J OURNAL OF ANALYTICAL ATOMI C SPECTROMETRY , SEPTEMBER 1994, VOL.

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
<20 pm, was investigated. The dissolution procedure, optimized for A1203, included treatment with HCI and
H2S04. For ICP-MS analyses the maximum tolerable AI,O, content in the solutions to be measured was
found to be 400 pg ml-' , for which detection limits in the range 0.002-2 pg g-' were obtained. Analyses of
real samples in the concentration range of 0.05 to several hundred pg g-' will be discussed in terms of
precision and accuracy and it will be shown that leaching of the powders with acids could provide information
on the localization of the impurities. The influence of the removal of CI from the analyte solutions on spectral
interferences in the low mass range and of cooling the spray chamber on the power of detection will be
discussed. A further method of improving the power of detection could lie in matrix removal, based on the
on-line complexation of Co, Cu, Cr, Fe, Ga, Mn, Ni and V with hexamethylenedithiocarbamate. For Sic
powders dissolution by treatment with HN03, H2S04 and HF will be shown to lead to a number of spectral
interferences and to limit the tolerable analyte concentration to 500 pg ml-', for which detection limits range
from 0.002 (for heavy elements) to 10 pg g-' for elements such as Mg. Results for the determination of 6,
Na, Al, V, Cr, Mn, Fe, Ni, Co, Cu, Ga, Sr, Y, Zr, In, Sn, Ba, La, Hf, Pb and U in ceramic powders of industrial
importance will be presented.
Keywords: Ceramic powders; inductively coupled plasma mass spectrometry; aluminium oxide; silicon
carbide
Advanced ceramics now find wide interest as working materials
in diverse areas of science and technology. Their sometimes
extreme properties in terms of hardness, corrosion and tem-
perature resistance or electrical as well as thermal conductivity
often depend greatly on their composition.' In a number of
cases this is now known to apply down to the trace element
level. Therefore, not only is the determination of bulk impurities
important but also the micro-distribution of elements in
advanced ceramics is crucial. I n addition to the characteriz-
ation of compact ceramics, the analysis of the basic products
is also important so as to be able to optimize production
procedures, including the exclusion of contamination at the
various production stages and tailoring the properties of the
material by controlling the levels of impurities. For analysis of
the basic products, atomic spectrometric methods are very
important, as multi-element characterization down to the sub-
pg g-' level is required.2 By applying inductively coupled
plasma atomic emission spectrometry (ICP-AES), this goal
can be reached for a number of elements in the matrices A1203,
Si c and Zr02. Indeed, after careful optimization of the working
conditions of ICP-AES, eventually with the aid of simplex
procedures, a range of trace elements can be determined in
A1203 (Ca, Co, Cu, Fe, Mg, Mn and Zn),3 Si c (Ca, Cd, Cr,
* Presented at the 1994 Winter Conference on Plasma Spectro-
t Also at Institut fur Spektrochemie und angewandte Spektroskopie,
chemistry, San Diego, CA, USA, January 10-15, 1994.
Postfach 101352, D-44013 Dortmund, Germany.
Cu, Mg, Mn and Zn)4 and ZrO, (Al, B, Ca, Cu, Fe, Mg, Mn,
Na, Ti, V and Y),5*6 however, severe limitations occur especially
for the heavier elements.
In the present work it will be shown that for many elements,
in the case of A1203 and Sic, reliable multi-element trace
characterization at lower concentration levels can be performed
by applying inductively coupled plasma mass spectrometry
(ICP-MS) instead of ICP-AES. Herefore, the sample prep-
aration procedures known from previous ICP-AES work in
these laboratories had to be adapted to the requirements of
ICP-MS in terms of sample concentrations and also for the
acids used during the sample pre-treatment. Special precautions
such as cooling of the spray chamber and removal of C1from
the measurement solutions will be discussed for the case of
A1203. Also, a method of matrix removal, which leads to
possibilities for further improvement of the power of detection
will be presented. In the case of Sic, optimization of the
dissolution procedure, a detailed discussion of spectral inter-
ferences in ICP-MS and possibilities for the analysis of compact
Si c will be also discussed. Results for commercially available
A1203 and Si c materials used for the production of advanced
ceramics will be presented.
Experiment a1
Instrumentation
All measurements were performed with a PlasmaQuad PQ2
Turbo Plus ICP-MS instrument (Fisons Instruments, VG
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1064 J OURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, SEPTEMBER 1994, VOL. 9
Elemental, Winsford, UK), the instrumental data and working
parameters for which are listed in Table 1. The analytical
parameters used were as proposed for the instrument by the
manufacturer. For the 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 chamber7 was used. In the on-line matrix
removal using complexation of the trace elements, adsorption
of the hexamethylenedithiocarbonate (HMDC) 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 mortar made of high-purity Si c (Elektroschmelzwerk,
Kempten) was used for grinding the compact Si c granulate
material. The mortar vessel was held in a steel enclosure
(Fig. 1). With this device it was found that Si c granules with
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 seemed that a certain size is required for the
pressure to work on the granules. Below this size Si c pieces
were found not to be split.
Samples and Reagents
The A1,0, powders analysed included AKP-20 (mean particle
size 0.57 pm, as indicated by the manufacturer, Sumitomo,
J apan) and AKP-30 [mean particle size measured by auto-
mated electron probe microanalysis (EPMA) 0.35 and 0.43 pm,
as indicated by the manufacturer, Sumitorno] as well as ME/03
(mean particle size measured by automated EPMA 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 Chemiker Ausschul3 der Gesellschaft
Deutscher Metallhiitten- und Bergleute (GDMB). The particle
size distribution of the powders was determined by both
automated EPMA (for a description of the method, 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
1.35 kW forward
10-15 W reflected
14lmin-'
0.9-1.5 1 min-'
0.9- 1.1 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 Si c
Dual mode, 640 ps, pulse
counting mode, 320 ps
Analogue-pulse counting
'L
mortar
d
Rotating
vibrator
i
Steel hol der
Fig. 1 Grinding device for compact Si c
and by laser stray radiation measurements (laser particle sizer,
Analysette 22- Fritsch, Idar-Oberstein, Germany). 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
EPMA (Fig. 2).
The Si c samples analysed were A10 (mean particle size
xl pm, as indicated by the manufacturer, H.C. Starck,
Goslar, Germany) and S-933 (Elektroschmelzwerk, Kempten,
Germany) in the form of a powder (mean particle size ~0 . 8 pm,
as indicated by the manufacturer) and granules (grain size
x 1-10 mm).
The HCl and the H2S0, used for the sample decomposition
were purified by sub-boiling distillation. All dilutions were
20 I
100
80
I 60
40
20
0
( b) 0.1 oF.o 2.0
/
20
A
10
B
0
0.5 1 5 10
D i a m et e r/pm
Fig. 2 Particle size distribution obtained for the A1,0, powder
AKP-30 (Sumitomo, J apan) by: (a) EPMA (mean diameter =0.35 pm);
and (b) laser light scattering (mean diameter=0.59 pm) * 1 bar=1 x lo5 Pa.
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J OURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, SEPTEMBER 1994, VOL. 9
made with H20 doubly distilled in quartz equipment. The HF
used (Merck, Darmstadt, Germany) was of Suprapur 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) (PTFE) vessels (Berghof DAB
111, Tubingen, Germany). In the matrix removal studies,
HMDC (Merck) and C,, RP18 columns (Fa. Knauer) were
used.
Results and Discussion
Analysis of A1203 Powders
After initial tests with an AlCl, solution, it was found that the
analyte solution for ICP-MS investigations should not contain
more than ~2 0 0 pg 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 standard deviations (RSDs)
and long-term drifts.
15
A 1
3t
0 50 100 150 200 250
Time/mi n
Fig.3 Long-term stability in ICP-MS analyses of A1203 after acid
decomposition: A, 24Mg; B, 66Zn; C, '39La; D,139 La:'I5In and E, 24Mg:
45Sc. Sample solutions: 10 ng 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- ' H2S04.
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 400pgml-' of A120,, the
RSDs were 2-5% for impurity concentrations of 10 ng ml-'
and in a 0.04mo11-1 HC1 and 6 . 4 ~ l op3 moll-' H2S04
solution, which are the concentrations of acid present after
acid decomposition of the samples. However, when adding
10 ng ml-' of In and 50 ng ml-' of Sc as internal standards,
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 order of 1-2% and drifts [with an intermediate
washing stage of 2.5 min after each sample (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 with 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 PTFE vessel (Fa.
Berghof) and 10 ml of sub-boiled HCl plus 1 ml of sub-boiled
H,SO, and 5ml of H20 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 4ml of sub-boiled HCl
and 0.4 ml of sub-boiled H,S04 in 1 1 of H,O.
For analyte concentrations of 400 pg ml-' 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 are higher for the low
mass elements. However, severe blanks (Na) or spectral 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 masses this situation
changes, as, with ICP-AES, 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)
CLIPgg -
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:
CJ Pg ! 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 1 +50; 2 kW ICP, 0.9 m Czerny-Turner monochromator.
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1066 J OURNAL OF ANALYT1CA.L ATOMIC SPECTROMETRY, SEPTEMBER 1994, VOL. 9
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 t
12~160160, 2 7 ~1 1 6 0 ~
3 3 ~ 1 4 ~
3 2 ~ 1 6 0
3 5 CPO
37~1160
4 0 ~~1 6 0
35C1160H, 40Ar12C, 36Ar160, 36S160
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 AKP-30 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 jumping mode
agreed well with those of the scanning mode. Even with the
semiquantitative programe, the results deviated by less than a
factor of two with 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 on ICP-MS (see for example,
ref. lo), than to blank limitations. The accuracy of the ICP-MS
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-' f the standard deviations from four
replicate analyses; final dilution, 1 +2500; and internal standard, Rh
Anal yte
l l B
47Ti
"Cr
"Mn
60Ni
63cu
71Ga
'OZr
138Ba
I3'La
l4OCe
Semiquantitative Scanning mode Peak jumping
2.2 f 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 f 0.07
1.1 fO.1 0.7 f 0.15 0.25 f 0.09
1.5f0.1 0.7 f 0.05 1.1 f0.04
- 0.05 f 0.02
<0.08
0.4 f 0.2 0.4 f 0.25 0.5 f 0.3
1.0f0.3 1.1 k0.2 1.1 k0.3
0.14f0.01 0.16f0.01 0.13f0.01
0.4 f 0.02 0.5 f 0.02 0.4 f 0.02
0.12 f 0.06 -
-
ment of the ICP-MS results with those of other methods was
obtained at levels ranging from concentrations of sub-pg g-'
to 700 pg g-', which clearly illustrates the analytical features
Further possibilities for ICP-MS are shown by the results
from leaching experiments performed with the AKP-20 and
AKP-30 powders. Indeed, when leaching the samples with
dilute HNO, (22 ml of sub-boiled HNO, in 11 of H20)
overnight and then analysing the leaching liquid and the
residue after acid decomposition by ICP-MS, the sums of the
results obtained are in good agreement with those from
independent methods (Table 6). This shows that ICP-MS
should be of great use for monitoring sources of contamination
during the stages of powder processing but also that it could
be of use for showing differences in the localization of the
different elements in the individual grains, which could again
indicate their origin.
Based on experience, of the limitations of the actual power
of detection, several measures could be taken so as to realize
progress in detection limits for Alz03. The first improvements
in the power of detection resulted from the use of a cooled
spray chamber. This measure was shown to lead to a reduction
of the white noise in particular, as described el~ewhere.~ This
leads directly to an improvement in the short-term fluctuations
as expressed by the RSDs, but also to a reduction of the
spectral interferences, as reflected by the signals obtained on
the different channels for doubly distilled HzO (Table 7).
Accordingly, it was found that the power of detection could
be considerably improved by cooling the spray chamber down
to 10C. The use of a quartz spray chamber and rinsing of
the spray chamber injector tube assembly by steaming with
vapours of HNO, brought further improvement. The improved
detection limits for the A1203 samples, taking into account the
blanks, obtained with a cooled and pre-cleaned quartz spray
chamber in the pulse counting mode are given in a separate
column of Table 2.
It was also found that for a number of powders the use of
H,SO, was not strictly required. Indeed, with the same reaction
time (6 h) it was found that the decomposition could be
performed with 10ml of sub-boiled HC1 and 5ml of HzO,
added to 1 g of sample, provided the temperature was increased
from 225 to 240"C, as experienced with the AKP-20 and
AKP-30 powders. It was further found that the interferences
could be considerably reduced when Cl was removed from the
sample solutions, by treatment with sub-boiling HNO,. When
working under clean-room conditions, recoveries for Rb, Sr,
Y, Zr, Rh, La, Ce, Sm, Eu, W and Th at the 20ngml-' level
of ICP-MS.
Table 5
analyses. Final dilution, 1 +2500; internal standard Rh
Results for analysis of A1203 powder ME/03 by ICP-MS. All concentrations are in pg g fthe standard deviations from four replicate
ICP-MS Comparison with ICP-AES
Anal yte
l l B
23Na
24Mg
44Ca
52Cr
"Mn
57Fe
59c0
60Ni
63cu
66Zn
71Ga
'OZr
138Ba
13'La
"OCe
Scanning
0.4 f 0.2
781 f 33
492 f 21
404 k 30
1.5fO.l
1.6f0.02
359 f 20
0.4 f 0.02
10.2 f0.5
1.4 f 0.1
3.8 k0.5
87 f 2.4
7.5k0.15
20.2 & 2.8
0.03 & 0.01
0.1
Peak jumping
735 f 32
464 f 20
268 38
1.0 & 0.4
1.2k0.2
326 f 8
0.4 f 0.01
9.7 f0.3
1.3f0.05
3.0 f 0.08
90f 1.3
6.6 f 0.6
17.3 f 2.0
0.01 f 0.01
0.07 f 0.02
-
Our work
<3
777
456 f 7
191 f 10
1.4 k 0.01
251 k 3
<6
9.0 f 0.2
<3
<13
92 f 0.8
-
-
-
-
-
Other laboratories
2.2 k 0.5
755 +42
463 k 16
178 k 17
3.3 f 1.9
2.0 f 0.7
245 k 10
11.4 f 5.9
1.0 * 0.1
6.2f4
87+5
9.2f 1.0
1.1
-
0.1*
0.3*
* Results from neutron activation analysis.
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J OURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, SEPTEMBER 1994, VOL. 9 1067
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
co
Ni
cu
Zn
Ga
Zr
Ba
La
Ce
AKP- 20-
AKP- 30-
B
Na
Mg
Ca
Ti
V
Cr
Mn
Fe
co
Ni
cu
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)
0.01 5 (0.0003)
0.22 (0.004)
0.29 (0.005)
0.11 (0.002)
Non-leachable
6.5
<1.1
1.1
0.33
1 .o
1.9
0.16
9.9
0.04
0.31
0.57
<0.8
0.17
<0.23
0.01
0.04
0.17
<24
2.3
<1.1
1.6
0.19
1.5
1.4
0.10
6.8
0.11
0.21
1.0
<0.8
0.08
<0.23
0.02
0.17
0.52
<24
Sum
9.3
<3.9
2.2
1.31
0.84
2.05
0.19
0.042
0.41
1.12
<1.13
0.18
<0.245
0.056
0.077
0.27
<24.2
10.9
3.12
<2.9
2.8
1.21
1.6
<24.1
1.49
0.117
7.6
0.1 12
0.28
1.62
<1.13
0.09
<0.245
0.24
0.28
0.8 1
Alternative method
8.2 (ICP-AES)
4.0 (NAA)*
2.4 (ICP-AES)
1.26 (ICP-AES)
0.77 (ICP-AES)
<10 (TXRF)?
1.35 (NAA)
<0.3 (ICP-AES)
10.2 (ICP-AES)
0.032 (NAA)
<3 (TXRF)
1.6 (NAA)
0.12 (NAA)
1.1 (NAA)
0.087 (NAA)
0.24 (NAA)
1.4 (ICP-AES)
-
3.3 (ICP-AES)
-
2.06 (ICP-AES)
1.26 (ICP-AES)
1.06 (ICP-AES)
-
1.0 (ICP-MS)
<0.3 (ICP-AES)
7.1 (ICP-AES)
<2.1 (ICP-AES)
0.25 (ICP-MS)
1.29 (ICP-AES)
-
<0.08 (ICP-MS)
0.5 (ICP-MS)
1.1 (ICP-MS)
0.1 3 (ICP-MS)
0.4 (ICP-MS)
* NAA, neutron activation analysis.
TXRF, total-reflection X-ray fluorescence.
and in the presence of 400 pg ml-I of A1,0, were better than
loo+10%. However, for a number of elements the losses soon
became larger with this procedure (Table 8).
Another method of improving the power of detection could
result from separation of the trace elements to be determined
from the aluminium matrix, as is possible by on-line separation
from the complexes of a number of elements with dithiocarb-
oxylates such as HMDC. This can be realized with the aid of
a high-performance liquid chromatography (HPLC) system,
where the HMDC complexes are sorbed onto a suitable
column and released by solid-phase extraction. The eluate can
then be brought into aerosol form by high-pressure nebuliz-
ation, desolvated and released into the ICP-MS instrument."
In the present work complexation of the trace elements was
performed by adding 500 pl of a 4% HMDC solution to the
decomposition solution. Subsequently, dilution to a final
volume of 100 ml was performed and the pH was adjusted to
2-3 with concentrated ammonia solution. When passing 1 ml
of the solution through a C18 RP column and using a
methanol-H,O mixture of 70 +30 as the eluent, recoveries of
better than 97% could be found for a number of trace elements
( V, Fe, Ni, Co, Cu and Ga) at the 100ng ml-1 level. Over
99.5 +0.3% of the A1matrix could be removed at the 2 mg ml-1
concentration level.
These measures certainly will enable a considerable improve-
ment in the actual power of detection to be realized for the
case of Al,O,. With the present state-of-the-art, improvements
in the power of detection of ICP-MS with respect to the one
achieved with ICP-AES for the low mass range are possible,
whereas up till now for some elements the actual power of
detection of ICP-MS obtained with respect to solid samples
was not improved as compared with ICP-AES (Table 2). Such
progress is clearly required in view of the requirements for the
determination of a number of elements in powders used for
the production of advanced ceramics.
Analysis of Sic Powders
For the case of Si c powders, sample decomposition prior to
ICP-MS analysis was found to be achieved efficiently by
treatment of the powders with a mixture of HF, HNO, and
H2S04, according to the procedure described below.
For the decomposition of Sic, 250mg of powder were
treated for 12 h at 250C with 4 ml of concentrated HF
(Suprapur) and 4 ml of concentrated HNO,, as well as 4 ml
of concentrated H2S04, both of which were purified by sub-
boiling distillation. The resulting solution was then diluted to
500 ml and accordingly the solution used for measurement
contained 500pgml-' of Si c in 0.8% HNO,, 1.5% H2S04
and 0.5% HF. Analyses by ICP-MS included five measure-
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1068 J OURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, SEPTEMBER 1994, VOL. 9
Table7
aqueous standard solution, 20 ng ml-'; and short-term stability (30 min)
Influence of a cooled spray chamber made of quartz on the stability and on the blank signal levels in ICP-MS. Meinhard nebulizer;
Without cooling With cooling to 10C
Standard
deviation
3.0
(Yo)
-
-
2.2
-
2.2
2.0
-
-
2.5
-
3.1
-
3.1
3.5
3.7
3.4
Blank
concentration*/
ng ml-'
-
0.7
22.0
2.1
0.11
0.03
0.56
0.03
0.75
0.37
0.44
0.1 1
0.01
0.03
0.02
0.02
112
-
-
Standard
deviation
2.5
W O )
-
2.7
-
2.3
1.8
-
2.3
-
1.3
-
1.3
1.4
1.6
2.0
Blank
concentration/
ng ml-'
0.5
3.00
0.7
0.07
0.02
0.20
0.004
0.11
0.13
0.26
0.1 1
0.04
0.12
0.005
0.008
-
14
-
-
* Blank signal for doubly distilled H,O converted into concentrations.
Table 8 Recoveries obtained for a series of trace elements on removal
of C1from AlCl,-containing solutions: Procedure involved dissolution
of 3.3 g of A1Cl3.6H2O in 18 ml of H2 0 and addition of 1 pg of the
trace elements, addition of 2 ml sub-boiled HN03, adjusting to 50 ml
with H20 and evaporation of the sample on a heating plate under
clean-room conditions
Element
Be
Ti
Mn
Co
Rb
Sr
Y
Zr
Mo
Rh
La
Ce
Sm
Eu
W
T1
Mg
Concentration found/
ng ml-I
15.72
17.84
16.45
17.81
17.49
18.45
19.00
19.12
18.85
17.86
18.15
18.69
19.25
19.98
19.29
20.85
19.71
Recovery
W)
78.6
89.2
82.3
89.1
87.5
92.3
95.0
95.6
94.3
89.3
90.8
93.5
96.3
99.9
96.5
104.3
98.6
ments for each sample and calibration was achieved with four
independent blanks and five standard solutions. In order to
carry this out, the I CP Multielement Standard IV (Merck)
was used, to which Ti, V, Zr, Zn, La, Hf and U were added
and of which dilutions of 0.1, 0.5, 1, 10 and 100 ng ml-1 were
made, with the addition of 40ngml-' of Rh as an internal
standard. A sample concentration of 500 pg ml-1 appeared to
be the maximum tolerable matrix concentration because of the
risk of deposition on the cones and especially on the skimmer.
The analytical short-term precision was found to be between
1 and 3%, depending on the mass and concentration. At the
maximum sample concentration of 500 pg ml-', the detection
limits found for Li, B, Na, Mg, Al, V, Cr, Mn, Fe, Ni, Co, Cu,
Zn, Ga, Sr, Y, Zr, Ag, Cd, In, Sn, Ba, La, Hf, T1, Pb, Bi and
U were found to be between 0.002 and 17 pg g-' (Table 9).
The high values for Fe, Zn and Mg certainly relate to spectral
interferences whereas, for Na, contamination could be the
predominant problem (Table 10). It could be shown, however,
that for the case of the Si c powder S-933, the ICP-MS results
obtained subsequent to dissolution agreed well with results for
ICP-AES after sample dissolution as well as with those from
instrumental NAA ( INAA),12 the ICP-AES suspension tech-
niqueI3 and electrothermal atomic absorption spectrometry
(ETAAS) using slurry atomi~ation,'~for all of which the
detection limits are listed in the same table.
I n the case of ICP-MS for Si c powders, it could be expected
that removal of the Si and the C arising from the matrix, as
well as of the decomposition acids by heating the solutions to
near dryness, could improve the limit of detection. However,
whether such procedures would lead to high analyte losses for
a number of relevant elements must be investigated. Further
progress in the analysis of Si c powders by ICP-MS could
result from the application of slurry nebulization, which,
however, could be hampered by abrasion of the sampler and
deposits on the skimmer, hence also limiting the sample
concentrations in the slurries. The application of electrothermal
evaporation, as applied in ICP-AES for ceramic powders by
Nickel et could be useful as well, but this would certainly
necessitate detailed investigations of the calibration.
In order to make progress in the analysis of compact
ceramics, the possibilities of advanced grinding devices could
be useful. With a device made of high-purity Si c (Fig. l), it
has been found that it is possible to grind a Si c granulate
material (1-20 mm side lengths of the grains) in less than 15 s,
to a powder with a particle size of <20 pm for the majority
of the milled sample. However, possible contaminations during
the grinding procedure will have to be investigated, so as to
evaluate the feasibility of the device as compared with other
direct solids procedures, such as laser ablation ICP-MS.
Conclusion
The results presented for A120, and Si c powders show that
ICP-MS is a very powerful tool for multi-element trace charac-
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JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, SEPTEMBER 1994, VOL. 9 1069
Table 9 Detection limits for Si c and results for analysis (pg g-') of Si c powder S-933 obtained with ICP-MS (present work), INAA and ICP-
AES after sample decomposition and ETAAS using slurry atomization. Figures in parenthesis are the cL (pgg-') based on the 3s concept
including blank limitations. Sample, S-933. Values & are the standard deviations calculated from four replicate analyses and five repetitive
measurments of each sample solution obtained by acid decomposition
ICP-MS
decomposition
<CL
(0.034)
2.7 f 0.5
(0-9)
35.8 f 1.2
(7.3)
<CL
(9.5)
(6)
Interference
192f 15
Interference
80.7 f 2.0
(0.5)
8.2 kO.8
(0.4)
7.8 f 0.6
(0.4)
0.79 f 0.05
(0.06)
348f13
(17)
5.6 f 0.4
(0.2)
0.079 f 0.01 3
(0.01)
3.37 f 0.24
(0.09)
<CL
0.082 f 0.01 1
(0.03)
0.061 f 0.01 5
(0.023)
0.066 f 0.003
(0.006)
18.5 f0.4
(0.29)
<CL
<CL
0.0088 k 0.0024
(0.0027)
2.8 f 0.4
(0.06)
3.0 f 0.3
(0.04)
0.23 & 0.03
(0.11)
0.22 f 0.03
(0.08)
0.24 f 0.03
(0.05)
0.14 f 0.02
(0.005)
0.99 f 0.03
(0.02)
1 .OO f 0.05
(0.06)
<CL
(0.005)
(3.3)
(0.6)
(0.02)
ICP-OES
Decomposition*
<CL
(0.15)
2.7 f 0.2
(0.6)
36.1 f 0.4
(2-5)
3.7 f 0.2
(0.02)
5.5 f 1.34
178&4
(2.5)
1702 13
9.71 f 0.34
(2.3)
9.6 f 0.q
158f 1
(0.6)
131 f 59
83.7 f 1.8
(2)
6.9 f 0.5
(1.5)
-
0.28 f 0.01
(0.06)
INAA*
-
-
35.9 f 0.1
(0.05)
-
-
<CL1
(60)
-
-
7.1 & 0.2
(0.01)
-
0.70 f 0.01
(0.004)
322 & 14
(0.6)
3.8 k0.2
(0.1)
0.063 f 0.002
(0.0005)
< CL
( 5 )
<CL
(0.5)
<CL
(0.7)
<CL
(0.29)
<CL
(0.5)
21.4f 1.1
(1)
0.021 f 0.003
(0.002)
<CL
(0.1)
<CL
(0.03)
3.6 k 0.4
(0.4)
-
<CL
(1)
-
-
0.1 7 f 0.02
(0.0005)
0.58 f0.03
(0.0008)
-
-
ETAAS
slurry
atomization':
-
-
-
5.2 f 0.8
177& 19
-
130f 13
( 5 )
(2)
(0.2)
84f 1
7.1 k0.5
0.72 f 0.08
(0.02)
340 L 20
(2)
4.8 k 0.7
(0.8)
3.2 k 0.6
(0.05)
0.3 1 & 0.03
(0.01)
-
-
-
-
-
<CL
(0.02)
-
-
-
-
-
-
-
-
-
-
(continued on next page)
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1070
Table 9 (continued)
JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, SEPTEMBER 1994, VOL. 9
206Pb 2.36 k 0.06
07Pb 2.54 Ifi 0.12
08Pb 2.51 kO.11
(0.04)
(0.05)
(0.04)
<CL
(0.004)
(0.002)
209~i
2 3 8 ~ 0.043 & 0.002
<CL
(1.6)
0.085f0.017
(0.005)
* Ref. 12.
t Ref. 13.
$, Ref. 15.
fj Measurements fromour laboratories using ICP-AES.
Table 10 Spectral interferences in ICP-MS for Sic. Decomposition
with H2S04-HN03-HF in PTFE vesselsL4
terization of ceramic powders. However, restrictions arise from
the low sample concentrations that can be tolerated. Because
of this and also of the spectral interferences, serious limitations
of the actual levels of detection were found, especially for the
light elements, which are very important for advanced ceramics.
These limitations, however, certainly in part, can be overcome
with appropriate measures as has been indicated and are under
further investigation.
The work presented has been supported by the Deutsche
Forschungsgemeinschaft (Bonn) within the framework of the
SPP Keramische Hochleistungswerkstoffe.
1
2
3
7
8
9
10
11
12
13
14
15
16
References
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Paper 4/00375F
Received January 20, 1994
Accepted March 8, 1994
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