Application

Note: 41225
Analysis of Pure and Ultra-Pure Copper
by Optical Emission
ARL 4460 Metals Analyzer

Introduction Depending on the purity requested, a second

Key Words Due to its high electrical and thermal conductivity, copper pyrometallurgical procedure may also be applied.
is the preferred and predominant metal used in the electrical • Different levels of purity are required for various
• ARL 4460
industry. In order to obtain the required properties, applications
• Pure and Ultra- unalloyed high purity copper is almost always used. • High purity copper (electrolytic cathode copper) for
Pure Copper Composition is one of the most important criteria electrical power transmission or electronic applications
governing high electrical conductivity. Impurities such as • Fire-refined copper, mostly used to produce alloys like
• Metals Analyzer
Fe, As and P can significantly decrease the conductivity, brass or bronze or Cupro-Nickel
• Optical Emission modifying the mechanical properties of the copper and
must be kept as low as possible. For OFHC (oxygen-free
Sampling copper cathodes
high conductivity) copper,
Sampling is a major concern for pure copper analysis, due
99,99% Cu, with limited
to the difficulty in producing a representative copper
S and P content is
cathode sample. Norms (i.e ASTM B115) outline
essential.
optimum sampling method procedures.
Our long experience
in metals analysis comes
Current Controlled Source (CCS)
from an installed base of
The Thermo Scientific Current Controlled Source presents
over 10,000 spectrometers
significant advantages in comparison to any other spark
worldwide. The Thermo
generator currently used for OES. It is the only
Scientific ARL 4460 is the
servo-controlled “digital source” on the market.
answer to your
The current waveform is computer controlled and can
metallurgical analysis needs, whether they be incoming
be selected for each type of metal. The high degree of
material control or metal QC and production analysis.
flexibility in selection of peak current (250 A max.),
Working 24 hours a day and 7 days a week, the ARL 4460
frequency (1000 Hz max.) and current waveforms enables
delivers dependable performance year after year.
the optimization of all analytical figures.
The ARL 4460 Metals Analyzer can determine
The very compact design close to the spark stand,
simultaneously up to 60 elements in one minute. Specific
enclosed in a Faraday cage, suppresses RF leakage and
performance is detailed in this application summary.
improves general stability (less current lost in
Using the ARL 4460 Metals Analyzer, sample analysis
connecting cables).
time, sensitivity, precision, accuracy and maintenance
operations have all been substantially improved in the
analysis of pure and ultra-pure copper. Current [A]

The high performance of the ARL 4460 will not only Peak (30-250 A)

completely meet your analytical needs of today, but also

those of tomorrow.
Plateau (any form: 256 points)

Pure and ultra-pure copper

Two main refining processes are used to produce pure and
ultra pure copper:
• Pyrometallurgy
• Wetmetallurgy enrichment Time [µs]
Time Resolved Spectroscopy (TRS) Accuracy
For the duration of an individual spark, the line-to- Accurate analysis can be attributed to a number of
background ratio varies significantly. The selection of the factors:
most appropriate period of the spark when data • The accuracy and quality of the calibration standards
acquisition takes place, improves sensitivity and precision • Precision
for trace analysis.
• Matrix matched calibration standards
TRS removes the first peak of current (high
background) and selects a “window” (the best section of • High energy pre-burn, to reduce or eliminate matrix
effects
the “plateau” current) for each element.
In the case of spectral line interferences, where there is • Applying appropriate correction equations to reduce
a significant difference in the excitation potential of the spectral interferences
analyte and of interfering lines, the accuracy of calibration The example shown below illustrates a calibration
can be substantially improved using TRS. curve obtained for oxygen in pure copper.

Current [A] E=0.1476E-02

Concent.
0.40 %Ratio
Window#1
DEG = 3
0.35 CO = -0.324E-01
C1 = 0.748E-01
C2 = 0.811E-02
Window#2 C3 = 0.458E-03
0.30

0.25

0.20

0.15
Time [µs]

0.10

Sample preparation 0.05 Intensity

A lathe or milling machine is used to prepare the surface Ratio
of the sample, since grinding may contaminate the sample 0.5 1 1.5 2 2.5 3 3.5 4

surface.
The table below shows the analysis of the CRM 075
Sample analysis time (International Certified Reference Material) and the
The analysis time taken between the start of the analysis comparison to the certified values.
and the display of the result is 19 s (also if O is analyzed).
Using the CCS source, the sample analysis time is EL. CERTIFIED INTERLABO. MEASURED DIFFERENCE
reduced by 40 to 55 % when compared to conventional VALUE 3S VALUE
excitation methods. [PPM] [PPM] [PPM] [PPM]

Ag 12.2 0.6 12.1 -0.1

Factory calibration (CARL) As 3.74 0.3 3.7 -0.04
Thermo Scientific optical emission spectrometers can be Bi 1.44 0.11 1.7 0.26
factory calibrated for pure and ultra-pure copper utilizing Cd 2.57 0.18 2.9 0.33
CARL, a very sophisticated multi-variable regression tool Co 2.5 0.18 2.4 -0.1
that corrects for matrix effects as well as spectral Cr 0.89 0.08 1.1 0.21
interferences. CARL can provide an immediate "turn-key" Fe 9 0.6 8.4 -0.6
system which gives the user the highest accuracy possible. Mn 3.23 0.3 3.1 -0.13
For each quality we use certified materials as standard Ni 1.45 0.15 1.4 -0.05
samples and supplies setting-up samples with each O 14 18 4
instrument to maintain the accuracy of the calibration. Pb 3.27 0.15 3 -0.27
Our company provides calibrations for 2 qualities of S 7 5.2 -1.8
copper: Sb 2.56 0.23 2.9 0.34
• Ultra-pure copper Se 1.26 0.11 1.4 0.14
Sn 1.09 0.1 1.1 0.01
• Pure copper
Te 1.52 0.08 1.3 -0.22
Zn 3.47 0.12 3.59 0.12
Table 1: ARL 4460 - Typical detection limits (3 sigma) and precision values (1 sigma) for PURE COPPER
ELEMENT Ag Al As Au B Be Bi Cd Co Cr Fe Mg Mn
TYPICAL DL [PPM] < 0.1 < 0.1 0.3 0.2 0.2 < 0.1 0.3 0.1 0.5 0.3 0.3 < 0.05 < 0.1
GUARANTEED DL [PPM] 0.2 0.2 0.5 0.5 0.4 0.2 0.6 0.3 1.0 0.6 0.6 0.1 0.1

Level [ppm] SD SD SD SD SD SD SD SD SD SD SD SD SD
1 < 0.1 0.15 0.15 < 0.1 0.15 < 0.1 0.15 0.1 0.05 < 0.1
5 < 0.1 0.2 0.2 < 0.1 0.2 0.1 0.2 0.15 0.5 0.1 0.2 0.1 < 0.1
10 0.10 0.2 0.3 0.1 0.3 0.2 0.3 0.25 0.5 0.1 0.2 0.1 0.1
20 0.2 0.3 0.4 0.15 0.5 0.4 0.5 0.4 0.6 0.15 0.3 0.15 0.1
50 0.35 0.5 0.8 0.3 0.7 1.0 1.0 1.0 0.25 0.5 0.3 0.2
100 0.7 0.8 1.5 1 2.0 1.7 1.7 0.5 1.0 0.5 0.4
200 1.3 1.5 3.0 1.6 4.0 3.5 3.0 1.0 1.7 1.0 0.7

ELEMENT Ni O P Pb S Sb Se Si Sn Te Ti Zn Zr
TYPICAL DL [PPM] 0.2 8 0.2 0.6 0.15 1.0 0.2 0.2 0.3 1.0 0.1 1.0 0.1
GUARANTEED DL [PPM] 0.4 15 0.4 1.3 0.3 2.0 0.4 0.3 0.5 1.8 0.15 1.5 0.3

Level [ppm] SD SD SD SD SD SD SD SD SD SD SD SD
1 0.15 0.3 0.1 0.1 0.1 < 0.1 0.1
5 0.2 0.3 0.4 0.2 0.3 0.2 0.1 0.25 0.8 0.12 0.4 0.2
10 0.25 0.4 0.5 0.3 0.4 0.25 0.15 0.35 0.9 0.2 0.5 0.3
20 0.3 0.6 0.6 0.5 0.5 0.5 0.2 0.5 1.0 0.4 0.6 0.5
50 0.6 3.5 1.0 1.2 1.2 1.0 1.0 0.5 1.0 1.5 0.9 1.0 1.2
100 1.0 5 1.5 2.0 2.5 2.0 2.0 0.7 2.0 2.5 1.7 1.7 2.5
200 2.0 8 3.0 4.0 5.0 3.5 4.0 1.3 4.0 4.0 3.5 3.0 4.0
1000 27

Table 2: ARL 4460 - Typical detection limits (3 sigma) and precision values (1 sigma) for ULTRA-PURE COPPER
ELEMENT Ag Al As Au B Be Bi Cd Co Cr Fe Mg Mn Ni O
TYPICAL DL [PPM] 0.05 0.08 0.1 0.12 0.05 < 0.01 0.25 0.1 0.1 0.05 0.2 0.02 0.04 0.15 6.5
GUARANTEED DL 0.15 0.15 0.2 0.25 0.1 0.1 0.5 0.15 0.2 0.15 0.4 0.05 0.07 0.3 10
[PPM]

Level [ppm] SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD

0.5 0.025 0.025 0.015 0.005 0.02 0.015 0.007 0.01

1 0.045 0.03 0.03 0.045 0.03 0.007 0.07 0.02 0.05 0.02 0.05 0.01 0.015 0.065
2 0.05 0.04 0.04 0.05 0.06 0.015 0.08 0.03 0.05 0.02 0.05 0.02 0.015 0.07
5 0.06 0.075 0.06 0.075 0.15 0.03 0.1 0.07 0.07 0.03 0.07 0.05 0.03 0.09
10 0.08 0.15 0.09 0.1 0.25 0.06 0.2 0.15 0.1 0.05 0.08 0.1 0.04 0.1
20 0.1 0.25 0.15 0.25 0.5 0.15 0.3 0.25 0.15 0.08 0.1 0.2 0.08 0.15 2
50 0.25 0.6 0.35 0.45 1 0.3 0.75 0.6 0.3 0.2 0.2 0.5 0.2 0.25 3
100 0.5 1 0.7 0.8 2.5 0.7 1.5 1.5 0.6 0.4 0.4 1 0.4 0.4 4
200 1.5 2.5 1.5 1.5 5 1.5 4.5 2.5 1 1 0.75 2 0.95 0.75 7

ELEMENT P Pb Pd Pt Rh S Sb Se Si Sn Te Ti Zn Zr
TYPICAL DL [PPM] 0.12 0.4 0.06 0.6 0.3 0.1 0.6 0.2 0.15 0.25 0.5 0.1 0.1 0.1
GUARANTEED DL 0.25 0.7 0.25 2 0.5 0.2 1.8 0.4 0.3 0.4 1.0 0.15 0.2 0.25
[PPM]

Level [ppm] SD SD SD SD SD SD SD SD SD SD SD SD SD SD
0.5 0.015 0.01 0.02
1 0.04 0.085 0.02 0.035 0.06 0.05 0.07 0.015 0.05 0.03
2 0.045 0.1 0.025 0.1 0.05 0.25 0.08 0.06 0.08 0.03 0.06 0.045
5 0.07 0.15 0.045 0.45 0.2 0.1 0.3 0.15 0.07 0.1 0.3 0.06 0.08 0.1
10 0.1 0.2 0.07 0.45 0.35 0.2 0.4 0.2 0.09 0.2 0.4 0.1 0.1 0.2
20 0.2 0.35 0.15 0.5 0.5 0.35 0.55 0.4 0.15 0.3 0.5 0.25 0.15 0.35
50 0.4 0.75 0.3 0.6 1.5 0.8 1 0.9 0.25 0.7 0.9 0.6 0.3 0.9
100 0.85 1.5 0.6 0.9 2.5 1.5 2 1.5 0.5 1.5 1.5 1.5 0.6 2
200 2 3 1 1.5 4 3 3.5 3.5 1 2.5 3.5 3 1 4

Remarks: This data applies when homogeneous samples are prepared by recommended sample preparation methods.
The precision given is typical performance. Guaranteed values will be 1.5 times higher.
For multibase instruments, some analytical performance may vary based on the analytical line selected.
Guaranteed DLs are calculated at 95 % confidence limit.
Memory effects The DL (Detection Limit) is defined as three times the In addition to these
For testing purposes, a copper alloy (Al 8.7 %, Fe 6.5 %, standard deviation of the background expressed in offices, Thermo Fisher
Ni 0.73 %, Mn 0.35 %) was analyzed just before a pure concentration units. Scientific maintains
Cu sample. The levels of pure Cu are obtained after 6 runs. a network of represen-
Therefore when the instrument is also used for the Conclusion tative organizations
analysis of alloys, we recommend the utilization of The ARL 4460 provides not only state of the art technology, throughout the world.
different tables, electrodes and cups to avoid memory effects. but also has all the total system features which meet the
critical needs of the metals analysis markets.
14
Concentration [ppm]

12 Al • Unmatched hardware for stability and reliability

10
8 Fe
• Exceptional performance in detection limits, precision,
6 accuracy, stability and memory effects, all this in minimum Africa-Other
Ni +27 11 570 1840
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2
Mn Australia
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Stability of the instrument is of the utmost importance when • Widest range of metals analysis Canada
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below two times the precision value, which is excellent. Denmark
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The example below shows the long-term stability of
• Laboratory accreditation guidance Europe-Other
element Bi in ultra-pure copper recorded over a period of +43 1 333 50 34 0
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The standard deviation achieved remains in the range of the All these features allow you to optimize your +46 8 556 468 00
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23.000 • Your production costs are reduced by the fact that more
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22-01-2002 23-01-2002 28-01-2002 31-01-2002
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• Your operating and maintenance costs are reduced through New Zealand
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Performance guarantee Russia/CIS
simple maintenance
Our company guarantees the precision shown in Tables 1 +43 1 333 50 34 0
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The precision is calculated from the formula: UK
leader in OES metals analysis. We work with our customers +44 1442 233555
where:
to improve the efficiency of their analytical tasks and thereby USA
X i the individual readings
i=n
Σ(Xi-Xi ) 2 X the arithmetic mean of
increase productivity. +1 800 532 4752
i To see our complete OES product portfolio, visit
SD(1σ)=± i=1
n–1 the individual readings www.thermoscientific.com/oes.
n the number of determinations

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