Evaluation of the uncertainty of

determination cadmium in aluminum copper

alloy by photoelectric spectrometry
Cite as: AIP Conference Proceedings 1829, 020011 (2017); https://doi.org/10.1063/1.4979743
Published Online: 03 April 2017

Yichun Dai, Lunfu Tian, Deshuang Zou, Lili Wang, and Dong Tian

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AIP Conference Proceedings 1829, 020011 (2017); https://doi.org/10.1063/1.4979743 1829, 020011

© 2017 Author(s).
Evaluation of the Uncertainty of Determination Cadmium in
Aluminum Copper Alloy by Photoelectric Spectrometry
Yichun Dai a), Lunfu Tian, Deshuang Zou, Lili Wang and Dong Tian

Institute of Machinery Manufacturing Technology, China Academy of Engineering Physics, Mianyang, 621900,
China
a)
daiweiv@163.com

Abstract. According to JJF 1059.1-2012 of Evaluation and Expression of Uncertainty, uncertainty evaluation of
measurement cadmium in copper aluminum alloy had proposed by photoelectric spectrometry. The sources of the
measurement uncertainty were analyzed in the process of analysis and the corresponding mathematical model was
established. The uncertainty of standard of A and B, the synthetic standard uncertainty, the expansion uncertainty and
confidence interval of determined results were determined. The uncertainty of the B standard was the main source of
uncertainty in the spectral analysis between uncertainty of class A and B, and the uncertainty of the sample properties
was much larger than the uncertainty of other factors. The established method had certain model significance on the
uncertainty evaluation of other substances measurement by spectroscopic method.

INTRODUCTION
According to JJF 1059.1-2012 Evaluation and Expression of Uncertainty[1], uncertainty was an important data
for the quality assessment of the determination result and was used for evaluated standard. With the promotion of
the laboratory accreditation, evaluation of uncertainty measurement was attracting a great deal of attention [2-10].
The method for determination elements in copper aluminum alloy by photoelectric direct reading spectrometry
was widely available in aluminum alloy for its characteristics of simple sample pretreatment, rapid analysis and so
on[11-15]. The paper discussed how to evaluate the uncertainty of determination cadmium in copper aluminum alloy
by photoelectric direct reading spectrometer on the basis of GB/T7999-2007 of Optical Emission Spectrometric
Analysis Method of Aluminum and Aluminum Alloys [16]. The method also was used to evaluate the uncertainty of
determination other elements in cast aluminum alloy by optical emission spectrometry.

EXPERIMENTS

Apparatus
SPECTROLAB M10 photoelectric direct reading spectrometry was made in Germany Spectro. Its wavelength
was from 120nm to 780mm. It was equipped with high purity argon of double optical room of constant temperature
17±0.2 degrees centigrade, two of 750mm gratings of holographic focus, detector of photomultiplier +CCD which
could set more than 60 channels and characteristic sensitivity lines for measured elements with free choice and no
interference. ZJA-4Q automatic argon–purification machine and Gc0625 table lathe were made in China Sichuan
Purui purification equipment Co., Ltd and China Shandong Lin-yi Jinxing Machine Tool Co., Ltd respectively.

Advances in Energy Science and Environment Engineering

AIP Conf. Proc. 1829, 020011-1–020011-6; doi: 10.1063/1.4979743
Published by AIP Publishing. 978-0-7354-1497-6/$30.00

020011-1
 Conditions of Experiment
The experiment condition was over 99.999 % of the argon purity with 5L/h of stationary flow, 25 L/h of constant
flow, 180L/h of analytic flow. The electrode was tungsten electrode with a diameter of 4 mm, 90 degrees vertex
angle and 3.4mm of polar distance. Characteristic wavelength of Cd was 214.4nm. The wavelength of
internal standard element Al was 174.3nm. The standard sample was GBW E2238 from
South West aluminum products (Group) co., Ltd.

Analytical Method
According to GB/T7999-200716 of Method for Photoelectric Direct Reading Spectrometry, the intensity of
element Cd was determined after a particular surface finish of samples processed by lathe. Then, the content
of measured elements was obtained from intensity-content of the calibration curve of a series of standard samples.
The calibration curve with wide linear range was plotted by international standard samples. Samples was
determined on the basis of using Al standard samples (SUS RA10/2, SUS RA18/69, SUSRA19/29) as high content
of standard samples and low content of standard samples calibrated, GBW E2238 reference materials
(South West aluminum products co., ltd) as type standard sample. Calibration results of type standard were used as
the analysis results of samples.

MATHEMATICAL MODEL AND SOURCES OF THE UNCERTAINTY

Establishment of the Uncertainty Mathematical Model

The linear function I˙aˇbc (c: cadmium mass fraction of samples from the calibration curve) was obtained in
line with least squares regression; I: the ratio of spectral intensity of standard substance of cadmium and aluminum).
The mathematical model was established as follow.
Y=X (1)
In the formula, Y represented the test results of cadmium content and X represented instrument display value of
cadmium content.

Sources of the Uncertainty

The sources of the measurement uncertainty were A-type and B-type of uncertainty. A-type uncertainty which
was characterized as the standard deviation was gained by statistical distribution and measures of the analysis results.
B-type uncertainty resulted from the uncertainty of Ł(homogeneity and treatment of sample),
analyst and the environment.

EVALUATION OF THE UNCERTAINTY

Evaluation of A-type Uncertainty Components

Cd of GBW E2238 of cast aluminum standard was determined for 6 parallel determinations, and
the standard deviation SˈA- type uncertainty and A-type relative uncertainty were calculated as the formulas from
(2) to (4). The results were shown in table 1.
TABLE 1. Determination results of standard sample GBW E2238
Number 1 2 3 4 5 6

Valueδ%ε 1.64×10-1 1.66×10-1 1.65×10-1 1.61×10-1 1.62×10-1 1.62×10-1

Averageδ%ε 1.63×10-1
Standard Deviation 1.80×10-3
A- type Uuncertainty 7.33×10-4
A-type Relative Uncertainty 4.49×10-3

020011-2
 1 n 1 6 (2)
S ( xi ) ¦ ( xi  x ) 2
n 1 i 1
¦ ( xi  1.63 ×10 -1%) 2
6 1 i 1
1.80 × 10 -3

S ( xi ) 1.80 u 10 3 (3)
U A( x ) 7.33 u 10  4
n 6

U A( x ) 7.33 u 10 4 (4)
U rel ( A) 4.49 u 10 3
x 1.63 u 10 1

In the formulas, standard deviation of the single analysis, the test value of n_(th) time, average value of N tests,
the number of tests, A- type uncertainty and A-type relative uncertainty was denoted by S(xi), xi,Cx, n, UA(Cx) and U
rel(A), respectively.

Evaluation of B-type Uncertainty Components

Evaluation of Uncertainty of Type Standard Sample

As the standard sample of GBW E2238, Cd standard value of standard material certificate identification was
1.64×10-1%, and standard deviation was 5×10-3. According to the uniform distribution and k = 3 , B type standard
sample uncertainty U(B1) was in the following formulas.

S 5 u 10 3 (5)
U ( B1) 2.89 u 10 3
k 3

U ( B1) 2.89 u 10 3 (6)

U rel ( B1) 1.76 u 10  2
B1 1.64 u 10 1

In the formula, U(B1) and Urel(B1) stood for the uncertainty of standard sample and the relative uncertainty of
standard sample.

The uncertainty of analytical method

The uncertainty of the method represented the influence on the calibration curve. Each analysis was obtained in
type standard of analytical instrument conditions. The results were shown in table 2 by six successive analyses for
the determination Cd of GBW E2238.
TABLE 2. Six analysis results of GBW E2238 standard of type standard
Sample 1 2 3 4 5 6
Measured Value˄%˅ 1.64×10-1 1.65×10-1 1.66×10-1 1.66×10-1 1.63×10-1 1.66×10-1
Uncertainty of Method 1.50×10-3
Relative Uncertainty of Method 9.14×10-3

Table 2 was shown that the maximum difference between the standard value 1.64×10-1% and the determination
value of standard sample was 3×10-3%, which coincided with the precision of GB/T7999-2007 of Optical Emission
Spectrometric Analysis Method of Aluminum and Aluminum Alloys(The relative standard deviation was less than
5%)16. Analysis results followed normal distribution (The confidence interval was 95% and k was 2.) and
the calculation of the uncertainty of analytical approach was in the following formulas.

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 3 u10 3
U ( B 2) 1.50 u10 3 (7)
2

U ( B 2) 1.50 u10 3 (8)

U rel ( B 2 ) 9.14 u10 3
B2 1.64 u10 1

In the formula 7 and 8, the uncertainty of analytical approach and the relative uncertainty of analytical approach
was denoted by U(B2) and Urel(B2).

The Uncertainty of Analytic Apparatus Stability

The standard sample of GBWE2161 was determined once every two days for consecutive six times. The results
were shown in table 3.
The calculation of the uncertainty of analytic apparatus stability was in the following formula 9 and 10.

S ( xi ) 1.07 u 10 3 (9)
U ( B 3) 4.36 u 10  4
n 6

U A( x ) 4.36 u10 4
U ( B 3) 2.66 u10 3 (10)
x 1.64 u10 1

In the formula, the uncertainty of analytic apparatus stability and the relative uncertainty of analytic apparatus
stability was denoted by U(B3)) and Urel(B3).
TABLE 3. Determination results of standard sample GBW E2238 at intervals 1 days
Number 1 2 3 4 5 6
Valueδ%ε 1.64×10-1 1.65×10-1 1.62×10-1 1.64×10-1 1.65×10-1 1.63×10-1
Averageδ%ε 1.64×10-1
Standard Deviation 1.07×10-3
Uncertainty of Instrument Stability 4.36×10-4
Relative Uncertainty of Instrument Stability 2.66×10-3

The Uncertainty of Sample Characteristic

6 of homemade aluminum samples (Sample preparation and treatment were in line with the requirements of
GB/T5678-201317) were determined for 6 times respectively. Each test needed sample preparation. The uncertainty
of sample characteristic (homogeneity and treatment of sample etc.) was calculated in the following formula and the
results were shown in table 4.
TABLE 4. Results of uncertainty component of the sample properties
Sample Number 1 2 3 4 5 6
2.29×10-1 2.09×10-1 2.34×10-1 2.18×10-1 2.20×10-1 2.04×10-1
2.25×10-1 2.15×10-1 2.35×10-1 2.27×10-1 2.11×10-1 2.09×10-1
-1 -1 -1
2.25×10 2.15×10 2.28×10 2.31×10-1 2.10×10-1 2.21×10-1
Valueδ%ε
2.24×10-1 2.11×10-1 2.15×10-1 2.32×10-1 2.13×10-1 2.14×10-1
-1 -1 -1
2.20×10 2.11×10 2.24×10 2.17×10-1 2.19×10-1 2.19×10-1
-1 -1 -1
2.20×10 2.12×10 2.04×10 2.27×10-1 2.06×10-1 2.15×10-1
Averageδ%ε 2.24×10-1 2.12×10-1 2.23×10-1 2.25×10-1 2.13×10-1 2.14×10-1
-3 -3 -2
Standard Deviation 3.30×10 2.50×10 1.2×10 6.50×10-3 5.50×10-3 6.30×10-3
-3 -3 -3
Uncertainty of Sample Characteristics 1.35×10 1.02×10 4.90×10 2.65×10-3 2.24×10-3 2.57×10-3
Relative Uncertainty of Sample Characteristics 6.01×10-3 4.81×10-3 2.20×10-2 1.18×10-2 1.05×10-2 1.20×10-2

In the formula 11, the relative uncertainty of samples characteristic was denoted by Urel(B4) and 3.06×10-2.

020011-4
 U rel ( B 4) U 2 rel (1)  U 2 rel ( 2)  U 2 rel (3)  U 2 rel ( 4)  U 2 rel (5)  U 2 rel (6) 3.06 u 10 2 ˄11˅

The Uncertainty of Analyst and Environment

The experiment used automation analytic apparatus for testing. Analyst and environment almost had no
influence on the uncertainty of determination, which was negligible.

Evaluation of B-type Relative Uncertainty of Determination Cadmium in Copper Aluminum Alloy

Some factors that influenced B-type relative uncertainty were independent of each other. Therefore, there
were unrelated between them. The calculation of B-type relative uncertainty of determination cadmium in copper
aluminum alloy and the result was in the following formula 12.

U rel ( B ) U 2 rel ( B1)  U 2 rel ( B 2)  U 2 rel ( B 3)  U 2 rel ( B 4)

(1.76 u10 2 ) 2  (9.14 u10 4 ) 2  (2.66 u10 3 ) 2  (3.06 u10 2 ) 2 (12)

3.54 u10 2

Evaluation of the Combined Relative Uncertainty of Determination Cadmium in Copper Aluminum Alloy

On the basis of A-type relative uncertainty and B-type relative uncertainty, the calculation of
the combined relative uncertainty Urel(C) of determination cadmium in copper aluminum alloy was in the following
formula 13.

U rel (C ) U 2 rel ( A)  U 2 rel ( B ) (4.49 u10 3 ) 2  (3.54 u10 2 ) 2 3.57 u10 2 (13)

Evaluation of the Relative Expanded Uncertainty of Determination Cadmium in Copper Aluminum Alloy

In industry, k was 2 for 95% of confidence probability. The calculation of

the relative expanded uncertainty Urel(i) of determination cadmium in copper aluminum alloy was in the following
formula 14.

U rel (i) 2 u 3.57 u10 2 7.14 u10 2 (14)

Determination of Cadmium Content in Copper Aluminum Alloy by Photoelectric Direct Reading Spectrometry

Cadmium standard content in copper aluminum alloy was 2.24×10-1% by photoelectric direct reading
spectrometry. Consequently, U was in the following formula 15.

U 2.24 u101% uU rel 2.24 u101% u 7.14 u102 1.60 u102% (15)

Therefore, the test result was expressed by C as the below formula 16.

C = (2.24×10-1±1.60×10-2)%ˈk = 2. (16)

The Relative Contribution of Each Uncertainty Component

Standard uncertainty component was shown in Table 5. It could be seen from table 5 that B-type uncertainty
was a major source of uncertainty of spectroscopic analysis. Among B-type uncertainty, the relative uncertainty of
sample characteristic was the largest.

020011-5
 TABLE 5. Standard uncertainty component
Uncertainty Component Relative Standard Uncertainty ˄%˅
Uncertainty of A 4.49×10-3
Uncertainty of B 3.54×10-2
Type Standard Sample 1.76×10-2
Analysis Method 9.14×10-3
Instrument Stability 2.66×10-3
Characteristic of the Sample 3.06×10-2

CONCLUSION
The uncertainty of determination cadmium in copper aluminum alloy samples by photoelectric direct reading
spectrometer was evaluated. The results showed that the uncertainty was composed of multiple components, which
contained the uncertainty of the system effect and random effect. B-type uncertainty
was a major source of uncertainty of spectroscopic analysis and the relative uncertainty of sample characteristic was
the largest among B-type uncertainty.

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