Carbon/Sulfur, Oxygen/Nitrogen & Hydrogen Analyzer

TECHNICAL NOTE 28

Quality Assurance for the Analysis of Steel by Gas Component

Analysis

Alain Salaville, Jérôme Barraqué, JOBIN YVON SAS, Longjumeau, FRANCE

Keywords: quality assurance, steel

1 Overview precision of analysis, and the types of samples

required.
Quality assurance of analysis is often demanded
by a wide range of users interested in the analy- 3. Sampling method:
sis of raw steel or finished steel products. These Standards for how the samples are collected.
users include international public and private
organizations, such as the ISO, JIS, ASTM, 4. Sampling arrangement:
ASME, LA, and Defense Agencies, manufactur- Standards for how the samples are handled and
ers, such as automobile makers, and individual stored.
users.
5. Analysis method selection:
The most important factor required by any quali- Standards for the selection method of analysis
ty assurance is the accuracy of analysis making based on the expected quantities of analysis ele-
it possible for all values analyzed to meet author- ments, required precision of analysis, and
ized standards. The second most important fac- required time of analysis.
tor is the ease of tracking back to find when,
how, by who, and under what conditions or envi- 6. Analysis method
ronments the analysis was made. Standards for a whole procedure for analysis.

In order to satisfy these factors, the above tasks 7. Analyzer operation maintenance:
must be standardized and prepared in writing as Standards for the operation, maintenance, and
guidelines or references. Their contents must improvement methods of the analyzer to keep it
provide steps to make it possible to ensure that in good operating condition.
the results of analysis will be obtained by taking
the provided steps. As an example, quality assur- 8. Analyzer accuracy maintenance:
ances of analysis are explained below with the Standards for the maintenance and improvement
carbon detection method (EMIA) and nitrogen methods of the analyzer so that the analyzer can
detection method (EMGA) provided in Steel Anal- maintain its accuracy of analysis.
ysis (Analysis of Control of Processes in 24-hour
Operation). The example introduced here is typi- 9. Analysis criteria:
cal. Other quality assurance systems may be Standards for criteria of analysis results obtained
applied if they are proper and suitable. from unknown samples in accordance with the
above standards.
2 System configuration 10. Analysis result reporting:
Standards for the means and destinations of cor-
The system configuration is divided into the fol- rect analysis results to be reported.
lowing 10 items.
Others:
1. Manufacturing stage and analysis position: Control of analysis materials, training and author-
Standards for the analysis position and timing at ization of analysis engineers, countermeasures
manufacturing stage according to the product. against errors, quality control and records, and
more.
2. Sampling and analysis instructions:
Standards for the elements to be analyzed, the
 Carbon/Sulfur, Oxygen/Nitrogen & Hydrogen Analyzer

TECHNICAL NOTE 28

3 Carbon analysis in steel

3.1 Analysis method selection

Table 1 : Method Selection

Pig iron Carbon Alloy Stainless

steel steel steel
1 Gas capacity method z z z z
2 High frequency heating and infrared z z z z
absorption method
3 Combustion and infrared absorption z z z z
method
4 Carbon trace quantitative method z z z

Table 3: Standard for performance check

3.2 Analyzer operation maintenance and
analyzer accuracy maintenance Standard sample name Standard value (%)

1. Creation of Calibration Curve (Once a Year) WS 205 0.0027

a. Standard Sample JSS 155 0.041

b. Analysis
Standard sample name Standard value (%) Analyze each sample 10 times in succession and
obtain the dispersion as a standard deviation.
Table 2: Standard sample for calibration curve
JSS 152 0.186 c. Criteria
JSS 514 0.098 The standard deviation obtained from each sample
JSS 512 0.090 analyzed 10 times must be within the correspon-
JSS 168 0.053 ding value in the Table 3.
JSS 169 0.047
JSS 155 0.041 Table 4: Reference standard deviation
JSS 174 0.031 Standard sample name Reference standard
JSS 003 0.0011 Deviation

b. Analysis WS 205 0.0002

Analyze each sample twice in succession to obtain JSS 155 0.0010
the mean value.

c. Calculation of Calibration Curve

Obtain the relationship between the analysis value
and standard value from the linear regression for-
mula.

d. Check 2
The sensitivity slope (a) must be within 1.5.

2. Performance Check (Once a Year)

a. Standard Sample
 Carbon/Sulfur, Oxygen/Nitrogen & Hydrogen Analyzer

TECHNICAL NOTE 28

3. Regular Inspection (Once a Month) The mean value must be within the corresponding
permissible limitation range in the Table 7.
Table 5: Inspection item
Table 8: Tolerance
Inspection item Key point
Standard sample name Tolerance
Extraction line cleaning Use a brush or vac-
uum cleaner
Dust disposal line cleaning Use a brush or vac- WS 205 0.0027 ± 0.0002
uum cleaner JSS 155 0.041 ± 0.001
Do not leave any dust.
Moving board and pot board Check that there is The dispersion range must be within the correspon-
no crack or chipping ding dispersion permissible range in the Table 8.
Combustion tube replacement
Interior cleaning Use a vacuum Table 9: Dispersion range
cleaner
Ground inspection Check that the
ground line is Standard sample name Tolerance
securely connected.

4. Daily Inspection (Once a Day) WS 205 0.0002

JSS 155 0.001
Table 6: Standard for daily inscpection
Describe the mean value and range in the X-R
Inspection item Standard control chart and check improper values and errors
in periodicity, tendency, and dispersion from the
Dust cleaner cleaning Within 100 analyses chart.
Cylindrical filter Within 300 analyses
replacement 6. Calibration (Whenever Necessary)
Magnesium perchlorate Within 300 analyses
replacement on sample side a Standard Sample
Ascarite replacement on Within 600 analyses
zero gas side Table 10: Standard for calibration
Operation gas pressure 3.5 kg/cm2
Oxygen pressure 3.0 kg/cm2 Standard sample name Standard value (%)

5. Analysis Check (Once a Shift) JSS 003 0.0011

a. Standard sample JSS 512 0.090

Table 7: Standard for analysis check b Analysis

Analyze each sample twice and obtain the me an
Standard sample name Standard value (%) value to calibrate the calibration curve.

WS 205 0.0027 c Check

JSS 155 0.041 The sensitivity slope (a) must be within 1.5.

b. Analysis
Analyze each sample twice in succession to obtain
the mean value and dispersion range.
3
c. Criteria
 Carbon/Sulfur, Oxygen/Nitrogen & Hydrogen Analyzer

TECHNICAL NOTE 28

4 Nitrogen analysis in steel

4.1 Analysis method selection

Table 11: Analysis method selection

Pig iron Carbon Alloy Stainless

steel steel steel
1 Ammonia-distilled amidesulfuric acid z z z z
titration method
2 Ammonia-distilled bis extinction method z z z z
3 Ammonia-distilled indophenol blue ex- z z z z
tinction method
4 Inert gas fusion and thermal conduction z z z z
method

4.2 Analysis method 3. Ammonia-distilled Indophenol Blue Extinction

Method
JIS or 180 standards are often applied to analysis
methods. In such cases, a company's standards In this method, a sample is decomposed with
usually do not specify analysis methods in detail. hydrochloric acid and filtered to get a solution. The
residual liquid is added with sulfuric acid and potas-
1. Ammonia-distilled Amidesulfuric Acid Titration sium sulfate, heated, decomposed, and then mixed
Method with the filtered solution. This solution is alkalized
with sodium hydroxide. Next, the solution is distilled
In this method, a sample is decomposed with to extract ammonia to be absorbed by diluted sul-
hydrochloric acid and oxidized with hydrogen per- furic acid. This liquid is added with phenol, sodium
oxide. The residual liquid is processed with sulfuric hypochlorite, and pentacyanonitrosylferrate (III)
acid mixed with potassium sulfate and copper sul- sodium to generate a blue complex. Finally a pho-
fate, which generates white smoke. This solution is tometer is applied to measure the optical density of
alkalized with sodium hydroxide. Next, the solution the complex.
is distilled to extract a liquid to be absorbed by boric
acid. Finally, the quantity of ammonium ions is 4. Inert Gas Fusion and Thermal Conduction
measured by amidesulfuric acid titration. Method

2. Ammonia-distilled Bis Extinction Method In this method, a sample is put into a graphite pot,
melted in inert gas to extract nitrogen to be trans-
In this method, a sample is decomposed with ferred to a heat conductive cell to measure the
hydrochloric acid and filtered to get a solution. The change in heat conductivity.
residual liquid is added with sulfuric acid and potas-
sium sulfate, heated, decomposed, and then mixed The following analysis items are described.
with the filtered solution. This solution is alkalized 1) Outline
with sodium hydroxide. Next the solution is distilled 2) Applicable range and quantity of samples
to extract ammonia to be absorbed by water. After 3) Instruments, materials, and reagents
citric acid, disodium phosphate, and p-toluenesul- 4) Equipment
fonchloroamido sodium (chloramine T) are added to 5) Quantitative operation
this liquid, bis-pyrazolone (1-phenyl, 3-methyl, and 6) Calculation and results 4
5-pyrazolone bis) is further added to generate a
color complex. Finally a photometer is applied to
measure the optical density of the complex.
 Carbon/Sulfur, Oxygen/Nitrogen & Hydrogen Analyzer

TECHNICAL NOTE 28

4.3 Analyzer operation maintenance and Table 14: Reference standard deviation
analyzer accuracy maintenance (inertg gas Standard sample name Reference Standard
fusion and thermal conduction method) (%)
WS 205N 0.0002
1. Creation of Calibration Curve (Once a Year) JSS 516 0.0003
a. Standard Sample 3. Regular Inspection (Once a Month)
Table 12: Standard for calibration curve
Table 15: Regular inspection
Standard sample name Standard value (%)
Inspection item Key point
JSS 003 0.0014
JSS 050 0.0027 Cooling water checking Check that there is
JSS 061 0.0038 no scale or clog-
JSS 512 0.0069 ging
JSS 515 0.0081 Vacuum cleaner checking Do not leave any
JSS 516 0.0090 and cleaning dust
JSS 517 0.0104 Upper electrode checking Check that there is
JSS513 0.0118 and cleaning no crack or
chipping
b. Analysis Lower electrode chip replacement
Analyze each sample twice in succession to obtain Interior cleaning Use a vacuum
the mean value. cleaner
Purifier line copper sulfate re-
c. Calculation of Calibration Curve placement
Obtain the relationship between the analysis value
and standard value from the linear regression for- 4. Daily Inspection (Once a Day)
mula.
Table 16: Daily inspection
d. Check
The sensitivity slope (a) must be within 1.5.
Inspection item Standard
2. Performance Check (Once a Year)
He gas pressure 3.5 kg/cm2
a. Standard Sample Air pressure 4.5 kg/cm2
Dust filter replacement
Table 13: Standard for performance check O-ring cleaning Removal and greasing
Plunger cleaning Removal and greasing
Analyzer magnesium Within 500 analyses
Standard sample name Standard value (%)
perchlorate replacement
Analyzer ascarite Within 500 analyses
WS 205N 0.0024 replacement
JSS 516 0.0090 Analyzer copper sulfate Once each 15-day peri-
replacement od
b. Analysis
Analyze each sample 10 times in succession and
obtain the dispersion as a standard deviation.

c. Criteria
The standard deviation obtained from each sample 5
analyzed 10 times must be within the correspon-
ding value in the Table 13.
 Carbon/Sulfur, Oxygen/Nitrogen & Hydrogen Analyzer

TECHNICAL NOTE 28

5. Analysis Check (Once a Shift) 6. Calibration (Whenever Necessary)

a. Standard Sample a. Standard Sample

Table 17: Analysis check Table 20: Calibration

Standard sample name Standard value (%)

Standard sample name Standard value (%)

WS 202N 0.0024 JSS 003 0.0014

JSS 516 0.0090 JSS 517 0.0104

b. Analysis b. Analysis
Analyze each sample twice in succession to obtain Analyze each sample twice and obtain the mean
the mean value and dispersion range. value to calibrate the calibration curve.

c. Criteria c. Check
The mean value must be within the corresponding The sensitivity slope (a) must be within 1.5.
permissible limitation range in the Table 15.

Table 18: Criteria

Standard sample name Standard value ±

tolerance

WS 202N 0.0024 ±O.0002

JSS 516 0.0090 ±0.0002

The dispersion range must be within the corre-

sponding tolerance in Table 16.

Table 19: Dispersion range

Standard sample name Tolerance

WS 202N 0.0003
JSS 516 0.0004

Describe the mean value and range in the X-R con-

trol chart and check improper values and errors in
periodicity, tendency, and dispersion from the chart.

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