ISO 17942:2014
(Main)Fine ceramics (advanced ceramics, advanced technical ceramics) — Methods for chemical analysis of boron nitride powders
Fine ceramics (advanced ceramics, advanced technical ceramics) — Methods for chemical analysis of boron nitride powders
ISO 17942:2014 specifies the methods for the chemical analysis of fine boron nitride powders used as the raw material for fine ceramics. It stipulates the analysis methods of total boron, free boron, total nitrogen, aluminium, cadmium, calcium, chromium, cobalt, copper, iron, lead, magnesium, manganese, nickel, potassium, silicon, sodium, titanium, vanadium, zinc, carbon, and oxygen in boron nitride powders for fine ceramics. Total boron is determined by using either a fusion?titration method or a fusion?inductively coupled plasma-optical emission spectrometry (ICP-OES). Free boron is determined by using either an acid digestion?ICP-OES or a methanol extraction?ICP-OES. If necessary, the boron amount which arises from the hydrolysis of boron nitride during sample treatment is corrected using spectrophotometry. Total nitrogen is determined by using either an acid pressure decomposition?distillation separation?titration method or an inert gas fusion?thermal conductivity method. Silicon is determined by using a fusion?ICP-OES. Aluminium, cadmium, calcium, chromium, cobalt, copper, iron, lead, magnesium, manganese, nickel, titanium, vanadium, zinc are determined by using an acid pressure decomposition?ICP-OES or a fusion?ICP-OES. Sodium and potassium are determined by using atomic absorption spectrometry (AAS), flame emission spectrometry (FES), or ICP-OES following acid pressure decomposition. Carbon is determined by using a combustion?IR absorption spectrometry or a combustion?thermal conductivity method. Oxygen is determined by using an inert gas fusion?IR absorption spectrometry.
Céramiques techniques — Méthodes pour l'analyse chimique de poudres de nitrure de bore
General Information
Standards Content (Sample)
INTERNATIONAL ISO
STANDARD 17942
First edition
2014-08-15
Fine ceramics (advanced ceramics,
advanced technical ceramics) —
Methods for chemical analysis of
boron nitride powders
Céramiques techniques — Méthodes pour l’analyse chimique de
poudres de nitrure de bore
Reference number
ISO 17942:2014(E)
©
ISO 2014
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ISO 17942:2014(E)
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ISO 17942:2014(E)
Contents Page
Foreword .v
Introduction .vi
1 Scope . 1
2 Normative references . 1
3 General rules in chemical analysis . 1
4 Analysis items . 1
5 Sampling, weighing, and drying of sample . 2
5.1 Sampling . 2
5.2 Weighing . 2
5.3 Drying . 2
6 Reporting analytical values . 3
6.1 Number of analyses. 3
6.2 Blank test . 3
6.3 Evaluation of analytical values . 3
6.4 Expression of analytical values . 3
7 Determination methods of total boron . 3
7.1 Classification of determination methods . 3
7.2 Fusion-acidimetric titration method . 4
7.3 Fusion-ICP-OES . 6
8 Determination methods of free boron . 8
8.1 Classification of determination methods . 8
8.2 Sulfuric acid digestion-ICP-OES and spectrophotometry . 9
8.3 Nitric acid digestion-ICP-OES .11
8.4 Methanol extraction-borate separation-ICP-OES and spectrophotometry .12
9 Determination methods of total nitrogen .16
9.1 Classification of determination methods .16
9.2 Acid pressure decomposition-distillation separation-acidimetric titration method .17
9.3 Fusion-ammonia separation-acidimetric titration method .22
9.4 Inert gas fusion-thermal conductivity method .22
10 Determination method of silicon .26
10.1 Determination method.26
10.2 Principle .26
10.3 Reagents.26
10.4 Apparatus and instrument .27
10.5 Amount of sample .27
10.6 Operation .27
10.7 Blank test .27
10.8 Drawing calibration curves .27
10.9 Calculation .28
11 Determination methods of aluminium, cadmium, calcium, chromium, cobalt, copper, iron,
lead, magnesium, manganese, nickel, titanium, vanadium, and zinc .28
11.1 Classification of determination methods .28
11.2 Acid pressure decomposition-ICP-OES .28
11.3 Fusion-ICP-OES .31
12 Determination methods of sodium and potassium .34
12.1 Classification of determination methods .34
12.2 Acid pressure decomposition-AAS.35
12.3 Acid pressure decomposition-FES .37
12.4 Acid pressure decomposition-ICP-OES .39
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ISO 17942:2014(E)
13 Determination methods of carbon .41
13.1 Classification of determination methods .41
13.2 Combustion (resistance furnace)-IR absorption spectrometry .42
13.3 Combustion (RF furnace)-conductometry .45
13.4 Combustion (RF furnace)-IR absorption spectrometry .47
13.5 Combustion (resistance furnace)-coulometry .49
13.6 Combustion (resistance furnace)-gravimetry .49
13.7 Combustion (resistance furnace)-conductometry .49
14 Determination method of Oxygen .49
14.1 Determination method.49
14.2 Inert gas fusion-IR absorption spectrometry .49
15 Test report .52
Annex A (informative) List of commercial certified reference materials .53
Annex B (informative) Analytical results obtained from a round robin test .54
Annex C (informative) Spectral lines for ICP-OES .58
Bibliography .59
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ISO 17942:2014(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
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The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
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The committee responsible for this document is ISO/TC 206, Fine ceramics.
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ISO 17942:2014(E)
Introduction
This International Standard describes the chemical analysis of boron nitride powders for use in fine
ceramics applications. Determination methods of both main and trace constituents of interest are fully
covered.
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INTERNATIONAL STANDARD ISO 17942:2014(E)
Fine ceramics (advanced ceramics, advanced technical
ceramics) — Methods for chemical analysis of boron
nitride powders
1 Scope
This International Standard specifies the methods for the chemical analysis of fine boron nitride
powders used as the raw material for fine ceramics.
This International Standard stipulates the analysis methods of total boron, free boron, total nitrogen,
aluminium, cadmium, calcium, chromium, cobalt, copper, iron, lead, magnesium, manganese, nickel,
potassium, silicon, sodium, titanium, vanadium, zinc, carbon, and oxygen in boron nitride powders for
fine ceramics. Total boron is determined by using either a fusion–titration method or a fusion–inductively
coupled plasma-optical emission spectrometry (ICP-OES). Free boron is determined by using either an
acid digestion–ICP-OES or a methanol extraction–ICP-OES. If necessary, the boron amount which arises
from the hydrolysis of boron nitride during sample treatment is corrected using spectrophotometry. Total
nitrogen is determined by using either an acid pressure decomposition–distillation separation–titration
method or an inert gas fusion–thermal conductivity method. Silicon is determined by using a fusion–
ICP-OES. Aluminium, cadmium, calcium, chromium, cobalt, copper, iron, lead, magnesium, manganese,
nickel, titanium, vanadium, zinc are determined by using an acid pressure decomposition–ICP-OES or
a fusion–ICP-OES. Sodium and potassium are determined by using atomic absorption spectrometry
(AAS), flame emission spectrometry (FES), or ICP-OES following acid pressure decomposition. Carbon is
determined by using a combustion–IR absorption spectrometry or a combustion–thermal conductivity
method. Oxygen is determined by using an inert gas fusion–IR absorption spectrometry.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated
references, the latest edition of the referenced document (including any amendments) applies.
EN 12698-1:2007, Chemical analysis of nitride bonded silicon carbide refractories - Part 1: Chemical methods
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 6353-3, Reagents for chemical analysis — Part 3: Specifications — Second series
ISO 9138, Abrasive grains — Sampling and splitting
ISO 21068-2:2008, Chemical analysis of silicon-carbide-containing raw materials and refractory products —
Part 2: Determination of loss on ignition, total carbon, free carbon and silicon carbide, total and free silica
and total and free silicon
3 General rules in chemical analysis
Chemical analysis shall be performed in accordance with general rules regulated as standards, if
available.
4 Analysis items
Analysis items specified in this International Standard shall be as follows:
a) Total boron (T.B)
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ISO 17942:2014(E)
b) Free boron (F.B)
c) Total nitrogen (T.N)
d) Silicon (Si)
e) Aluminium (Al)
f) Cadmium (Cd)
g) Calcium (Ca)
h) Chromium (Cr)
i) Cobalt (Co)
j) Copper (Cu)
k) Iron (Fe)
l) Lead (Pb)
m) Magnesium (Mg)
n) Manganese (Mn)
o) Nickel (Ni)
p) Titanium (Ti)
q) Vanadium (V)
r) Zinc (Zn)
s) Sodium (Na)
t) Potassium (K)
u) Carbon (C)
v) Oxygen (O)
5 Sampling, weighing, and drying of sample
The method of preparing samples shall be in accordance with ISO 9138 unless otherwise mutually
agreed upon between the analyser and customer.
5.1 Sampling
Take the sample in accordance with ISO 9138.
5.2 Weighing
Weigh the sample of the required quantity to the nearest 0,1 mg using an electric balance.
5.3 Drying
Take about 10 g of the sample into a flat-type weighing bottle (60 mm × 30 mm) and spread it uniformly
over the bottom of the bottle. Place the bottle in an air bath at (120 ± 5) °C for 2 h without a lid, and then
cool in a desiccator (desiccant: magnesium perchlorate for drying) with a lid for 1 h.
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ISO 17942:2014(E)
6 Reporting analytical values
6.1 Number of analyses
Analyse the sample twice on different days.
6.2 Blank test
Upon analysis, perform a blank test to correct the measured values.
6.3 Evaluation of analytical values
a) When the difference between two analytical values does not exceed the tolerance shown in Table 1,
the average value shall be reported.
b) When the difference between two analytical values exceeds the tolerance shown in Table 1, perform
additional two analyses. When the difference does not exceed the tolerance, the average value
thereof shall be reported. If the difference also exceeds the tolerance, the median of four analytical
values shall be reported.
6.4 Expression of analytical values
The analytical values shall be given in % (mass fraction) in dryness.
a) Total boron and total nitrogen — express the results with two to four figures according to the
method used.
b) Free boron — express the results with two to four figures according to the method used.
c) Others — express the results to the third decimal place.
Table 1 — Tolerance on analytical values
Unit: % (mass fraction)
Component total-B free-B total-N Si, Al, Cd, Ca, Cr, Co, Cu, Fe, Pb, Mg, C O
Mn, Ni, Ti, V, Zn,
K, Na
a c e
Tolerance 0,30 0,30 0,001 0.005 0,01
b d f
0,40 0,005 0,05
a
Acid pressure decomposition–distillation separation–acidimetric titration method.
b
Inert gas fusion–thermal conductivity method.
c
Applicable to the content of less than 0,01 % (mass fraction).
d
Applicable to the content of not less than 0,01 % (mass fraction).
e
Applicable to the content of less than 1,0 % (mass fraction).
f
Applicable to the content of not less than 1,0 % (mass fraction).
7 Determination methods of total boron
7.1 Classification of determination methods
Total boron shall be determined by either of the following methods. If analytical results with three or
four figures are required, use method A; whereas if two figures are required, method B can be used.
— Method A, fusion–acidimetric titration method
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ISO 17942:2014(E)
— Method B, fusion–ICP-OES
7.2 Fusion-acidimetric titration method
7.2.1 Principle
Fuse the sample with sodium carbonate and dissolve the melt in hydrochloric acid. Adjust the solution to
pH 6,4 after removal of carbon dioxide. Add mannitol, and then titrate with sodium hydroxide solution
to pH 6,4.
This method shall be used to obtain the results of three or four figures.
7.2.2 Reagents
Reagents of analytical grade shall be used. Reagent solutions shall be preserved in plastic bottles
(products made of polyethylene, polypropylene, and tetrafluoroethylene resin are available.). The
standard solutions being SI traceable shall be used.
7.2.2.1 Water, Grade 1 or superior as specified in ISO 3696.
7.2.2.2 Sodium carbonate, anhydrous, as specified in ISO 6353-3 or that of higher grade.
7.2.2.3 Hydrochloric acid (1+1), (1+50), prepare from hydrochloric acid, respectively.
7.2.2.4 Sodium hydroxide, more than 97,0 % (mass fraction) of purity.
7.2.2.5 Sodium hydroxide solution (200 g/l), (40 g/l), (20 g/l), prepare from sodium hydroxide,
respectively.
7.2.2.6 Ethanol (95).
7.2.2.7 Ethanol–Sodium hydroxide (1+1) mixed solution, prepare by mixing the same volume of
ethanol (95) and a sodium hydroxide solution (200 g/l).
7.2.2.8 Mannitol.
7.2.2.9 Boric acid, more than 99,5 % (mass fraction) of purity.
7.2.2.10 Standard boron solution, weigh 1 g of boric acid (7.2.2.9) in a platinum crucible (for example,
30 ml) and heat it initially at a low temperature and finally at about 1 100 °C. After cooling in a desiccator,
weigh the mass of boric oxide as B O . Take the product into a 200 ml beaker together with the crucible
2 3
and add 100 ml of hot water. Heat and dissolve it. After cooling, transfer the solution into a 200 ml
volumetric flask and dilute with water to the mark.
7.2.2.11 Methyl-red indicator solution, prepare by dissolving 0,10 g of methyl-red with 50 ml of
ethanol (95) (7.2.2.6) to make up to 100 ml by adding water.
7.2.2.12 0.2 mol/ l Sodium hydroxide solution, weigh 50 g of sodium hydroxide in a polyethylene
bottle and dissolve in 50 ml of water under cooling. Stand for a few days with a cap to precipitate sodium
carbonate. Take 20 ml of the supernatant and dilute with water to 2 000 ml. Preserve it into a polyethylene
bottle equipped with an absorption tube of carbon dioxide. The volume of equivalent to the boron shall
be obtained according to the following. Take exactly 50 ml of the standard boron solution (7.2.2.10) into a
200 ml beaker and add 12 ml of hydrochloric acid (1+1) (7.2.2.3) and a few drops of methyl-red indicator
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ISO 17942:2014(E)
solution (7.2.2.11). After neutralization with the sodium hydroxide solution (40 g/l) (7.2.2.5), operate in
accordance with 7.2.5 g). Calculate the factor of this solution according to the following formula:
0,174850
FG=× × (1)
V 200
0
where
F is the factor of boron content of 0,2 mol/l sodium hydroxide solution per 1 ml (g/ml);
G is the weighed amount of boric acid in 7.2.2.9 (g);
V is the consumed volume of 0,2 mol/l sodium hydroxide solution after addition of mannitol in
0
7.2.2.12 (ml).
7.2.3 Apparatus
Apparatus shall be as follows:
7.2.3.1 Platinum crucible (30 ml), with a platinum lid.
7.2.3.2 Electric furnace, adjustable to the temperature of (1 100 ± 25) °C.
7.2.3.3 pH meter, readable to the smallest value of 0,1 equipped with a glass electrode.
7.2.4 Amount of sample
The weighed amount of the sample shall be 0,10 g.
7.2.5 Operation
The operation shall be as follows.
a) Take the sample aliquot into a platinum crucible (30 ml) and 2 ml of the ethanol–sodium hydroxide
mixed solution (7.2.2.7).
b) Heat on a hot plate, and then evaporate until dry.
c) Add 2,0 g of sodium carbonate and heat initially at a low temperature. Elevate the temperature
gradually to start fusing (heat carefully to prevent the contents from scattering) by using an electric
furnace or a Bunsen burner and keep the temperature for 15 min ~ 30 min during fusion. Fuse the
sample at 950 °C ~ 1 000 °C. Keep the temperature as low as possible.
d) Stand the crucible for cooling with a lid and place the crucible into a 300 ml beaker. Add 50 ml of
water and 10 ml of hydrochloric acid (1+1) (7.2.2.3) and heat it on a hot plate with a watch glass to
dissolve the melt.
e) After dissolving, wash the crucible with small amount of water and add a few drops of the methyl-
red indicator solution (7.2.2.11). Neutralize the solution with a sodium hydroxide solution until its
colour turns yellow, and then add hydrochloric acid (1+50) (7.2.2.3) to return to red again.
f) Remove carbon dioxide in the solution by boiling or by purging nitrogen gas for 5 min with the
watch glass. Cool down to room temperature and wash the watch glass with small amount of water
before removing. Keep the total water volume not more than 150 ml while washing.
g) Stirring with a magnetic stirrer, titrate with 0,2 mol/l sodium hydroxide solution (7.2.2.12), depict
a titration curve around pH 6,4 using a pH meter, and determine the inflection point of the curve.
After removing the electrode, add 25 g of mannitol (7.2.2.8). Titrate again with the sodium hydroxide
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ISO 17942:2014(E)
solution (7.2.2.12), depict a titration curve around pH 8,5, and determine the inflection point of the
curve. Calculate the total volume of titrant between two inflection points.
7.2.6 Blank test
Perform operations of 7.2.5 a) to 7.2.5 g) without taking a sample to obtain the blank test value of boron.
7.2.7 Calculation
Calculate the content of total boron in the sample according to the following formula:
VV− ×F
()
10
TB. = ×100 (2)
m
where
T.B is the content of total boron in the sample [% (mass fraction)];
V is the total volume of the 0,2 mol/l sodium hydroxide solution after the first addition of man-
1
nitol in 7.2.5 g) (ml);
V is the total volume of the 0,2 mol/l sodium hydroxide solution of the blank test after the first
0
addition of mannitol in 7.2.6 (ml);
F is the factor of the 0,2 mol/l sodium hydroxide solution in 7.2.2.12 (g);
m is the weighed amount of the sample in 7.2.5 a) (g).
7.3 Fusion-ICP-OES
7.3.1 Principle
To prepare a test solution, decompose the sample using base, spray into the argon plasma flame of ICP-
OES, and measure the emission intensity at a selected wavelength.
This method can be used to obtain the results of two figures.
7.3.2 Reagents
Use only reagents of analytical grade unless stated to the contrary and prepare all solutions using
distilled or deionized water and store in polyethylene bottles.
WARNING — Hydrochloric acid causes burns and has an irritating vapour. Prevent inhalation
and contact with skin and eyes. Proceed as for sulfuric acid, carrying out the dilution in a fume
cupboard.
7.3.2.1 Hydrochloric acid, concentrated, density 1,095 g/ml.
7.3.2.2 Hydrochloric acid (1+1 solution), carefully add 50 ml of acid to 50 ml of water to a beaker
cooled in a water bath. Stir the mixture continuously. Allow to cool and store.
7.3.2.3 Nitric acid, ρ 1,42 g/ml.
7.3.2.4 Sodium peroxide (Na O ).
2 2
7.3.2.5 Sodium carbonate, anhydrous.
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ISO 17942:2014(E)
7.3.2.6 Ethanol.
7.3.2.7 Boron standard solution, containing 1,000 g of boron (B) per litre. Do not dry. Dissolve 5,716 g
of anhydrous H BO (B fraction = 0,174 9), accurately weighed to at least four significant figures, in
3 3
reagent water and dilute in a 1 l volumetric flask with reagent water. Transfer immediately after mixing in
a clean polytetrafluoroethylene (PTFE) bottle to minimize any leaching of boron from the glass container.
The use of a non-glass volumetric flask is recommended to avoid boron contamination from glassware. A
1 ml of this standard solution contains 1,0 mg of boron.
7.3.3 Apparatus
Apparatus are ordinary laboratory apparatus and the following:
7.3.3.1 Glass beaker, with a range of appropriate volumes (100 ml, 250 ml).
7.3.3.2 Volumetric flask, with a range of appropriate volumes (100 ml, 250 ml, 500 ml, and 1 000 ml).
7.3.3.3
...
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