 1 l of boiling distilled water. Allow to cool
to a temperature of 40 °C to 50 °C. Add ammonia ( 2) slowly until a blue-violet colour appears
which indicates the moment at which the precipitate dissolves in the surplus of reagent (about
100 ml of ammonia will be required). Wash the greenish precipitate of basic copper sulphate,
with cold distilled water, by decantation, until the washings are colourless.
Add 640 ml of the sodium hydroxide solution ( 3), drop by drop, to the moist precipitate of
basic copper sulphate. Stir carefully. The temperature shall not exceed 20 °C.
NOTE 1 The temperature should preferably be kept below 10 °C.
Allow to stand for 10 min. Wash the copper hydroxide precipitate with distilled water. Stop
washing when some drops of barium chloride solution ( 4) no longer produce a precipitate of
BaSO in the washings. Shake the moist hydroxide with 1 000 ml acetone ( 5), which has been
dehydrated by passing it through dry sodium sulphate ( 6). Filter through a Buchner funnel,
wash again on the filter with 100 ml acetone ( 5). Dry either in the air or in a vacuum, at room
temperature.
Store the copper hydroxide away from light, in a brown glass bottle with ground stopper.
NOTE 2 Blue copper hydroxide prepared this way is free from black copper oxide and agrees with the theoretical
formula Cu(OH) . It should dissolve in hydrochloric acid, concentrated ammonia and ethylene diamine without
leaving any insoluble residue and should be free from both sulphate and sodium ions.
60450 © IEC:2004+A1:2007 – 19 –
B.3 Determination of the copper content
In a 200 ml volumetric flask, dissolve 2 g of copper hydroxide in 50 ml of 1 mol/l hydrochloric
acid ( 7). Fill up to the mark with the same acid. Pipette out 25 ml from this solution, transfer
into a titration flask and add 25 ml of the 10 % potassium iodide solution ( 8).
Titrate with sodium thiosulphate ( 9), using the starch solution ( 10) as the indicator (1 ml to
2 ml of the starch solution shall be added when the titration is nearing the end).
The copper content, expressed in grams per 100 g of hydroxide, is
. .
(0,02) (63,5 ) n (B.1)
where n is the number of millilitres of the 0,05 mol/l sodium thiosulphate solution used for the
titration.
B.4 Preparation of the ethylene diamine solution
Ethylene diamine NH CH CH NH is sold commercially as a 70 % solution ( 11). However, it
2 2 2 2
is necessary to ensure the stability of the Cuen solution which will be used to dissolve the
paper by starting from a purer reagent.
Purify by distillation at a pressure just below atmospheric, if possible, otherwise at
atmospheric pressure.
If, during storage, the solution turns yellow, redistill before use.
B.5 Determination of the ethylene diamine content
Take 25,0 ml ± 0,1 ml of ethylene diamine, transfer to a 250 ml volumetric flask and fill up to
the mark with distilled water. Pipette out 20,0 ml ± 0,1 ml from this solution and titrate it with
0,5 mol/l sulphuric acid solution (B.1), using methyl-orange as the indicator (B.2). The
ethylene diamine content in g/100 ml of the original solution is
.
(1,5) n (B.2)
where n is the number of millilitres of 0,5 mol/l H SO (B.2) used.
2 4
Store the ethylene diamine solution away from light in a brown glass bottle with a ground
stopper.
B.6 Preparation of the Cuen solution
Tests are carried out with 1 mol/l Cuen (217,50 g Cuen/l). Weigh an amount of copper
hydroxide precipitate corresponding to (63,5 ± 0,5) g copper. Transfer to a 1 l volumetric flask
and moisten with about 50 ml distilled water.
– 20 – 60450 © IEC:2004+A1:2007
Using a burette, introduce into the flask a volume of ethylene diamine solution containing
120,0 g ± 0,5 g of anhydrous ethylene diamine whilst maintaining the temperature below
10 °C. Allow the solution to stand for 1 h at room temperature, shaking it from time to time.
Fill up to the mark with distilled water and shake again. Allow to settle for approximately 24 h,
and filter through a fine (grade 4) sintered glass filter.
60450 © IEC:2004+A1:2007 – 21 –
Annex C
(normative)
c
En
Procedure for the verification of the ratio of the Cuen solution
c
Cu
C.1 Reagents
a) 10 % potassium iodide solution (KI)
b) Standard 0,1 mol/l solution of sodium thiosulphate (Na S O )
2 2 3
c) 0,5 mol/l sulphuric acid (H SO )
2 4
d) 2 mol/l sulphuric acid (H SO )
2 4
e) Methyl-orange indicator
C.2 Copper content
Dilute 25 ml of the 1 mol/l Cuen solution to 250 ml, with distilled water, in a 250 ml volumetric
flask. Pipette out 25 ml and transfer to a titration flask. Add 50 ml of the 10 % potassium
iodide solution ( a). Acidify with 100 ml of 2 mol/l sulphuric acid ( d). Titrate with the sodium
thiosulphate solution ( b) until solution turns cloudy. The copper molarity of the solution is
.
p = (0,04) n (C.1)
where n is the number of millilitres of sodium thiosulphate solution used.
C.3 Ethylene diamine content
Take 20 ml of the diluted solution and titrate them with 0,5 mol/l sulphuric acid ( c) until the
methyl orange ( e) used as the indicator shows a faint pink colouration.
Part of the acid used reacts with copper hydroxide.
The ethylene diamine molarity of the solution is given by
.
(0,25) (q – 4p) (C.2)
where q is the number of millilitres of 0,5 mol/l H SO ( c) used and p is the copper
2 4
hydroxide molarity as determined previously.
When the symbols c and c are used for the copper and ethylene diamine molarities, then
Cu En
the ratio becomes
C
En
= 2,0 ± 0,1 (C.3)
C
Cu
– 22 – 60450 © IEC:2004+A1:2007
Annex D
(informative)
.
Numerical values of the product [ν]c
as a function of ν according to Martin's formula
s
.
Table D.3 – [ν]c as a function of ν
s
(k = 0,14)
.
[ν]c
0,00 0,01 0,02 0,03 0,04 0,05 0,06 0,07 0,08 0,09
ν
s
0,0 0,010 0,020 0,030 0,039 0,049 0,059 0,068 0,078 0,087
0,1 0,097 0,106 0,116 0,125 0,134 0,143 0,152 0,161 0,170 0,179
0,2
0,188 0,197 0,206 0,215 0,223 0,232 0,241 0,249 0,258 0,266
0,3 0,275 0,283 0,291 0,300 0,308 0,316 0,324 0,332 0,340 0,349
0,4 0,357 0,365 0,372 0,380 0,388 0,396 0,404 0,412 0,419 0,427
0,5 0,435 0,442 0,450 0,457 0,465 0,472 0,480 0,487 0,495 0,502
0,6 0,509 0,516 0,524 0,531 0,538 0,545 0,552 0,559 0,566 0,574
0,7 0,581 0,588 0,594 0,601 0,608 0,615 0,622 0,629 0,636 0,642
0,8 0,649 0,656 0,662 0,669 0,676 0,682 0,689 0,695 0,702 0,708
0,9 0,715 0,721 0,728 0,734 0,740 0,747 0,753 0,759 0,766 0,
...
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