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A N A L Y TI CA L A T O M I C S P E C T R O M E T R Y , S E P T E M B E R 1994, V O L .
9 1063
Analysis of Aluminium Oxide and Silicon Carbide Ceramic Materials
by Inductively Coupled Plasma Mass Spectrometry
Invited Lecture
J. A. C. Broekaert
Universitat Dortmund, Fachbereich Chemie, 0-44227 Dortmund, Germany
R. Brandt
Max-Planck-lnstitut fur Metallforschung, Stuttgart, Laboratorium fur Reinststoffanalytik, Postfach 722652,
0-44073 Dortmund, Germany
F. Leis
C.
Pilger
and
D. Pollmann
lnstitut fur Spektrochemie und angewandte Spektroskopie, Postfach 707352,D-44073, Germany
P. Tschopel and G. Tolgt
Max-Planck-lnstitut fur Metallforschung, Stuttgart, Laboratorium fur Reinststoffanalytik, Postfach 122652,
0-44073 Dortmund, Germany
The use of inductively coupled plasma mass spectrometry (ICP-MS) for trace element determinations in
A1203 and Sic powders as well as in compact Sic ceramics, subsequent to grinding to a particle size of
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Elemental, Winsford, UK) , the instrumental d ata and working
parameters for which are listed in Table 1. The analytical
parameters used were as proposed for the instrument by the
manu facturer. For th e direct analyses of the samples subsequent
to dissolution, pneumatic nebulization with a concentric glass
nebulizer (Meinhard Associates, Santa Ana, CA, USA) and
also with a Babington-type nebulizer (V-groove nebulizer,
Fisons Instruments, VG Elemental) positioned in a laboratory -
made cooled spray ch am ber 7 was used. In the on-line matrix
removal using complexation of the trace elements, adsorption
of the hexamethylenedithiocarbonate (H M D C ) complexes on
an RP18 column, solid-phase extraction and high-pressure
nebulization of the effluent were applied. A high-pressure
nebulization system (Fa. Knauer, Berlin, Germany), as devel-
oped by Berndt, was used in conjunction with desolvation,
including both water and a Peltier cooling.'
A combined knocking-grinding machine with a pestle as
well as
a
mor tar m ade of high-purity S i c (Elektroschmelzwerk,
Kempten) was used for grinding the compact S i c granulate
material. The mortar vessel was held in a steel enclosure
(Fig. 1). With this device it was found th at S i c granules w ith
grains of between 1 and 20 mm side lengths can be pulverized.
Below this grain size the grinding action of the machine was
not effective, as it seem ed that a certain size is required for the
pressure to w ork o n the granules. Below this size S i c pieces
were found not to be split.
Samp les and Reagents
Th e A1,0, powd ers analysed included AKP-20 (mean particle
size 0.57 pm, as ind icated by the m anufacturer, Sum itomo,
Japan) and AKP-30 [mean particle size measured by auto-
mated electron p robe microanalysis (EP MA ) 0.35 and 0.43 pm,
as indicated by the manufacturer, Sumitorno] as well as ME/03
(mean particle size measured by auto ma ted EP M A 0.35 pm).
The ME/03 is a powder which has been characterized
previously in a round-robin organized by the Arbeitskreis:
Refraktarwerkstoffe in the Chem iker Ausschul3 der Gesellschaft
Deutscher M etallhiitten- un d Bergleute (G DM B). The particle
size distribution of the powders was determined by both
autom ated EP M A (for a description of the m ethod, see ref. 9)
Table
1
Plus ICP-MS instrument
Instrumental and working parameters for the PQ2 Turbo
~~
Generator
Nebulizers
V-groove nebulizer
Concentric glass nebulizer
Spray chamber
Peristaltic pump
Interface
Sampler
Skimmer
Power
Gas flows
Outer
Intermediate
Aerosol carrier
Sample uptake rate
Sampling depth
Vacuum
1st stage
2nd stage
Mass spectrometer
Mass range
Dwell time
Detector
Henry, 2.0 kW, 27.12 MHz
Meinhard Associates
Scott-type made of quartz
Gilson Minipuls 3
Ni, aperture 1.0 mm
Ni, aperture 0.7 mm
1.35kW forward
10-15 W reflected
14lmin-'
0.9-1.5 min-'
0.9- 1.1 min 3 bar*)
0.75-1.1 ml min-'
10-12 mm
2.0-3.0 mbar
-=1 x mbar
2.0-3.0 x mbar
10-141 u for A1,0,, 5-239 u
for Sic
Dual mode, 640
ps,
pulse
counting mode, 320
ps
Analogue-pulse counting
'L
ortar
Rotating
vibrator
i
teel ho l de r
Fig.
1
Grinding device for compact Sic
and by laser stray radiation measurements (laser particle sizer,
Analysette 22- Fritsch, Idar-Ob erstein, Ge rm any ). Reasonable
agreement between the results was obtained, considering that
deviations possibly can arise from differences in the ultrasonic
treatment of the suspension being measured and artifacts from
the nuclepore filter loading encountered in the case of
EPM A (Fig. 2).
The S i c samples analysed were A10 (mean particle size
xl pm, as indicated by the manufacturer, H.C. Starck,
Gos lar, Germany) an d S-933 (Elektroschmelzwerk, Kem pten,
Germany) in the form of a powder (mean part ic le s ize ~ 0 . 8m,
as indicated by the manufacturer) and granules (grain size
-10
mm).
The HC l and the
H2S0,
used for the sam ple decomposition
were purified by sub-boiling distillation. All dilutions were
20
100
80
40
20
0
b) 0.1 oF o 2.0
/
20
10
B
0
0 5 1
5 10
D
a
m
ete
r/pm
Fig. 2 Particle size distribution obtained for the A1,0, powder
AKP-30 (Sumitomo, Japan) by:
a)
EPMA (mean diameter= 0.35 pm);
and b) aser light scattering (mean diameter=0.59 pm)
1bar= 1 x lo5 Pa.
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made with H 2 0 doubly distilled in qu artz equipment. The H F
used (Merck, Darm stadt, Germany) was of Suprap ur quality.
For the preparation of the standard solutions the respective
Titrisol stock solutions (Merck) were used. Sample decompo-
sitions were performed at high temperature and pressure in
closed poly( tetrafluoroethylene) (P T F E ) vessels (Berghof DAB
111, Tubing en, Ger ma ny) . In the m atrix removal studies,
HMDC (Merck) and C,, RP18 columns (Fa. Knauer) were
used.
Results
and
Discussion
Analysis
ofA1203
Powders
After initial tests with an AlCl, solution, it was found th at the
analyte solution for ICP-MS investigations should not contain
more than ~ 2 0 0g ml of Al, which corresponds to a concen-
tration of 400 pg ml-' of A1,0,. Indeed, at higher concen-
trations high ablation of the sampler was observed and also a
glassy deposit was soon formed on the skimmer. Both lead to
clogging as well as to a deterioration of the short-term
precision, expressed by the relative stan dard deviations (RSDs)
and long-term drifts.
15
A
t
0 50
100
150
200 250
Time/min
Fig .3 Long-term stability in ICP-MS analyses of A1203 after acid
decomposition: A, 24Mg;B, 66Zn;C, '39La; D,139La:'I5In and E, 24Mg:
45Sc. Sample solutions: 10ng ml-' of
B,
Na, Mg, Ti, V, Cr, Mn, Co,
Ni,
Zn, Ga, Zr, Ba, La and Ce;
400
pg ml- of A1203,
10
ng ml-' In
and 50 ng ml-' of Sc in 0.04 moll- HC1-0.0064 moll- ' H 2 S 0 4 .
ICP-MS:
PQ2
Turbo Plus with quartz spray-chamber
(10
C)
(measurement conditions as in Table 1 . Measurement cycle: pre-flow,
90 s; measurement time, 5
x 60
s; rinsing with acid solution,
2.5
min
1065
At a sample concentration of 4 0 0 p g m l - ' of A120,, the
RSD s were 2-5% for impurity concen trations of 10 ng ml -'
a n d in a 0.0 4m o 11 -1 H C1 a nd 6 . 4 ~op3m o l l - ' H 2 S 0 4
solution, which are the concentrations of acid present after
acid decomposition of the samples. However, when adding
10
ng ml -' of In an d 50 ng ml -' of Sc as internal stand ards ,
the short-term precision for all elements investigated (B, Na,
Mg, Ti, V, Cr, Mn, Co, Ni, Zn, Ga, Zr, Ba, La and Ce)
becomes
of
the orde r of 1-2% an d drifts [with an intermediate
washing stage of 2.5 min after each sam ple (measurement cycle:
pre-flow 90 s, integration 5 x 60
s)]
after an initial period are
below 5% over a period of 4 h (Fig. 3).
For dissolution of the Al,O, powders treatment w ith HC1
and H,SO, at 225C according to the following procedure
was found to be optimum. A 1+0.001 g sample of A120,
powder was transferred into a 150 ml PT FE vessel (Fa.
Berghof) and 10ml of sub-boiled HCl plus 1 ml of sub-boiled
H,SO, and 5m l of H 2 0 were also added. The mixture was
allowed to react for 6 h at 225 C in the closed vessel. The
resulting solution had been diluted 1
+
2500. Four solutions
with matched acid concentrations and analyte concentrations
of 0.4, 4, 40 and 400 ng ml -' and containing 5 ng ml -l of Rh
as an internal standard were used for calibration purposes.
The rinsing solution used contained 4m l
of
sub-boiled HCl
and 0.4 ml
of
sub-boiled
H , S 0 4
in 1 1 of H,O.
For analyte concen trations of 400 pg m l-' of A1203 , the
detection limits obtained for ICP-MS (based on the 3s cri-
terion), with a non-cooled spray chamber and considering the
blank limitations of all reagents used, are listed in Table2.
They range from 0.1 to
4
pg g- ' and a re higher for the low
mass elements. However, severe blanks (N a) or sp ectral inter-
ferences (Ca, Fe and Zn) are seen to occur. In the case
of
the
instrument used, no systematic differences could be noticed
when comparing the detection limits obtained in the scanning
mode with those of the peak jumping mode for a dwell time
of 640ps per channel and 25 scan cycles. Furthermore, the
increased values found for a number of elements were clearly
due to spectral interferences by oxygen, chlorine or sulfur
containing cluster ions of argon (see Table
3).
Under the
conditions originally used, the detection limits with ICP-MS
for a number of elements with respect to the solid samples
were even lower than with ICP-AES, however, only for
elements with a mass below 60. At higher m asses this situation
changes, as, with IC P-AE S, it is no longer possible to determine
elements of interest in the concentration range required for the
analysis of advanced ceramics.
Table 2 Detection limits cL)
(3s
concept) of ICP-MS and ICP-AES for the analysis of A1203. Values in parentheses are for analyte solutions in
distilled H20. Other values based on four replicates (ICP-MS)
or
12 replicates (ICP-AES)
of
the decomposition with all acids
ICP-MS*
Scanning mode,
c,/ng ml
-
1.0
(0.25)
6.5 (0.4)
2.0 (1.9)
32 (6.4)
0.8 (0.4)
0.3 (0.1)
36 (4.3)
0.3 (0.07)
2.0 (0.4)
0.6 (1.4)
0.06 (0.03)
0.05 (0.04)
(0.01)
(0.02)
0.01 (0.01)
0.01)
Peak jumping
c,/ng ml-'
1.3 (0.1)
8.3 (1.3)
1.4 (1.4)
30 (3.8)
1.4 (0.1)
0.3 (0.06)
35 (2.6)
0.08
(0.06)
0.5
(0.07)
0.07 (0.07)
1.8
(0.2)
0.8 (1.1)
0.13
(0.07)
0.16 (0.16)
0.06 (0.05)
0.07 (0.05)
CLIPg g
-
3.2
18.0
3.5
75
3.5
0.75
0.75
1.2
0.18
4.5
1.5
0.32
0.32
0.15
0.17
87
Actual?
c,,lClg
g
0.6
1.1
0.7
1.2
0.04
0.024
0.08
0.04
0.8
0.008
0.23
0.002
0.008
0.008
ICP-AES:
C J P g
3
-
0.6
0.03
0.05
0.3
0.8
2.1
0.9
~~~~~~~ ~ ~
*
Sample dilution 1 +2500; PQ2 Turbo Plus.
7 Values obtained after cooling the quartz spray chamber down to
10
C.
$
From
ref.
3.
Sample
dilution
+50; 2 kW ICP, 0.9 m Czerny-Turner monochromator.
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Table 3
with HCl-H2S04 in a PTFE vessel
Spectral interferences in ICP-MS for Alz03. Decomposition
Analyte
44Ca
47Ti
48Ti
51v
Cr
53Cr
Mn
56Fe
Fe
60Ni
64Zn
66Zn
71Ga
Interferen
12~160160, 2 7 ~ 1 1 6 0 ~
3 3 ~ 1 4 ~
3 2 ~ 1 6 0
35CPO
3 7 ~ 1 1 6 0
4 0 ~ ~ 1 6 0
35C1160H, 0Ar12C, 6Ar160, 6 S 1 6 0
40Ar'4NH
40Ar160H
Cones
3 2 ~ 1 6 0 1 6 0
34~160160,
3 2 ~ 3 4 s
36Ar35C1
In the case of the AK P-3 0 powder, results in the 0.1-2 pg g-'
range were obtained for B, Ti, Cr, Mn, Ni,
Cu,
Zr, Ba, La and
Ce (Table 4). The results obtained in the peak jump ing mode
agreed well with those of the scanning mode. Even with the
semiquantitative programe, the results deviated by less than a
factor of two w ith only a few exceptions. In the case
of
Fe and
Ca, however, severe deviations were obtained, which could
relate more to interference problems, as these are known
already from the early literature o n IC P- M S (see for example,
ref. lo), than to blank limitations. The accuracy of the IC P-M S
results obtained was evaluated by performing analyses of the
ME/03 powder, which has also been analysed extensively by
other techniques (Table 5 ) . Excepted for Fe, reasonable agree-
Table 4 Results for analysis of Al,03 powder (AKP-30) by ICP-MS.
All concentrations are in
pg
g- he standard deviations from four
replicate analyses; final dilution, 1
+
2500; and internal standard, Rh
Anal yte
l l B
47Ti
Cr
Mn
60Ni
6 3 c u
71Ga
'OZr
138Ba
I3'La
l4OCe
Semiquantitative Scanning mode
Peak jumping
2.2 0.2 4.5 10 .6 4.8 f0 .3
1.3f0.3
0.15 f O l
2.6
_+
0.2 1.3f0.15 1.0 .07
1.1 fO.1 0.7 .15 0.25 .09
1.5f0 .1 0.7 .05 1.1 f0 .04
0.05 .02
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Table
6 Determination of the leachable and the non-leachable impurities in the A1,0, samples AKP-20 and AKP-30 by ICP-MS when leaching
with
2
(v/v) HN03. Figures in parentheses are the standard deviations from four replicate analyses. The results given for the alternative
methods are from acid decomposition of the sample without applying leaching with
2
HNO, (v/v)
Concentration/pg g-
'
Analyte
B
Na
Mg
Ca
Ti
V
Cr
Mn
Fe
c o
Ni
c u
Zn
Ga
Zr
Ba
La
Ce
A K P - 2 0 -
A K P - 3 0 -
B
Na
Mg
Ca
Ti
V
Cr
Mn
Fe
c o
Ni
c u
Zn
Ga
Zr
Ba
La
Ce
Leachable
2.8 (0.05)
2.8 (0.09)
0.98 (0.007)
0.07 (0.001)
0.2 (0.003)
0.15 (0.004)
0.026 (0.0003)
1.0
(0.1)
0.002 (0.00005)
0.1 (0.002)
0.55
(0.005)
0.33 (0.01)
0.006
(0.0003)
0.015 (0.0003)
0.046 (0.003)
0.037 (0.0005)
1.1 (0.02)
0.1 (0.002)
0.82 (0.02)
1.8 (0.04)
1.2 (0.3)
1.02 (0.02)
0.1 (0.001)
0.1 (0.002)
0.09 (0.002)
0.017 (0.0005)
0.8
(0.1)
0.002 (0.0003)
0.07
(0.001)
0.62 (0.003)
0.33 (0.002)
0.01 (0.0005)
0.015 (0.0003)
0.22 (0.004)
0.29 (0.005)
0.11 (0.002)
Non-leachable
6.5