SIST ENV 14273:2007

Advanced technical ceramics - Ceramic powders - Determination of crystalline phases in zirconia

This European Prestandard specifies a method for the routine qualitative and quantitative determination of the crystalline phases (monoclinic, tetragonal and cubic) present in zirconia powders using X-ray powder diffraction.

Hochleistungskeramik - Keramische Pulver - Bestimmung der kristallinen Phasen in Zirconiumoxid

Diese Europäische Vornorm legt ein Verfahren für qualitative und quantitative Routinebestimmungen von (monoklinen, tetragonalen und kubischen) kristallinen Phasen in Zirconiumoxid-Pulvern durch Röntgen-diffraktometrie am Pulver fest.

Sodobna tehnična keramika - Keramični praški - Določanje kristalnih faz v cirkonijevem oksidu

General Information

• Status: Withdrawn
• Publication Date: 31-Dec-2006
• Withdrawal Date: 25-Jun-2023
• ICS: 81.060.30 - Advanced ceramics
• Technical Committee: SS SPL - Technical Board for the general field
• Current Stage: 9900 - Withdrawal (Adopted Project)
• Start Date: 17-Jun-2023
• Due Date: 10-Jul-2023
• Completion Date: 26-Jun-2023
• Mandate: M/076 - Mandate to CEN/CENELEC for standardization in the field of advanced ceramics
• Ref Project: ENV 14273:2002 - Advanced technical ceramics - Ceramic powders - Determination of crystalline phases in zirconia

Standards Content (Sample)

SLOVENSKI STANDARD
SIST ENV 14273:2007
01-januar-2007
6RGREQDWHKQLþQDNHUDPLND.HUDPLþQLSUDãNL'RORþDQMHNULVWDOQLKID]Y
FLUNRQLMHYHPRNVLGX
Advanced technical ceramics - Ceramic powders - Determination of crystalline phases in
zirconia
Hochleistungskeramik - Keramische Pulver - Bestimmung der kristallinen Phasen in
Zirconiumoxid
Ta slovenski standard je istoveten z: ENV 14273:2002
ICS:
81.060.30 Sodobna keramika Advanced ceramics
SIST ENV 14273:2007 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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EUROPEAN PRESTANDARD
ENV 14273
PRÉNORME EUROPÉENNE
EUROPÄISCHE VORNORM
May 2002
ICS 81.060.30
English version
Advanced technical ceramics - Ceramic powders -
Determination of crystalline phases in zirconia
Céramiques techniques avancées - Poudres céramiques - Hochleistungskeramik - Keramische Pulver - Bestimmung
Détermination des phases cristallines dans la zircone der kristallinen Phasen in Zirconiumoxid
This European Prestandard (ENV) was approved by CEN on 11 April 2002 as a prospective standard for provisional application.
The period of validity of this ENV is limited initially to three years. After two years the members of CEN will be requested to submit their
comments, particularly on the question whether the ENV can be converted into a European Standard.
CEN members are required to announce the existence of this ENV in the same way as for an EN and to make the ENV available promptly
at national level in an appropriate form. It is permissible to keep conflicting national standards in force (in parallel to the ENV) until the final
decision about the possible conversion of the ENV into an EN is reached.
CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece,
Iceland, Ireland, Italy, Luxembourg, Malta, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36  B-1050 Brussels
© 2002 CEN All rights of exploitation in any form and by any means reserved Ref. No. ENV 14273:2002 E
worldwide for CEN national Members.

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ENV 14273:2002 (E)
Contents
page
Foreword 3
1 Scope 3
2 Normative references 3
3 Principle 3
4Apparatus 4
5 Sample preparation 4
6 Test procedure 4
6.1 Qualitative analysis 5
6.2 Quantitative analysis – Method A: Polymorph method 5
6.3 Quantitative analysis – Method B: Full pattern method 5
7 Qualitative and quantitative analysis of the recorded X-ray diffraction pattern 5
7.1 Qualitative analysis 5
7.2 Quantitative analysis – Method A: Polymorph method 6
7.2.1 Calculation 6
7.3 Quantitative analysis – Method B: Full pattern method 9
7.3.1 Symbols and definitions 9
7.3.2 Calculation 10
7.4 Limitations to the quantitative analysis 11
7.4.1 General limitations 11
7.4.2 Method A: Polymorph method 11
7.4.3 Method B: Full pattern method 11
8 Test report 11
8.1 Qualitative analysis 11
8.2 Quantitative analysis 12
Annex A (normative) Determination of stabiliser amount from cell parameters 13
Bibliography 14
2

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ENV 14273:2002 (E)
Foreword
This document (ENV 14273:2002) has been prepared by Technical Committee CEN/TC 184
"Advanced technical ceramics", the secretariat of which is held by BSI.
Annex A is normative.
This Prestandard includes a Bibliography.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the
following countries are bound to announce this European Prestandard: Austria, Belgium, Czech
Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Malta,
Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom.
1 Scope
This European Prestandard specifies a method for the routine qualitative and quantitative
determination of the crystalline phases (monoclinic, tetragonal and cubic) present in zirconia powders
using X-ray powder diffraction.
2 Normative references
This European Prestandard incorporates by dated or undated reference provisions from other
publications. These normative references are cited at the appropriate places in the text and the
publications are listed hereafter. For dated references, subsequent amendments to or revisions of any of
these publications apply to this European Prestandard only when incorporated in it by amendment or
revision. For undated references the latest edition of the publication referred to applies (including
amendments).
EN ISO/IEC 17025 General requirements for the competence of testing and calibration laboratories
(ISO/IEC 17025:1999).
3 Principle
The qualitative and quantitative determination of the crystalline phases present in a given zirconia
powder is derived from the X-ray diffraction analysis of a representative sample of this powder.
The qualitative analysis relies on a comparison of the recorded spectrum with available reference data
(e.g. ICDD-JCPDS data base).
For the quantitative analysis, two methods are used: the polymorph method and the full pattern
method. The latter consists of determining scale factors by a least squares procedure involving all
recorded diffraction peaks [1,2]. The former is a well-established method, details of which can be
found in basic text books [3]; it relies on a comparison of the measured intensities of selected
reflections from the previously identified phases.
NOTE A third method available for quantitative analysis is the Rietveld method. This method determines the
phase constitution of the sample by fitting the whole X-ray diffraction spectrum through an iterative refinement
approach. This refinement can be limited to the scale factors of each phase present (i.e. the volume fraction of
the phases) or can address a whole set of parameters (e.g. cell parameters, atomic positions). Although it is
3

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ENV 14273:2002 (E)
recognised that Rietveld refinement is probably the most reliable method and is more and more proposed in
commercial XRD packages for quantitative analysis, this method is at present beyond the scope of this
Prestandard.
4 Apparatus
Data acquisition is performed using a Bragg-Brentano diffractometer. The following experimental
settings are recommended:
 Copper X-ray tube;
 Precise goniometer (two-theta error £ 0,5°);
 Primary soller slit with a divergence £ 2,5°;
 5 £ Divergence slit £ 1°;
 Receiving slit £ 2 mm;
 Scatter slit £ 1°;
 Secondary monochromator;
 Narrow line focus.
NOTE In those cases where the sample preparation leads inevitably to an inhomogeneous grain structure
and/or composition (e.g. grains with an inhomogeneous radial phase distribution), the use of an X-ray tube with
shorter wavelength, for instance, a molybdenum X-ray or silver X-ray tube, is recommended. The shorter X-ray
wavelength provides a greater depth of penetration resulting in a more representative analysis in these cases.
5 Sample preparation
In order to avoid primary extinction and assure good statistics, the powder to be analysed shall have a
homogeneous grain size less than 40 μm.
By an adequate sampling procedure, a representative test sample of this powder is taken and pressed
into the cavity of the sample holder. Use the backfill pressing technique to obtain a flat and smooth
sample surface and to reduce preferred orientation. The dimensions of the sample holder will be such
that X-rays irradiating outside of the sample volume can be avoided.
NOTE If the powder is obtained from a solid monolithic sample by comminution (e.g. using a crushing jaw in
combination with a vibratory mill or alike) it is necessary to be aware that the sample preparation may affect the
type and amount of the crystalline phases present and that, accordingly, the phase composition determined may
be irrelevant.
6 Test procedure
Set the excitation voltage to at least 40 kV and the current intensity at the anode of the copper X-ray
tube to at least 35 mA.
NOTE If a different X-ray tube is used, change the excitation parameters accordingly.
Data acquisition is preferably performed in the step-scanning mode, the step size being set between
0,01° and 0,05° two-theta. Alternatively record the spectrum under continuous mode with an
integration width of 0,01 or 0,02.
4

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ENV 14273:2002 (E)
6.1 Qualitative analysis
Set the scanning range from 10 to 80° two-theta and record the whole X-ray diffraction pattern. Select
a counting time such that a good peak to background signal ratio is obtained. Practically, it should be
£ 0,02 for the maximum peak in the range scanned. The relative
sufficiently long to obtain a srel
standard deviation, s, is given by
rel
+
N t N b

= (1)
rel
-
N N
t b
with N the total counts and N the counts of the background.
t b
6.2 Quantitative analysis – Method A: Polymorph method
For the polymorph method collecting the data under the following specific conditions is recommended.
Define two measurements programs:
 The first, scan between 26,5 ° and 33,5 ° two-theta, with a counting time suitable for
achieving a s £ 0,01 on the maximum peak;
rel
 The second, scan between 70 ° and 77 ° two-theta, with a counting time suitable for
achieving s £ 0,02 on the maximum peak;
rel
6.3 Quantitative analysis – Method B: Full pattern method
For the full pattern method the X-ray spectrum recorded for the preliminary qualitative analysis shall be
used.
7 Qualitative and quantitative analysis of the recorded X-ray diffraction
pattern
7.1 Qualitative analysis
Use an automatic or manual search and identify the crystalline phases present according to the ICDD-
JCPDS PDF reference databank.
NOTE The following data sets are recommended, based on the present available information. However, as the
ICDD-JCPDS PDF databank is regularly upgraded, for an exact analysis, updated data sets should be used.
5

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ENV 14273:2002 (E)
Crystalline phase JCPDS-PDF Nr.
Monoclinic (Baddeleyite, syn) 37-1484
Tetragonal 42-1164 or 17-0923
Cubic (pure) 27-0997
Cubic (yttria doped) 37-1307
Cubic (calcia doped) 26-0341
7.2 Quantitative analysis – Method A: Polymorph method
7.2.1 Calculation
Calculation of the integrated intensities I(h k l)
phase
The intensities I(h k l) to be used in subsequent calculation are the integrated intensities computed from fitted
phase
and separated peaks.
NOTE 1 Due to overlapping of the peaks of different phases it is recommended for the determination of peak intensities to use
a profile fitting method. The program used should incorporate a profile shape function sufficiently flexible (e.g. Pseudo-Voigt,
Voigt or Pearson VII; not only Gaussian or Cauchy). Profile fitting programs are available in most of the instrumental software
packages on the market. Alternatively they can be obtained from various sources [4].
NOTE 2 The use of graphical methods is in all cases discouraged.
Calculation of the intensity factors R(h k l)
phase
A reliable determination of the crystalline phase composition of the powder sample by the polymorph method
requires the use of correct intensity factors values. This in turn implies a precise knowledge of the crystallographic
structure of the phases present.
The recommended intensity factor values are reported in Table 1 below. For any other zirconia/stabiliser system
and/or reflection, derivation of the intensity factors should be done according to equation (2) using relevant
crystallographic data available from the literature.
2
LP
p F
(2 ). .
hkl hkl
R(hkl) = (2)
phase
2
.V
with LP(2q) the Lorentz-Polarization factor, corrected if needed for the influence of the monochromator crystal, p
hkl
the multiplicity factor of the specific reflection, F the structure factor and V, the volume of the unit cell. For a
hkl
detailed explanation of these factors, one should refer to the "International Tables for X-ray Crystallography" [5].
6

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ENV 14273:2002 (E)
Table 1 — Recommend
...