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Received: 5 October 2009 Revised: 4 March 2010 Accepted: 22 March 2010 Published online in Wiley Interscience: 7 May 2010
widely used grinding tools in the ceramic sector and a quality Cerámicas, Universitat Jaume I, Castellón 12006, Spain
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c 2010 John Wiley & Sons, Ltd. X-Ray Spectrom. 2010, 39, 267–278
Chemical characterisation of grinding tools by WD-XRF and XRD
The sample was milled in a tungsten carbide ring mill for the All the samples were measured in powder form. For this purpose,
minimum time required to obtain an optimum sample particle a sample milled below 60 µm was used.[24] The milled sample was
size for the various determinations, since excessive milling could back-filled into an appropriate specimen holder for the instrument
oxidise SiC to SiO2 . It is recommended that milling be performed used. The amount of specimen was just enough to underfill the
for the shortest time needed to obtain a particle size below holder when slightly pressed.
150 µm.[15] As bead preparation needs small particle size, two A quantitative phase analysis was also performed.[25,26] Data
millings of the sample were necessary: first, the sample was milled were processed in a Rietveld refinement.[27,28] The Rietveld analysis
to obtain a particle size below 150 µm and, subsequently, a second program DIFFRACplus TOPAS version 4.2 was used in this study,
milling was carried out to obtain a particle size below 60 µm. For assuming a pseudo-Voigt function to describe the peak shapes.
the determination of both particle sizes, the residues below 2% at The refinement protocol included the background, the scale
150 and 60 µm were calculated by sieving the samples through factors as well as the global-instrument, lattice, profile and texture
150 and 60 meshes, respectively. The sample milled below 150 µm parameters. The basic approach was to get the best diffraction
was used for the determination of organic, inorganic and total data, using, in this case, fluorite as an internal standard, identify
carbon as well as sulfur, while the sample milled below 60 µm all the crystalline phases present in the sample and input basic
was used for the determination of the crystalline phases and the structural data for all phases. Then, the computer modelled the
chemical analysis. There was a specific milling of a fraction of the data until the best fit to the experimental pattern was obtained.
sample below 150 µm in an agate ring mill to obtain a fraction
below 60 µm, at which the analysis of tungsten was carried out.
In addition to the oxidation problem that might occur in SiC WD-XRF analysis
milling, milling in a tungsten carbide mill poses a possible sample
First, pressed pellets were prepared for semi-quantitative WD-XRF
contamination problem: if the typical hardness values of the
analysis of the elements present in the grinding tools, using a semi-
material to be analysed are compared with those of the tungsten
quantitative analysis program based on fundamental parameters.
carbide mill, SiC has a Knoop hardness of 2400 HK, while that
On the basis of the semi-quantitative and XRD analysis, samples
of tungsten carbide is 1900 HK.[3] As a result, ring wear occurs
were then prepared as pellets and beads, depending on the
and the sample is contaminated with tungsten carbide, thereby
element to be analysed. By bead preparation, elements not
making it necessary to correct the total carbon determination for
susceptible of volatilising during the process were analysed: Si, Al,
the amount of contamination.[19,22] This is done by analysing the
Fe, Ca, Mg, K, Ti, Mn, P and W. Na and Cl are elements that, in
tungsten concentration, there being no tungsten in the grinding
these materials, form phases that volatilise during the calcination
tools. The resulting value is then used to determine the carbon
process because of the high temperatures involved, and therefore
resulting from the milling contamination, which will subsequently
sample preparation was in the form of pellets.
need to be subtracted from the total carbon value.
Table 3. Chemical composition and uncertainty of the kaolin used Table 4. Composition of the CSs for WD-FRX measurement, samples
for the dilutions of the samples for the analysis of Na and Cl in pellets being prepared as beads
SiO2 49.8 ± 0.2 SRM 1886a Portland Cement 4.9 1.0 15.0 10.0 3.0
Al2 O3 36.10 ± 0.15 BCS-CRM No 267 silica Brick 10.5 19.0 10.0 13.0 30.0
Fe2 O3 0.46 ± 0.02 BCS-CRM No 319 Magnesite 40.0 49.0 58.0 44.7 43.8
CaO 0.10 ± 0.02 BCS-CRM No 348 Ball Clay 43.5 30.0 – – –
MgO 0.08 ± 0.01 SRM 70a potassium Feldspar 0.5 – – – –
Na2 O <0.01 ± 0.01 CERAM AN41 China Clay – – 15.0 32.0 22.0
K2 O 0.45 ± 0.02 WO3 Merck 0.6 1.0 2.0 0.30 1.2
TiO2 0.14 ± 0.02
MnO <0.01 ± 0.01
P2 O 5 0.06 ± 0.01
Cl <0.01 ± 0.01 Table 5. Composition of the CSs for WD-FRX measurement, samples
Loss on ignition (1025 ◦ C) 12.7 ± 0.1 being prepared as pellets
Composition (wt%)
Certified reference material CS 6 CS 7 CS 8 CS 9 CS 10
In a previous study,[6] it had been verified that samples with
a high SiC content could not be prepared as beads. In the GBW03102 Kaolin 99.0 97.0 94.0 90.0 85.0
present study, it was verified that beads could be prepared when NaCl from Fluka 1.0 3.0 6.0 10.0 15.0
the SiC concentration was smaller than 10% and the particle
size was below 60 µm. Therefore, for bead preparation, the SiC
concentration and particle size needed to be below 10% and the types of samples being studied are commercially unavailable,
60 µm, respectively. reference materials were appropriately mixed in order to obtain
As a result, the sample obtained in the first milling step was compositions similar to those of the samples to be analysed.
milled again to obtain a residue below 2% at 60 µm by sieving it The WD-XRF measurements were calibrated and validated with
through a 60-µm mesh, as was explained in sample preparation the following reference materials and chemical standards:
section. This sample with a particle size below 60 µm was used not
only for bead preparation but also for pellet preparation. For bead 1. Reference materials for calibration using WD-XRF: SRM 98b
preparation, the samples were weighed into a platinum crucible Plastic Clay, BCS-CRM No 348 Ball Clay, SRM 70a Potassium
and the flux (a 50 : 50 mixture of lithium metaborate and lithium Feldspar, CAS 5 Ball Clay, CERAM AN41 China Clay, CERAM
tetraborate) was added in a 1 : 10 sample/flux ratio. A 250 g l−1 so- 2CAS1 Ball Clay, BCS-CRM No 267 Silica Brick, GBW03102 Kaolin,
lution of LiI from Merck was used as a bead-releasing agent, added BCS-CRM No 319 Magnesite, SRM 1886a Portland Cement, NaCl
at a concentration of 2% of the total weight of the sample and flux. from Fluka and WO3 from Fluka.
The samples were calcined at a temperature of 1025 ◦ C to 2. Reference materials for validation using WD-XRF: BCS-CRM
eliminate volatile components, and partially oxidise the carbide, No. 389 High-purity Magnesite, BCS No. 394 Calcined Bauxite,
before being prepared as beads. The resulting beads then allowed EURONORM-ZRM No. 777-1 Silikastein, EURONORM-CRM No.
Si, Al, Fe, Ca, Mg, K, Ti, Mn, P and W to be analysed. Loss on ignition 782/1 Dolomite, GBW03123 Wollastonite, GBW03122 Kaolin,
was determined at a temperature of 1025 ◦ C using a LECO model IPT-72 Sodium Feldspar, NaCl from Merck, MgCl2 from Merck
TGA-701 thermogravimetric analyser. and WO3 from Merck.
Table 4 shows the composition of each calibration standard (CS)
Pellet preparation. Na and Cl were characterised using an for the analysis of Si, Al, Fe, Ca, Mg, K, Ti, Mn, P and W, the samples
uncalcined sample milled at a particle size below 60 µm, prepared being prepared as beads.
as pressed pellets, weighing out 9.0000 g sample, adding 2.5 ml Table 5 shows the composition of each CS for the analysis of Na
of a 13.7% solution of n-butyl methacrylate in acetone as a binder, and Cl, the samples being prepared as pellets. The mixing of both
mixing them in an agate mortar and forming at a pressure of materials was done in a tungsten carbide ring mill.
100 kN in a hydraulic press.[29] Different dilutions of the samples Table 6 details the element concentration ranges, together with
were made by mixing the sample in a tungsten carbide ring mill the root mean square (RMS) values for the corresponding calibra-
with high-purity kaolin with controlled composition, free of the tion curves. The RMS value is obtained from the following equation:
elements to be analysed, in order to obtain a matrix similar to
that of the calibration and validation standards used in the WD-
(C ∗ − C)2
XRF measurement and to minimise any possible errors due to
matrix effects. The chemical composition of the kaolin used for the RMS = (1)
n−p
dilutions, along with the uncertainty, is presented in Table 3.
where C ∗ is the theoretical concentration, C is the calculated
WD-XRF measurement calibration and validation. Quantitative concentration, n is the number of CS and p is the number of
WD-XRF chemical analysis requires the availability of reference parameters calculated from the regression (slope, ordinate at the
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materials. However, since reference materials corresponding to origin and inter-element coefficients)
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c 2010 John Wiley & Sons, Ltd. X-Ray Spectrom. 2010, 39, 267–278
Chemical characterisation of grinding tools by WD-XRF and XRD
carbonates.
Table 11[32] ; cknown was calculated from the values of the standards
Table 9. Crystalline phases identified in the studied grinding tools
used, while cexp was obtained from the measurements.
Crystalline phases The uncertainty was calculated from the expression:
Name Formula
s
u=t× √ (3)
Silicon carbide SiC n
Halite NaCl
Magnesium hydroxychloride hydrate (Mg3 (OH)5 Cl)· 4H2 O where u is measurement uncertainty with a 95% level of
Bassanite CaSO4 (0.5·H2 O) confidence, t is statistical value of Student’s-t for 95% probability
Dolomite CaMg(CO3 )2 and (n − 1) degrees of freedom and n is the number of
Calcite CaCO3 measurements of the sample.
Magnesite MgCO3 At least three measurements were made under reproducibility
Periclase MgO conditions.
Talc Mg3 (OH)2 Si4 O10 In order to compare the results obtained with the known
Brucite Mg(OH)2 values of the validation standards, the difference between both
Quartz SiO2 was compared with the related uncertainty, i.e. the combined
Corundum α-Al2 O3 uncertainty of the known and measured values, as set out in the
Sodalite Na4 Cl(Al3 Si3 O12 ) literature.[33]
The absolute value of the difference between the average
measurement value and the known value is calculated as follows:
Table 10. Composition of the validation standards for WD-XRF
measurement, samples being prepared as beads m = |cexp − cknown | (4)
Composition (wt%)
where m is the absolute value of the difference between the
Reference material A B C D G H measurement and the known value, cexp is the measured value
and cknown is the known value.
BCS No. 389 49.9 49.9 53.7 53.2 52.0 50.1
The uncertainty of m is calculated from the uncertainty of
BCS No. 394 18.7 13.5 15.5 12.1 15.6 14.2
the known value and the uncertainty of the measurement result
EURONORM-ZRM Nr. 777-1 21.5 11.8 11.3 16.8 11.1 12.3
according to the following formula:
GBW03123 2.5 19.8 7.9 5.9 7.9 8.9
IPT-72 7.4 5.0 11.6 12.0 11.6 12.0
WO3 MERCK – – – – 1.8 2.5 um = u2exp + u2known (5)
validation standards, along with their uncertainty, are listed in known value in the Cl and Na measurement are given in Table 15.
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X-Ray Spectrom. 2010, 39, 267–278
Table 11. Results obtained in the WD-XRF measurement of the validation standards
Validation A B C D G H
standard
components (wt%) cknown cexp cknown cexp cknown cexp cknown cexp cknown cexp cknown cexp
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SiO2 28.0 ± 0.2 27.9 ± 0.2 25.7 ± 0.2 25.9 ± 0.2 23.6 ± 0.2 23.7 ± 0.2 27.9 ± 0.2 28.0 ± 0.2 23.5 ± 0.2 23.4 ± 0.2 25.3 ± 0.2 25.1 ± 0.2
Al2 O3 18.40 ± 0.06 18.5 ± 0.1 13.30 ± 0.06 13.2 ± 0.1 16.40 ± 0.06 16.4 ± 0.1 13.40 ± 0.06 13.3 ± 0.1 16.44 ± 0.06 16.4 ± 0.1 15.29 ± 0.06 15.4 ± 0.1
Chemical characterisation of grinding tools by WD-XRF and XRD
Fe2 O3 0.59 ± 0.02 0.57 ± 0.03 0.53 ± 0.02 0.54 ± 0.03 0.53 ± 0.02 0.53 ± 0.03 0.47 ± 0.02 0.49 ± 0.03 0.53 ± 0.02 0.51 ± 0.03 0.50 ± 0.02 0.49 ± 0.03
CaO 2.48 ± 0.04 2.51 ± 0.05 9.20 ± 0.05 9.24 ± 0.10 4.44 ± 0.04 4.42 ± 0.05 3.78 ± 0.04 3.79 ± 0.05 4.40 ± 0.04 4.43 ± 0.05 4.81 ± 0.04 4.84 ± 0.05
MgO 48.3 ± 0.2 48.5 ± 0.2 48.4 ± 0.2 48.2 ± 0.2 52.1 ± 0.2 52.2 ± 0.2 51.6 ± 0.2 51.7 ± 0.2 50.4 ± 0.2 50.5 ± 0.2 48.6 ± 0.2 48.8 ± 0.2
K2 O 0.15 ± 0.01 0.17 ± 0.01 0.13 ± 0.01 0.13 ± 0.01 0.21 ± 0.01 0.21 ± 0.01 0.22 ± 0.01 0.23 ± 0.01 0.21 ± 0.01 0.22 ± 0.01 0.22 ± 0.01 0.23 ± 0.01
TiO2 0.68 ± 0.01 0.66 ± 0.04 0.48 ± 0.01 0.47 ± 0.04 0.54 ± 0.01 0.55 ± 0.04 0.46 ± 0.01 0.48 ± 0.04 0.54 ± 0.01 0.52 ± 0.04 0.51 ± 0.01 0.50 ± 0.04
MnO 0.01 ± 0.01 0.01 ± 0.01 0.02 ± 0.01 0.02 ± 0.01 0.01 ± 0.01 0.01 ± 0.01 0.01 ± 0.01 0.01 ± 0.01 0.01 ± 0.01 0.01 ± 0.01 0.01 ± 0.01 0.01 ± 0.01
P2 O 5 0.12 ± 0.01 0.12 ± 0.01 0.09 ± 0.01 0.09 ± 0.01 0.16 ± 0.01 0.16 ± 0.01 0.15 ± 0.01 0.14 ± 0.01 0.16 ± 0.01 0.15 ± 0.01 0.16 ± 0.01 0.15 ± 0.01
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M. F. Gazulla et al.
Table 12. Comparison of the measurement result of the validation standards with the known value, where m is the difference between the
measured and the known value, and Um is the expanded uncertainty
Validation A B C D G H
standard
components (wt%) m Um m Um m Um m Um m Um m Um
SiO2 0.1 0.57 0.2 0.57 0.1 0.57 0.1 0.57 0.1 0.57 0.2 0.40
Al2 O3 0.1 0.23 0.1 0.23 0 0.23 0.1 0.23 0.04 0.23 0.11 0.23
Fe2 O3 0.02 0.07 0.01 0.07 0 0.07 0.02 0.07 0.02 0.07 0.01 0.07
CaO 0.03 0.13 0.04 0.22 0.02 0.22 0.01 0.13 0.03 0.13 0.03 0.13
MgO 0.2 0.57 0.2 0.57 0.1 0.57 0.1 0.57 0.1 0.57 0.2 0.57
K2 O 0.02 0.03 0 0.03 0 0.03 0.01 0.028 0.01 0.03 0.01 0.03
TiO2 0.02 0.08 0.01 0.08 0.01 0.08 0.02 0.08 0.02 0.08 0.01 0.08
MnO 0 0.03 0.01 0.03 0 0.03 0 0.03 0 0.03 0 0.03
P2 O 5 0 0.03 0.01 0.03 0 0.03 0.01 0.03 0.01 0.03 0.01 0.03
W – – – – – – – – 0.02 0.04 0.01 0.04
Composition (wt%)
Results of the analysis of grinding tool samples
Chemical standards E F
Analysis of W. In order to determine the carbon from the silicon
Kaolin 97 93
carbide phase, the WC concentration in the sample (resulting from
NaCl 3 7
sample contamination caused by milling in the tungsten carbide
ring mill) needs to be determined. This was done by analysing the
W concentration by WD-FRX, using this value to calculate the WC
Table 14. Results of the validation standards for the WD-XRF concentration and, from this, calculating the C concentration. The
measurement of Cl and Na results obtained for W, WC and C from the sample contamination
in milling are presented in Table 18.
E F
Element cknown cexp cknown cexp
Analysis of Si, Al, Fe, Ca, Mg, Na, K, Ti, Mn, P, S, Cl, Corg, Ctotal and C950 ◦ C .
Cl (wt%) 1.82 ± 0.05 1.84 ± 0.05 4.24 ± 0.05 4.31 ± 0.05 Corg , Ctotal , C950 ◦ C , Na, Cl and S were analysed in the uncalcined
Na2 O (wt%) 1.59 ± 0.05 1.64 ± 0.05 3.71 ± 0.05 3.75 ± 0.05 sample, while Si, Al, Fe, Ca, Mg, K, Ti, Mn and P were analysed in
the calcined sample.
Number of replicates: at least n = 3 in reproducibility conditions.
The results obtained for organic carbon, carbon at 950 ◦ C, total
carbon and carbon from the silicon carbide phase are listed in
Table 19. Carbon from SiC was calculated by subtracting the value
Table 15. Comparison of the measurement results of the validation of carbon at 950 ◦ C and the value of carbon from the WC phase,
standards with the known value in the Cl and Na measurement, where caused by milling contamination, from total carbon.
m is the difference between the measured and the known value and The complete analysis of each sample, the value of SiO2 , which
Um is the expanded uncertainty includes all the silicon present in the sample (expressed as an
E F oxide), comprising the silicon forming SiC and the silicon forming
SiO2 , is presented in Table 20.
Element m U m U
so that there are no significant differences, which validates the Good adjustment factors were obtained in all cases.
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X-Ray Spectrom. 2010, 39, 267–278
Table 16. Results obtained in the determination of organic carbon, carbon at 950 ◦ C, total carbon and sulfur of the analysed reference materials
Copyright
Concentration (wt%) Concentration (wt%) Concentration (wt%) Concentration (wt%) Concentration (wt%)
Chemical characterisation of grinding tools by WD-XRF and XRD
Element Certified Experimental Certified Experimental Certified Experimental Certified Experimental Certified Experimental
C950 ◦ C 0.26 ± 0.03 0.24 ± 0.03 0.65 ± 0.10 0.64 ± 0.04 – – 0.75 ± 0.10 0.75 ± 0.04 – –
Ctotal 29.43 ± 0.08 29.48 ± 0.15 0.65 ± 0.10 0.66 ± 0.05 23.46 ± 0.13 23.50 ± 0.15 0.75 ± 0.10 0.77 ± 0.05 – –
S – – 180 ± 36 (ppm) 190 ± 50 (ppm) – – 210 ± 43 (ppm) 230 ± 50 (ppm) 0.834 ± 0.032 0.846 ± 0.05
Corg – – 0.62 ± 0.08 0.63 ± 0.04 – – 0.49 ± 0.08 0.50 ± 0.03 – –
Table 17. Comparison of the measurement result of the validation standards with the known value for organic carbon, carbon at 950 ◦ C, total
carbon and sulfur, where m is the difference between the measured and the known value and Um is the expanded uncertainty
Grinding tool 36 Grinding tool 150 Grinding tool 280 Grinding tool 600 Grinding tool 1500
W (wt%) 0.90 ± 0.01 0.82 ± 0.01 0.85 ± 0.01 0.90 ± 0.02 0.96 ± 0.01
WC (wt%) 0.96 ± 0.01 0.87 ± 0.01 0.90 ± 0.01 0.96 ± 0.02 1.02 ± 0.01
CWC (wt%) 0.06 ± 0.01 0.05 ± 0.01 0.06 ± 0.01 0.06 ± 0.01 0.06 ± 0.01
Table 19. Results of total carbon, carbon at 950 ◦ C and carbon from the silicon carbide phase
C content (wt%) Grinding tool 36 Grinding tool 150 Grinding tool 280 Grinding tool 600 Grinding tool 1500
Ctotal 6.39 ± 0.06 4.58 ± 0.05 6.29 ± 0.06 4.83 ± 0.05 5.44 ± 0.06
Corg 3.19 ± 0.04 3.10 ± 0.04 3.21 ± 0.04 3.09 ± 0.04 3.12 ± 0.04
C950 ◦ C 3.65 ± 0.04 3.63 ± 0.04 4.41 ± 0.04 3.57 ± 0.04 3.88 ± 0.04
CSiC 2.70 ± 0.10 0.90 ± 0.09 1.80 ± 0.10 1.20 ± 0.09 1.50 ± 0.10
SiO2 total 24.0 ± 0.2 15.8 ± 0.1 14.1 ± 0.1 9.9 ± 0.1 13.4 ± 0.1
Al2 O3 9.8 ± 0.1 13.6 ± 0.1 7.66 ± 0.05 10.1 ± 0.1 7.2 ± 0.1
Fe2 O3 0.41 ± 0.01 0.13 ± 0.01 0.69 ± 0.02 0.61 ± 0.01 0.69 ± 0.01
CaO 1.41 ± 0.04 0.70 ± 0.02 4.62 ± 0.04 1.83 ± 0.03 1.47 ± 0.03
MgO 31.4 ± 0.3 31.2 ± 0.3 29.3 ± 0.3 28.4 ± 0.3 29.5 ± 0.3
Na2 O 5.88 ± 0.04 8.08 ± 0.04 8.68 ± 0.04 12.6 ± 0.05 12.8 ± 0.06
K2 O 0.04 ± 0.01 0.06 ± 0.01 0.02 ± 0.01 0.03 ± 0.01 0.04 ± 0.01
TiO2 0.27 ± 0.01 0.37 ± 0.01 0.27 ± 0.01 0.25 ± 0.01 <0.01 ± 0.01
MnO 0.03 ± 0.01 <0.01 ± 0.01 0.03 ± 0.01 0.03 ± 0.01 0.04 ± 0.01
P2 O 5 <0.01 ± 0.01 <0.01 ± 0.01 0.02 ± 0.01 0.02 ± 0.01 0.01 ± 0.01
SiC 9.0 ± 0.3 3.0 ± 0.3 6.0 ± 0.3 4.0 ± 0.3 5.0 ± 0.3
LOI (1025 ◦ C) 36.1 38.5 44.9 49.4 47.6
S 0.65 ± 0.04 0.56 ± 0.04 0.35 ± 0.03 0.31 ± 0.03 0.38 ± 0.03
Cl 14.0 ± 0.1 15.8 ± 0.1 15.8 ± 0.1 18.2 ± 0.1 23.2 ± 0.1
Characterization of the grinding tools. The complete analysis of calcite, periclase, talc, brucite and quartz, in variable quantities,
the SiC-based grinding tools, taking into account the phase analysis depending on the grinding tool.
obtained, is presented in Table 21. When the analysis results for the silicon carbide phase in the
The chemical and mineralogical analysis data show that the grinding tools obtained by XRD and elemental analysis of the
studied grinding tools are basically made up of SiC and corundum different forms of carbon are compared, no significant differences
as abrasives and magnesium oxychloride as binder, in addition are observed. Either method can therefore be used, depending on
276
to other minor constituents such as halite, bassanite, dolomite, the available equipment.
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c 2010 John Wiley & Sons, Ltd. X-Ray Spectrom. 2010, 39, 267–278
Chemical characterisation of grinding tools by WD-XRF and XRD
Table 21. Composition, expressed as a percentage by weight, of the components present in the studied grinding tools
Crystalline phases (wt%) Grinding tool 36 Grinding tool 150 Grinding tool 280 Grinding tool 600 Grinding tool 1500
Silicon carbide (SiC) 9.0 ± 0.5 3.0 ± 0.3 6.0 ± 0.5 4.0 ± 0.5 5.0 ± 0.5
Halite (NaCl) 11.0 ± 0.5 13.0 ± 0.5 13.0 ± 0.5 16.0 ± 0.8 21 ± 1
Magnesium hydroxychloride 53 ± 2 56 ± 2 58 ± 2 60 ± 3 53 ± 2
hydrate ((Mg3 (OH)5 Cl)·
4H2 O) + other organic
binders)
Bassanite (2CaSO4 (H2 O)) <1 1.0 ± 0.3 <1 1.0 ± 0.3 <1
Dolomite (CaMg(CO3 )2 ) <1 <1 5.0 ± 0.5 2.0 ± 0.3 2.0 ± 0.3
Calcite (CaCO3 ) <1 <1 5.0 ± 0.5 2.0 ± 0.3 1.0 ± 0.3
Magnesite (MgCO3 ) <1 <1 <1 <1 <1
Periclase (MgO) 1.0 ± 0.3 1.0 ± 0.3 <1 <1 1 ± 0.3
Talc (Mg3 (OH)2 Si4 O10 ) 9.0 ± 0.5 <1 5.0 ± 0.5 4.0 ± 0.5 4.0 ± 0.5
Brucite (Mg(OH)2 ) 3.0 ± 0.3 3.0 ± 0.3 <1 3.0 ± 0.3 3.0 ± 0.3
Quartz (SiO2 ) 5.0 ± 0.5 10.0 ± 0.5 1.0 ± 0.3 <1 4.0 ± 0.5
Alumina and corundum 10.0 ± 0.5 13.0 ± 0.5 6.0 ± 0.5 9.0 ± 0.5 6.0 ± 0.5
(α-Al2 O3 )
Sodalite (Na4 Cl(Al3 Si3 O12 )) <1 <1 2.0 ± 0.3 <1 <1
Figure 2. Synoptic scheme of the steps used in the full characterisation of silicon carbide-based grinding tools.
The method proposed in this paper for the complete quantities of other admixtures, such as sulfates, to provide
characterisation of SiC-based grinding tools is schematically il- individual grinding tools with different properties.
lustrated in Fig. 2. 3. Milling is an important step in grinding tool chemical analysis.
Milling can be performed in a WC mill provided milling
conditions are suitably controlled to obtain an appropriate
Conclusions particle size distribution; the contamination that the material
1. A method is presented for the complete chemical charac- undergoes during milling is also duly corrected by tungsten
terisation of SiC-based grinding tools, using elemental and analysis.
spectroscopic analysis techniques to determine all grinding 4. WD-XRF was used in analysing the elements in the grinding
tool components. The method can be used for grinding tool tools. Samples were prepared as beads and pellets, depending
quality control. on the element to be analysed. The absence of certified
2. The phases making up the grinding tools were analysed and reference materials with a composition similar to that of the
quantified by XRD. This provided the information needed to analysed samples made it necessary to prepare compositions
address the chemical analysis, since grinding tools, in addition by mixing the available reference materials in order to validate
277
5. Carbon elemental analysers with variable operating temper- [12] B Docekal, J. A. C. Broekaert, T. Graule, P. Tschöpel, G. Tölg Fresenius,
ature were used to determine the different forms of carbon: J. Anal. Chem. 1992, 342, 113.
organic carbon, carbon at 950 ◦ C (corresponding to organic [13] M. Franek, V. Krivan Fresenius J. Anal. Chem. 1992, 342, 118.
[14] EN 12698-1 2007 Chemical analysis of nitride bonded silicon carbide
carbon and carbon from the carbonates) and total carbon com- refractories. Part 1: chemical methods.
prising all forms of carbon: organic carbon, inorganic carbon [15] DIN 51075-01: 1982. Testing of ceramic materials; chemical analysis
and carbon from the silicon carbide phase. This information of silicon carbide, sample preparation and calculation of silicon
enabled the SiC concentration to be calculated, since SiC can- carbide content.
[16] DIN 51075-02: 1984. Testing of ceramic materials; chemical analysis
not be separated by the gravimetric method without oxidising of silicon carbide, direct determination of the free carbon content.
in the course of the process or other sample components [17] DIN 51075-03: 1982. Testing of ceramic materials; chemical analysis
being retained together with the SiC. of silicon carbide, determination of the total carbon content.
6. The SiC in these SiC-based grinding tools can be determined by [18] ISO 21068-2: 2008 Chemical analysis of silicon-carbide-containing
the two developed methods, namely by XRD or by elemental raw materials and refractory products. Part 2: Determination of loss
on ignition, total carbon, free carbon and silicon carbide, total and
analysis, since both methods yield good results. free silica and total and free silicon.
Acknowledgements [19] ISO 21068-1: 2008 Chemical analysis of silicon-carbide-containing
raw materials and refractory products. Part 1: General information
This study was funded by the Valencia Institute of Small and sample preparation.
[20] FEPA http://www.fepa-abrasives.org [12 January 2008].
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