CN108414470A - A kind of method of ultra-low sulfur in measurement wrought superalloy - Google Patents
A kind of method of ultra-low sulfur in measurement wrought superalloy Download PDFInfo
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- CN108414470A CN108414470A CN201810319111.7A CN201810319111A CN108414470A CN 108414470 A CN108414470 A CN 108414470A CN 201810319111 A CN201810319111 A CN 201810319111A CN 108414470 A CN108414470 A CN 108414470A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 72
- 239000011593 sulfur Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 71
- 238000005259 measurement Methods 0.000 title claims abstract description 68
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 56
- 239000005864 Sulphur Substances 0.000 claims abstract description 113
- 239000000126 substance Substances 0.000 claims abstract description 80
- 238000004458 analytical method Methods 0.000 claims abstract description 62
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 107
- 239000003795 chemical substances by application Substances 0.000 claims description 103
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 100
- 229910052742 iron Inorganic materials 0.000 claims description 50
- AWXLLPFZAKTUCQ-UHFFFAOYSA-N [Sn].[W] Chemical compound [Sn].[W] AWXLLPFZAKTUCQ-UHFFFAOYSA-N 0.000 claims description 47
- 230000000694 effects Effects 0.000 claims description 31
- 238000012360 testing method Methods 0.000 claims description 29
- 239000011800 void material Substances 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 24
- 239000000956 alloy Substances 0.000 abstract description 15
- 229910045601 alloy Inorganic materials 0.000 abstract description 14
- 238000003908 quality control method Methods 0.000 abstract description 2
- 239000011573 trace mineral Substances 0.000 abstract description 2
- 235000013619 trace mineral Nutrition 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 15
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000005242 forging Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000003749 cleanliness Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004164 analytical calibration Methods 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to alloy trace element analysis fields, are related to a kind of method measuring ultra-low sulfur in wrought superalloy, include the following steps：Reduce and stablize blank value, use high-content sulphur standard substance calibration instrument, measure the total blank value of sulfur content, by calibration process three times, measure the total blank value of sulfur content, low content sulphur standard substance is measured, confirms that measured value within the scope of standard substance tolerance, finally measures the ultra-low sulfur in wrought superalloy sample to be measured.The present invention improves the accuracy of measurement result, is smelted for wrought superalloy, quality control provides reliable technical guarantee.
Description
Technical field
The invention belongs to alloy trace element analysis technology, it is related to super-low sulfur in a kind of measurement wrought superalloy
The method of (0.00008%~0.0010%) content.
Background technology
Wrought superalloy be widely used in aero-engine manufacture high-pressure turbine disk, seal pan, turbine wheel shaft, casing,
The important spare parts such as fastener are the high temperature alloy materials that dosage is maximum, purposes is most wide, product category and specification are most complete in engine
Material.With the development of high-performance enginer, for the antioxygenic property of raising wrought superalloy material, corrosion resistance and have
Higher yield strength, welding fabrication performance, propose wrought superalloy material the requirement of high cleanliness.High cleanliness
It is mainly shown as in finished ingot that impurity content significantly reduces.The impurity element sulphur wherein contained influences material because aggregation is easy
The performance of material.Therefore, the content for controlling sulphur is an important indicator.In order to reach the requirement of high cleanliness, smelting process is from original
The two-link smelting process come is improved to three smelting processes, the content of sulphur can be made to drop to 0.0003%, even up to
0.00008%, just there is an urgent need to innovate the method for detection sulphur to adapt to smelt the progressive demand brought for this.
The analysis of sulfur content generally uses high frequency infrared ray carbon sulphur analyser in material, in the base of high frequency infrared ray carbon sulphur analyser
Corresponding analysis method is established on plinth.The prior art, such as CN103543122A are disclosed in a kind of measurement single crystal super alloy
Ultra low sulfur method, but its be only capable of measure sulfur content be 0.0002%-0.0020% single crystal super alloy, for
Sulfur content can not be measured accurately for 0.0002% or less.CN101975760B discloses sulphur in a kind of measurement powder metallurgy superalloy and contains
The method of amount is only capable of measuring the powder metallurgy superalloy that sulphur minimum content is 0.0008% with this method, low for sulfur content
High temperature alloy in 0.0008% also can not be measured accurately.In addition, above two method, do not differentiated between " blank value " in test process
With " blank show value ", cause measurement result inaccurate, and complex steps.
Well known to those skilled in the art, it is apparent poor that wrought superalloy has with powder metallurgy superalloy, single crystal super alloy
Not.Wrought superalloy is cast into ingot casting by techniques such as vacuum metlings, then passes through the thermal deformations such as forging, rolling, cogging, system
At proximate matters such as biscuit, stick, plate, pipes, last die forging is after heat treatment processed into the turbine disk and whirlpool at blanks such as the turbine disk and blades
The parts such as impeller blade.Smelting process largely uses two-link smelting process (vacuum induction melting+vacuum consumable remelting), and minority is adopted
With three techniques (vacuum induction melting+electroslag furnace under protective Ar gas remelting+vacuum consumable remelting).Three techniques can be such that sulfur impurity contains
Amount is reduced near 0.0001%.Sulphur is one of the harmful element generally acknowledged in high temperature alloy, and the height of sulfur content is to high temperature alloy
Plasticity and persistence of material etc. have a significant effect.Sulphur in high temperature alloy easily to crystal boundary segregation, and lasting longevity of alloy
Life and sulphur crystal boundary content there are direct relation, when sulphur with atomic state segregation in crystal boundary when, grain-boundary strength can be slackened.Especially
It is wrought superalloy, it is necessary to become uneven by thermal deformation techniques, the as-cast structures of alloy such as forging, rolling, coggings, partially
Analysis is further serious, and incident is the precipitation of harmful phase, and the cogging and forging and stamping for seriously affecting alloy are processed.Wrought superalloy
Because there is multiple deformation processing links, sulphur aggregation harm influences apparent therefore stringenter to the control of super-low sulfur requirement.It is surveying
In terms of amount, because of its alloying component complexity, high-melting point alloy element is more, and content is higher, and molten to sample touches the complete of super-low sulfur
Full release brings difficulty.
It can be seen that at present this field not yet super-low sulfur in accurate detection wrought superalloy (0.00008%~
0.0010%) method standard of content.Therefore, how accurately to measure super-low sulfur in wrought superalloy (0.00008%~
0.0010%) content is a problem.
Invention content
The object of the present invention is to overcome disadvantage of the existing technology, a kind of efficiently and accurately, easily to operate measurement are proposed
The method of super-low sulfur (0.00008%~0.0010%) content, can solve wrought superalloy in wrought superalloy
The measurement problem of super-low sulfur (0.00008%~0.0010%) content.
The solution of the purpose of the present invention and its technical problem is achieved through the following technical solutions.The technology of the present invention
Scheme is：A kind of method of super-low sulfur (0.00008%~0.0010%) content in measurement wrought superalloy, including following step
Suddenly：The preparation of bottomed crucible；Reduce and stablize blank value；The calibration of high frequency infrared ray carbon sulphur analyser；Measure the total blank of sulfur content
Value；Measure blank show value；The calculating of blank test effect value；Low content sulphur standard substance examines measurement and the survey of sample to be tested
Amount.
In embodiments of the invention, the method for measuring ultra-low sulfur in wrought superalloy includes following step
Suddenly：
1. a kind of method measuring ultra-low sulfur in wrought superalloy, it is characterised in that include the following steps：
The preparation of 1.1 bottomed crucibles：High purity iron fluxing agent is added in crucible, is put into high frequency infrared ray carbon sulphur analyser,
Burning, cooling obtain the bottomed crucible；
The measurement of the calibration of 1.2 high frequency infrared ray carbon sulphur analysers and the total blank value of sulfur content, including：
High frequency infrared ray carbon sulphur analyser is calibrated for the first time：
High-content sulphur standard substance is weighed, the bottomed crucible is put into, high frequency-infrared carbon sulphur described in mass input will be weighed
In analyzer, high purity tungsten tin grain fluxing agent 2g ± 0.5, high purity iron fluxing agent 0.5g ± 0.2 are added in the bottomed crucible, it will
The bottomed crucible is put into analysis in the high frequency infrared ray carbon sulphur analyser and obtains the first time of the high-content sulphur standard substance
Measured value carries out first time school according to the standard value of sulphur in the high-content sulphur standard substance to high frequency infrared ray carbon sulphur analyser
It is accurate；
1.2.1 first time mean blank value, is measured
High purity tungsten tin grain fluxing agent 2g ± 0.5, high purity iron fluxing agent 0.5g ± 0.2 are added in the bottomed crucible, it will
Its nominal mass inputs in the high frequency infrared ray carbon sulphur analyser, and the void item of the high frequency infrared ray carbon sulphur analyser is returned
Zero, the bottomed crucible is put into analysis in the high frequency infrared ray carbon sulphur analyser and obtains blank value, analyzes at least 3 times, calculates
Average value obtains first time mean blank value
1.2.2. second of calibration of high frequency infrared ray carbon sulphur analyser：
High-content sulphur standard substance is weighed, the bottomed crucible is put into, high frequency-infrared carbon sulphur described in mass input will be weighed
In analyzer, by the first time mean blank valueIt inputs in the void item of the high frequency infrared ray carbon sulphur analyser, by described
High frequency infrared ray carbon sulphur analyser deducts automatically, and high purity tungsten tin grain fluxing agent, high purity iron fluxing agent are added in the bottomed crucible,
The bottomed crucible is put into the high frequency infrared ray carbon sulphur analyser, is analyzed, the of the high-content sulphur standard substance is obtained
Secondary measurements carry out second according to the standard value of sulphur in the high-content sulphur standard substance to high frequency infrared ray carbon sulphur analyser
Secondary calibration；
1.2.3 second of mean blank value, is measured
High purity tungsten tin grain fluxing agent 2g ± 0.5, high purity iron fluxing agent 0.5g ± 0.2 are added in the bottomed crucible, it will
Its nominal mass inputs in the high frequency infrared ray carbon sulphur analyser, and the void item of the high frequency infrared ray carbon sulphur analyser is returned
Zero, and the bottomed crucible is put into analysis in the high frequency infrared ray carbon sulphur analyser and obtains blank value, it analyzes at least 3 times, meter
Average value is calculated, second of mean blank value is obtained
1.2.4 high frequency infrared ray carbon sulphur analyser third time is calibrated：
High-content sulphur standard substance is weighed, the bottomed crucible is put into, high frequency-infrared carbon sulphur described in mass input will be weighed
In analyzer, by second of mean blank valueIt inputs in the void item of the high frequency infrared ray carbon sulphur analyser, by described
Instrument deducts the blank value automatically, and high purity tungsten tin grain fluxing agent, high purity iron fluxing agent are added in the bottomed crucible, and
The bottomed crucible is put into the high frequency infrared ray carbon sulphur analyser and is analyzed, the high-content sulphur standard substance third time is obtained
Measured value carries out third time school according to the standard value of sulphur in the high-content sulphur standard substance to high frequency infrared ray carbon sulphur analyser
It is accurate；
1.2.5 measuring third time mean blank value：
High purity tungsten tin grain fluxing agent 2g ± 0.5, high purity iron fluxing agent 0.5g ± 0.2 are added in the bottomed crucible, it will
Nominal mass inputs in the high frequency infrared ray carbon sulphur analyser, and the void item of the high frequency infrared ray carbon sulphur analyser is zeroed,
Analysis obtains blank value, analyzes at least 3 times, calculates average value, obtains third time mean blank valueThis blank value is that sulphur contains
Measure total blank value；
1.2.6 blank show value, is measured
High purity tungsten tin grain fluxing agent 2g ± 0.5, high purity iron fluxing agent 0.5g ± 0.2 are added in the bottomed crucible, it will
Its nominal mass inputs in the high frequency infrared ray carbon sulphur analyser, and by third time mean blank valueIt is red to input the high frequency
The void item of outer carbon and sulfur analytical instrument is analyzed at least 3 times, obtains at least three blank show value；
1.2.7. the calculating of blank test effect value：
For the measurement range that this method limits as 0.00008%~0.0010%, blank test effect value should be less than measurement range
/ 10th of lower limit, i.e.,
0.00008% ÷ 10=0.000008%
Average value is calculated at least three blank show valueAnd standard deviation, and the blank is calculated according to following formula
Influence value：
When blank test effect value≤0.000008%, sample can be measured.
1.3. low content sulphur standard substance is measured：
Low content sulphur standard substance is weighed, the bottomed crucible is put into, high frequency-infrared carbon sulphur described in mass input will be weighed
In analyzer, high purity tungsten tin grain fluxing agent 2g ± 0.5, high purity iron fluxing agent 0.5g ± 0.2 are added in the bottomed crucible,
And the bottomed crucible is put into the high frequency infrared ray carbon sulphur analyser and is analyzed, it obtains the low content sulphur standard substance sulphur and contains
The measured value of amount.
The measurement of sulfur content in 1.4 wrought superalloy samples
Wrought superalloy sample is weighed, is placed in the bottomed crucible, the sample mass is inputted into the high frequency
In infrared carbon sulfur analyzer, high purity tungsten tin grain fluxing agent 2g, high purity iron fluxing agent 0.5g are added in the bottomed crucible, with
The sample mixed constitutes sample；Bottomed crucible containing the sample is put into the high frequency infrared ray carbon sulphur analyser, into
Row measures, and obtains measured value.At least analysis carries out 2 times.The average value of the measured value is the wrought superalloy sample
Sulfur content.
Before the bottomed crucible containing fluxing agent or sample is put into the high frequency infrared ray carbon sulphur analyser, to described
Bottomed crucible is heated.
The accuracy weighed described in first time calibration measurement, step 1.2.2,1.2.4,1.3 and 1.4 is
0.0001g。
In the step 1.3, if the measured value of the low content sulphur standard substance sulfur content does not fall within the low content
Within the scope of sulphur standard substance tolerance, then repeatedly step 1.2~1.3, until the survey of the low content sulphur standard substance sulfur content
Until magnitude is fallen within the scope of its tolerance.
In the measurement first time, second, third time mean blank value, the analysis carries out 5 times.
The heat treatment is carried out using micro-wave oven.
In the step 1.2.6, blank show value measures 5 times.
Compared with prior art, the present invention has apparent advantageous effects.Pass through above-mentioned technical proposal can be seen that
Method of the invention passes through differentiation " blank value " and " blank show value ", reduction and stable blank value, three times accurate measurement blank
Value makes blank test effect value be less than 1/10th of measurement range lower limit, improves the accuracy of measurement result, and it is high to solve deformation
The measurement problem of temperature alloy is smelted for wrought superalloy, quality control provides reliable technical guarantee, while measuring
The measurement method that above-mentioned two patent documents are omitted in journey is essential " preparing sulphur calibration sample step ", reduces process,
The material consumption in measurement process is reduced simultaneously.
Specific implementation mode
Nominal mass refers in the method：High frequency infrared ray carbon sulphur analyser is when calculating sulfur content, it is necessary to have quality
Value；When measuring sample, mass value corresponds to the quality of sample；Blank value is measured, blank is not no quality, but must be given
One mass value of high frequency infrared ray carbon sulphur analyser, could be calculated, this mass value that must be given is nominal mass, generally
1.0000。
Blank test effect value refers in the method：Blank after this method three times instrument calibration is horizontal, indicates empty
It is closely related with blank show value in vain to the influence degree of measurement.
The presence of blank will produce influence to the measurement of sulphur in sample.Blank can only be reduced as best one can to sample measurement
It influences, blank show value is the numerical value changed, cannot be used directly to characterization blank level, but blank show value and blank level are close
Cut phase is closed.
Blank test effect value is：Average value is calculated at least three blank show valueAnd standard deviation,
For the measurement range that this method limits as 0.00008%~0.0010%, blank test effect value should be less than measurement range
/ 10th of lower limit, i.e.,
0.00008% ÷ 10=0.000008%
When blank test effect value≤0.000008%, sample can be measured.
In method of the present invention, when calibrate for the first time, for the second time and for the third time, for school each time
Standard, the measured value of high-content sulphur standard substance at least 2 times or multiple, calculates its average value, it is contemplated that the accuracy and effect of measurement
Rate, preferably 5 times, and school is carried out to high frequency infrared ray carbon sulphur analyser according to the standard value of sulphur in high-content sulphur standard substance successively
It is accurate.
In method of the present invention, wherein in step 1.2.6, blank show value can measure 3,4,5,6,7,
8,9,10,11 is inferior, preferably measures 5 times.It can be in the case where ensureing measurement accuracy, it is ensured that efficiency.
In method of the present invention, wherein in step 1.4,2,3,4,5,6,7,8 grades can be measured, preferably 2
It is secondary.It in this way can be in the case where ensureing measurement accuracy, it is ensured that efficiency.
In method of the present invention, the method is measured using high frequency infrared ray carbon sulphur analyser, the instrument
Lower sensitivity limit be ± 0.0000005%, operating condition is as follows：Measurement 3.0 ± 0.2L/min of flow, measurement pressure 40 ±
2psi, power 40 ± 2psi of atmospheric pressure, minimum analysis time 40s；Environmental condition is：Indoor relative humidity is not more than 60%.
In the method for the invention, high-content sulphur standard substance for example can be U.S. AR-673 (0.0011 ±
0.0002), sulfur content is：0.0011% ± 0.0002%.
In the method for the invention, low content sulphur standard substance can be standard sample YSBC20117c-2009
(0.000 44 ± 0.00009), sulfur content are：0.000 44% ± 0.00009%；Japanese JSS 003-6 (0.00013 ±
0.00003), sulfur content：0.00013% ± 0.00003%.
In the method for the invention, crucible can be porcelain crucible, such as Al2O3 materials, φ 25mm × 25mm.
In the method for the invention, the S of high purity tungsten tin grain fluxing agent：≤ 0.00002%, such as can be
0.000018%, 0.000015%, 0.000010% etc..
In the method for the invention, S≤0.00005% of high purity iron fluxing agent.
In the method for the invention, the oxygen content of high purity oxygen gas is more than 99.999%, such as can be 99.9999%,
99.99999% etc..
In the method for the invention, in order to reduce and stablize blank value, effective drier is needed replacing, is ensured effectively
It purifies carrier gas and eliminates influence of the water to measurement；Clean combustion furnace, pipeline and filter etc. ensure that instrument system blank value is steady
It is fixed；And the bottomed crucible (being not added with sample when measuring blank) for having filled sample and fluxing agent is heated using micro-wave oven
Processing, is slightly changed colour with fluxing agent therein and is limited.
Embodiment one
Super-low sulfur in wrought superalloy GH4169 is measured using high frequency infrared ray carbon sulphur analyser in the present embodiment
The content of (0.00008%~0.0010%).In measurement process, the lower sensitivity limit of high frequency infrared ray carbon sulphur analyser is ±
0.0000005%, the operating condition of instrument is as follows：3.0 ± 0.2L/min of flow is measured, 40 ± 2psi of pressure, power gas are measured
40 ± 2psi of pressure, minimum analysis time 40s；Environmental condition is：Indoor relative humidity is not more than 60%.Made in measurement process
Material is as follows：
High-content sulphur standard substance：U.S. AR-673 (0.001 1 ± 0.0002), sulfur content are：0.0011% ±
0.0002%；
Low content sulphur standard substance：Standard sample YSBC 20117c-2009 (0.00044 ± 0.00009) sulfur content is：
0.00044% ± 0.00009%；
Porcelain crucible：Al2O3 materials, φ 25mm × 25mm；
High purity tungsten tin grain fluxing agent：S：≤ 0.00002%；
High purity iron fluxing agent：S≤0.00005%；
High purity oxygen gas：Content is more than 99.999%.
Measuring process is as follows：
1.1, the preparation of bottomed crucible：2.0 grams of high purity iron fluxing agent is added in porcelain crucible, is put into high frequency-infrared carbon sulphur
In analyzer, burning, cooling obtain bottomed crucible.
1.2, the measurement of the calibration of high frequency infrared ray carbon sulphur analyser and the total blank value of sulfur content, measuring process are as follows：
High frequency infrared ray carbon sulphur analyser is calibrated for the first time：Weighing high-content sulphur standard substance AR-673 (0.0011 ±
0.0002), 0.500 gram or so, it is accurate to 0.0001 gram, is put into bottomed crucible, in mass input high frequency infrared ray carbon sulphur analyser,
The void item of high frequency infrared ray carbon sulphur analyser is 0.0000000.It is fluxing that 2.00 grams of high purity tungsten tin grain is added in bottomed crucible
Agent, 0.500 gram of high purity iron fluxing agent, analysis, obtain high-content sulphur standard substance first time measured value：0.00123、0.00134、
0.00118,0.00133,0.00145, average value is：0.00131.According to the standard value (S of sulphur in high-content sulphur standard substance：
0.0011% ± 0.0002%), high-content sulphur standard substance measured value be calibrated to for the first time：0.00104、0.00113、
0.00099,0.00112,0.00122, average value is：0.00110.
1.2.1 first time mean blank value, is measured：In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent,
0.500 gram of high purity iron fluxing agent.The nominal mass for inputting high frequency infrared ray carbon sulphur analyser is 1.0000 grams, high frequency-infrared carbon sulphur content
The void item of analyzer is 0.0000000.Analysis obtains first time blank value.Analysis five times：0.0000910,0.0000895,
0.0000782,0.0000933,0.0000759, it is 0.0000856 to calculate average value, obtains first time mean blank value
1.2.2, second of calibration of high frequency infrared ray carbon sulphur analyser：Weigh high-content sulphur standard substance AR-673 (S：
0.0011 ± 0.0002), 0.500 gram or so, it is accurate to 0.0001 gram, is put into bottomed crucible, by mass input high frequency-infrared carbon
In sulphur content analyzer, first time mean blank valueInput the void item of high frequency infrared ray carbon sulphur analyser
In, it is deducted automatically by high frequency infrared ray carbon sulphur analyser.In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent,
0.500 gram of high purity iron fluxing agent.Analysis, obtains high-content sulphur second of measured value of standard substance：0.00101、0.00099、
0.00111,0.00089,0.00109, average value 0.00102.According to the standard value (S of sulphur in high-content sulphur standard substance：
0.0011% ± 0.0002%), high-content sulphur standard substance measured value is calibrated to for the second time：0.00109、0.00107、
0.00120,0.00096,0.00118, average value is：0.00110.
1.2.3 second of mean blank value, is measured：In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent,
0.500 gram of high purity iron fluxing agent.The nominal mass for inputting high frequency infrared ray carbon sulphur analyser is 1.0000 grams, high frequency-infrared carbon sulphur content
The void item of analyzer is 0.0000000.Analysis obtains second of blank value.Analysis five times：0.0000910,0.0001005,
0.0001012,0.0001103,0.0001290, it is 0.0001064 to calculate average value, obtains second of mean blank value
1.2.4, high frequency infrared ray carbon sulphur analyser third time is calibrated：Weigh high-content sulphur standard substance AR-673 (S：
0.0011 ± 0.0002), 0.500 gram or so, it is accurate to 0.0001 gram, is put into bottomed crucible, by mass input high frequency-infrared carbon
In sulphur content analyzer, second of mean blank valueInput the void item of high frequency infrared ray carbon sulphur analyser
In, it is deducted automatically by the instrument.The high purity tungsten tin grain fluxing agent, 0.500 gram of high purity iron of 2.00 grams of addition in bottomed crucible
Fluxing agent.Analysis, obtains high-content sulphur standard substance third time measured value：0.00121、0.00099、0.00111、0.00122、
0.00132, average value 0.00117.According to the standard value (S of sulphur in high-content sulphur standard substance：0.0011% ±
0.0002%), third time is carried out to high-content sulphur standard substance measured value to be calibrated to：0.00114、0.00093、0.00104、
0.00115,0.00124, average value is：0.00110.Five calibration values are fallen in its tolerance (0.00090~0.00130) range
It is interior.
1.2.5 third time mean blank value, is measured：In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent,
0.500 gram of high purity iron fluxing agent.The nominal mass for inputting high frequency infrared ray carbon sulphur analyser is 1.0000 grams, high frequency-infrared carbon sulphur content
The void item of analyzer is 0.0000000.Analysis obtains third time blank value.Analysis five times：0.0001275,0.0001151,
0.0001003,0.0001053,0.0000880, it calculates average value and obtains third time mean blank valueThis
Blank value is the total blank value of sulfur content.
1.2.6 blank show value, is measured：In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent, 0.500 gram
High purity iron fluxing agent.The nominal mass for inputting high frequency infrared ray carbon sulphur analyser is 1.0000 grams, third time mean blank valueIt inputs in the void item of high frequency infrared ray carbon sulphur analyser.Analysis obtains blank show value.Analysis five
It is secondary：0.0000021,0.0000042,0.0000000,0.0000031,0.0000009, average value is：0.00000206.Have leisure
White show value
1.2.7, the calculating of blank test effect value：
For the measurement range that this method limits as 0.00008%~0.0010%, blank test effect value should be less than measurement range
/ 10th of lower limit, i.e.,
0.00008% ÷ 10=0.000008%
To blank show value, calculating average value isStandard deviation is：0.00000168.
Blank test effect value=average value+3 × standard deviation.
This blank test effect value measured is=0.00000206+3 × 0.00000168=0.00000709.
Blank test effect value≤0.000008% can be measured subsequently.
1.3 low content sulphur standard substances, which are examined, to be measured：Weigh YSBC 20117c-2009 (0.00044 ± 0.00009), matter
Amount is m=0.50g, is accurate to 0.001g, and sample mass m inputs high frequency infrared ray carbon sulphur analyser, is subsequently placed in bottomed crucible,
Add 2.00 grams of high purity tungsten tin grain fluxing agents, 0.500 gram of high purity iron fluxing agent；It measures twice, measured value：0.00046,
0.00050.Two measured values are fallen in its tolerance (0.00035~0.00053) range.
The measurement of sulfur content in 1.4 wrought superalloy samples
Sampling and sample preparation：The wrought superalloy to be measured that client is provided is according to HB/Z 205-1991《Steel and high temperature alloy
The sampling specification of chemical analysis sample》Requirement be sampled and sample preparation, obtain wrought superalloy sample to be measured.
Prepare sample：In the wrought superalloy sample to be measured obtained from sample preparation, weigh quality be m=0.5001g,
The sample of 0.5010g, sample mass m input high frequency infrared ray carbon sulphur analyser, are subsequently placed in bottomed crucible, add 2.00 grams
High purity tungsten tin grain fluxing agent, 0.500 gram of high purity iron fluxing agent.
Measure the sulfur content in wrought superalloy sample to be measured：Sample is put into high frequency infrared ray carbon sulphur analyser, by height
The selected operating condition of frequency infrared carbon sulfur analyzer, carries out sulfur content measurement, measures twice.Obtain measured value：0.00010,
0.00011, this time measuring average value is：0.00010%.
In measurement process, in order to reduce and stablize blank value, effective drier is replaced, guarantee effectively purifies carrier gas
And influence of the water to measurement is eliminated, clean combustion furnace, pipeline and filter etc. ensure instrument system blank value stabilization, meanwhile,
The bottomed crucible (being not added with sample when measuring blank) for having filled sample and fluxing agent is heated using micro-wave oven, with
Fluxing agent therein, which slightly changes colour, to be limited.
Embodiment two
Super-low sulfur in wrought superalloy GH4169 is measured using high frequency infrared ray carbon sulphur analyser in the present embodiment
The content of (0.00008%~0.0010%).In measurement process, the lower sensitivity limit of high frequency infrared ray carbon sulphur analyser is ±
0.0000005%, the operating condition of instrument is as follows：3.0 ± 0.2L/min of flow is measured, 40 ± 2psi of pressure, power gas are measured
40 ± 2psi of pressure, minimum analysis time 40s；Environmental condition is：Indoor relative humidity is not more than 60%.
Material used in measurement process is as follows：
High-content sulphur standard substance：U.S. AR-673 (0.0011 ± 0.0002), sulfur content are：0.0011% ±
0.0002%；
Low content sulphur standard substance：Standard sample YSBC 20117c-2009 (0.00044 ± 0.00009) sulfur content is：
0.00044% ± 0.00009%；
Porcelain crucible：Al2O3 materials, φ 25mm × 25mm；
High purity tungsten tin grain fluxing agent：S：≤ 0.00002%；
High purity iron fluxing agent：S≤0.00005%；
High purity oxygen gas：Content is more than 99.999%.
Specific measuring process is as follows：
The preparation of 1.1 bottomed crucibles：2.0 grams of high purity iron fluxing agent is added in porcelain crucible, is put into high frequency-infrared carbon sulphur
In analyzer, burning, cooling obtains bottomed crucible.
The measurement of the calibration of 1.2 high frequency infrared ray carbon sulphur analysers and the total blank value of sulfur content, measuring process are as follows：
High frequency infrared ray carbon sulphur analyser is calibrated for the first time：Weighing high-content sulphur standard substance AR-673 (0.0011 ±
0.0002), 0.500 gram or so, it is accurate to 0.0001 gram, is put into bottomed crucible, in instrument described in mass input, the instrument
Void item is 0.0000000.It is fluxing that 2.00 grams of high purity tungsten tin grain fluxing agent, 0.500 gram of high purity iron are added in bottomed crucible
Agent, analysis, obtains high-content sulphur standard substance first time measured value：0.00132、0.00124、0.00128、0.00130、
0.00150, average value is：0.00133.According to the standard value (S of sulphur in high-content sulphur standard substance：0.0011% ±
0.0002%), high-content sulphur standard substance measured value be calibrated to for the first time：0.00109、0.00103、0.00106、
0.00108,0.00124, average value is：0.00110.
1.2.1 measuring first time mean blank value：In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent,
0.500 gram of high purity iron fluxing agent.The nominal mass for inputting high frequency infrared ray carbon sulphur analyser is 1.0000 grams, the blank of the instrument
Item is 0.0000000.Analysis obtains first time blank value.Analysis five times：0.0000890,0.0000885,0.0000762,
0.0000953,0.0000708, it is 0.0000840 to calculate average value, obtains first time mean blank value
1.2.2 second of calibration of high frequency infrared ray carbon sulphur analyser：Weigh high-content sulphur standard substance AR-673 (S：0.0011
± 0.0002), 0.500 gram or so, it is accurate to 0.0001 gram, is put into bottomed crucible, by mass input high frequency-infrared analysis of carbon and sulfur
In instrument, first time mean blank valueIt inputs in the void item of the instrument, certainly by the instrument
It is dynamic to deduct.The high purity tungsten tin grain fluxing agent, 0.500 gram of high purity iron fluxing agent of 2.00 grams of addition in bottomed crucible.Analysis, obtains
High-content sulphur second of measured value of standard substance：0.001 01,0.00086,0.00107,0.00098,0.00100, average value
It is 0.00098.According to the standard value (S of sulphur in high-content sulphur standard substance：0.0011% ± 0.0002%), to high-content sulphur mark
Quasi- physical measurements are calibrated to for the second time：0.00113,0.00096,0.00120,0.00110,0.00112 average value is：
0.00110。
1.2.3 measuring second of mean blank value：In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent,
0.500 gram of high purity iron fluxing agent.The nominal mass for inputting high frequency infrared ray carbon sulphur analyser is 1.0000 grams, the blank of the instrument
Item is 0.0000000.Analysis obtains second of blank value.Analysis five times：0.0001010,0.0000895,0.0000992,
0.0001003,0.0001209, it is 0.0001022 to calculate average value, obtains second of mean blank value
1.2.4 high frequency infrared ray carbon sulphur analyser third time is calibrated：Weigh high-content sulphur standard substance AR-673 (S：0.0011
± 0.0002), 0.500 gram or so, it is accurate to 0.0001 gram, is put into bottomed crucible, by mass input high frequency-infrared analysis of carbon and sulfur
In instrument, second of mean blank valueIt inputs in the void item of high frequency infrared ray carbon sulphur analyser, by
The instrument deducts automatically.It is fluxing that 2.00 grams of high purity tungsten tin grain fluxing agent, 0.500 gram of high purity iron are added in bottomed crucible
Agent.Analysis, obtains high-content sulphur standard substance third time measured value：0.00131、0.00109、0.00101、0.00139、
0.00122, average value 0.00120.According to the standard value (S of sulphur in high-content sulphur standard substance：0.0011% ±
0.0002%), third time is carried out to high-content sulphur standard substance measured value to be calibrated to：0.00120、0.00100、0.00092、
0.00127,0.00111, average value is：0.00110.Five calibration values are fallen in its tolerance (0.00090~0.00130) range
It is interior.
1.2.5 measuring third time mean blank value：In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent,
0.500 gram of high purity iron fluxing agent.The nominal mass for inputting high frequency infrared ray carbon sulphur analyser is 1.0000 grams, the blank of the instrument
Item is 0.0000000.Analysis obtains third time blank value.Analysis five times：0.0001105,0.0000870,0.0001093,
0.0000993,0.0001245, it calculates average value and obtains third time mean blank valueThis blank value is sulphur
The total blank value of content.
1.2.6 measuring blank show value：In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent, 0.500 gram
High purity iron fluxing agent.The nominal mass for inputting high frequency infrared ray carbon sulphur analyser is 1.0000 grams, third time blank valueIt inputs in the void item of the instrument.Analysis obtains blank show value.Analysis five times：0.0000021,
0.0000032, -0.0000001, -0.0000024,0.0000010, average value is：0.00000076.Obtain blank show value
1.2.7. the calculating of blank test effect value
For the measurement range that this method limits as 0.00008%~0.0010%, blank test effect value should be less than measurement range
/ 10th of lower limit, i.e.,
0.00008% ÷ 10=0.000008%
To blank show value, calculating average value isStandard deviation is：0.00000215.
Blank test effect value=average value+3 × standard deviation.
This blank test effect value measured is=0.00000076+3 × 0.00000215=0.00000722.
Blank test effect value≤0.000008% can be measured subsequently.
1.3 low content sulphur standard substances, which are examined, to be measured：Weigh YSBC 20117c-2009 (0.00044 ± 0.00009), matter
Amount is m=0.50g, is accurate to 0.001g, and sample mass m inputs high frequency infrared ray carbon sulphur analyser, is subsequently placed in bottomed crucible,
Add 2.00 grams of high purity tungsten tin grain fluxing agents, 0.500 gram of high purity iron fluxing agent；It measures twice, measured value：0.00043,
0.00039.Two measured values are fallen in its tolerance (0.00035~0.00053) range.
The measurement of sulfur content in 1.4 wrought superalloy samples
Sampling and sample preparation：The wrought superalloy to be measured that client is provided is according to HB/Z 205-1991《Steel and high temperature alloy
The sampling specification of chemical analysis sample》Requirement be sampled and sample preparation, obtain wrought superalloy sample to be measured；
Prepare sample：In the wrought superalloy sample to be measured obtained from sample preparation, weigh quality be m=0.5003g,
Sample mass m is inputted high frequency infrared ray carbon sulphur analyser, is subsequently placed in bottomed crucible, adds by the sample of 0.499 5g
2.00 gram high purity tungsten tin grain fluxing agent, 0.500 gram of high purity iron fluxing agent；
Measure the sulfur content in wrought superalloy sample to be measured：Sample is put into high frequency infrared ray carbon sulphur analyser, by height
The selected operating condition of frequency infrared carbon sulfur analyzer, carries out sulfur content measurement, measures twice.Obtain measured value：0.00040,
0.00036, this time measuring average value is：0.00038%.
In measurement process, in order to reduce and stablize blank value, effective drier is replaced, guarantee effectively purifies carrier gas
And influence of the water to measurement is eliminated, clean combustion furnace, pipeline and filter etc. ensure instrument system blank value stabilization, in addition
The bottomed crucible (being not added with sample when measuring blank) for having filled sample and fluxing agent is heated using micro-wave oven, with
Fluxing agent therein, which slightly changes colour, to be limited.
Embodiment three
Super-low sulfur in wrought superalloy GH4169 is measured using high frequency infrared ray carbon sulphur analyser in the present embodiment
The content of (0.00008%~0.0010%).The lower sensitivity limit of measurement process medium-high frequency infrared carbon sulfur analyzer be ±
0.0000005%, the operating condition of instrument is as follows：3.0 ± 0.2L/min of flow is measured, 40 ± 2psi of pressure, power gas are measured
40 ± 2psi of pressure, minimum analysis time 40s；Environmental condition is：Indoor relative humidity is not more than 60%.
Material used in measurement process is as follows：
High-content sulphur standard substance：U.S. AR-673 (0.0011 ± 0.0002), sulfur content are：0.0011% ±
0.0002%；
Low content sulphur standard substance：Japanese JSS 003-6 (0.00013 ± 0.00003), sulfur content：0.00013% ±
0.00003%；
Porcelain crucible：Al2O3 materials, φ 25mm × 25mm；
High purity tungsten tin grain fluxing agent：S：≤ 0.00002%；
High purity iron fluxing agent：S≤0.00005%；
High purity oxygen gas：Content is more than 99.999%.
Specific measuring process is as follows：
The preparation of 1.1 bottomed crucibles：2.0 grams of high purity iron fluxing agent is added in porcelain crucible, is put into high frequency-infrared carbon sulphur
In analyzer, burning, cooling obtains bottomed crucible.
The measurement of the calibration of 1.2 high frequency infrared ray carbon sulphur analysers and the total blank value of sulfur content, measuring process are as follows：
High frequency infrared ray carbon sulphur analyser is calibrated for the first time：Weighing high-content sulphur standard substance AR-673 (0.0011 ±
0.0002), 0.500 gram or so, it is accurate to 0.0001 gram, is put into bottomed crucible, by instrument described in mass input, the instrument
Void item be 0.0000000.2.00 grams of high purity tungsten tin grain fluxing agent is added in bottomed crucible, 0.500 gram of high purity iron helps
Flux, analysis, obtains high-content sulphur standard substance first time measured value：0.00122、0.00124、0.00148、0.00110、
0.00158, average value is：0.00132.According to the standard value (S of sulphur in high-content sulphur standard substance：0.0011% ±
0.0002%), high-content sulphur standard substance measured value be calibrated to for the first time：0.00101、0.00103、0.00123、
0.00091,0.00131, average value is：0.00110.
1.2.1 measuring first time mean blank value：In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent,
0.500 gram of high purity iron fluxing agent.The nominal mass for inputting high frequency infrared ray carbon sulphur analyser is 1.0000 grams, the blank of the instrument
Item is 0.0000000.Analysis obtains first time blank value.Analysis five times：0.0000896,0.0000925,0.0000862,
0.0000853,0.0000908, it is 0.0000889 to calculate average value, obtains first time mean blank value
1.2.2 second of calibration of high frequency infrared ray carbon sulphur analyser：Weigh high-content sulphur standard substance AR-673 (S：0.0011
± 0.0002), 0.500 gram or so, it is accurate to 0.0001 gram, is put into bottomed crucible, by instrument described in mass input, first
Secondary mean blank valueIt inputs in the void item of the instrument, is deducted automatically by the instrument.It is beating
The high purity tungsten tin grain fluxing agent, 0.500 gram of high purity iron fluxing agent of 2.00 grams of addition in the crucible of bottom.Analysis, obtains high-content sulphur mark
Second of measured value of quasi- substance：0.00095,0.00088,0.00106,0.00088,0.00100, average value 0.00095.Root
According to the standard value (S of sulphur in high-content sulphur standard substance：0.0011% ± 0.0002%), to high-content sulphur standard substance measured value
It is calibrated to for the second time：0.00110,0.00101,0.00122,0.00101,0.00115 average value is：0.00110.
1.2.3 measuring second of mean blank value：In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent,
0.500 gram of high purity iron fluxing agent.The nominal mass for inputting high frequency infrared ray carbon sulphur analyser is 1.0000 grams, the blank of the instrument
Item is 0.0000000.Analysis obtains second of blank value.Analysis five times：0.0001019,0.0001225,0.0000995,
0.0001063,0.0000972, it is 0.0001022 to calculate average value, obtains second of mean blank value
1.2.4 high frequency infrared ray carbon sulphur analyser third time is calibrated：Weigh high-content sulphur standard substance AR-673 (S：0.0011
± 0.0002), 0.500 gram or so, it is accurate to 0.0001 gram, is put into bottomed crucible, by instrument described in mass input, second
Secondary mean blank valueIt inputs in the void item of the instrument, is deducted automatically by the instrument.It is beating
The high purity tungsten tin grain fluxing agent, 0.500 gram of high purity iron fluxing agent of 2.00 grams of addition in the crucible of bottom.Analysis obtains high-content sulphur standard
Substance third time measured value：0.00137,0.00119,0.00131,0.00100,0.00099, average value 0.00117.According to
Standard value (the S of sulphur in high-content sulphur standard substance：0.0011% ± 0.0002%), to high-content sulphur standard substance measured value into
Row third time is calibrated to：0.00129,0.00112,0.00123,0.00094,0.00093 average value is：0.00110.Five schools
Quasi- value is fallen in its tolerance (0.00090~0.00130) range.
1.2.5 measuring third time mean blank value：In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent,
0.500 gram of high purity iron fluxing agent.The nominal mass for inputting high frequency infrared ray carbon sulphur analyser is 1.0000 grams, the blank of the instrument
Item is 0.0000000.Analysis obtains third time blank value.Analysis five times：0.0001100,0.0001010,0.0000893,
0.0000983,0.0001205, it calculates average value and obtains third time mean blank valueThis blank value is sulphur
The total blank value of content.
1.2.6 measuring blank show value：In bottomed crucible be added 2.00 grams high purity tungsten tin grain fluxing agent, 0.500 gram
High purity iron fluxing agent.The nominal mass for inputting high frequency infrared ray carbon sulphur analyser is 1.0000 grams, third time mean blank valueIt inputs in the void item of the instrument.Analysis obtains blank show value.Analysis five times：-
0.0000011,0.0000030, -0.0000011, -0.0000020,0.0000015, average value is：0.00000066.Have leisure
White show value X0=0.00000066.
1.2.7. the calculating of blank test effect value
For the measurement range that this method limits as 0.00008%~0.0010%, blank test effect value should be less than measurement range
/ 10th of lower limit, i.e.,
0.00008% ÷ 10=0.000008%
To blank show value, calculating average value isStandard deviation is：0.00000211.
Blank test effect value=average value+3 × standard deviation.
This blank test effect value measured is=0.00000066+3 × 0.00000211=0.00000700.
Blank test effect value≤0.000008% can be measured subsequently.
1.3 low content sulphur standard substances, which are examined, to be measured：Weigh JSS 003-6 (0.00013 ± 0.00003), quality m=
0.50g, is accurate to 0.001g, and sample mass m inputs high frequency infrared ray carbon sulphur analyser, is subsequently placed in bottomed crucible, adds
2.00 grams of high purity tungsten tin grain fluxing agents, 0.500 gram of high purity iron fluxing agent；It measures twice, measured value：0.00013,0.00010.Two
A measured value is fallen in its tolerance (0.00010~0.00016) range.
The measurement of sulfur content in 1.4 wrought superalloy samples
Sampling and sample preparation：The wrought superalloy to be measured that client is provided is according to HB/Z 205-1991《Steel and high temperature alloy
The sampling specification of chemical analysis sample》Requirement be sampled and sample preparation, obtain wrought superalloy sample to be measured,
Prepare sample：In the wrought superalloy sample to be measured obtained from sample preparation, weigh quality be m=0.5009g,
The sample of 0.4999g, sample mass m input high frequency infrared ray carbon sulphur analyser, are subsequently placed in bottomed crucible, add 2.00 grams
High purity tungsten tin grain fluxing agent, 0.500 gram of high purity iron fluxing agent.
Measure the sulfur content in wrought superalloy sample to be measured：Sample is put into high frequency infrared ray carbon sulphur analyser, by height
The selected operating condition of frequency infrared carbon sulfur analyzer, carries out sulfur content measurement, measures twice.Obtain measured value：0.00010,
0.00008, this time measuring average value is：0.00009%.
In measurement process, in order to reduce and stablize blank value, effective drier is replaced, guarantee effectively purifies carrier gas
And influence of the water to measurement is eliminated, clean combustion furnace, pipeline and filter etc. ensure instrument system blank value stabilization, in addition
The bottomed crucible (being not added with sample when measuring blank) for having filled sample and fluxing agent is heated using micro-wave oven, with
Fluxing agent therein, which slightly changes colour, to be limited.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features；
And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (7)
1. a kind of method measuring ultra-low sulfur in wrought superalloy, includes the following steps：
The preparation of 1.1 bottomed crucibles；
The measurement of the calibration of 1.2 high frequency infrared ray carbon sulphur analysers and the total blank value of sulfur content；
1.3. low content sulphur standard substance is measured；
The measurement of sulfur content in 1.4 wrought superalloy samples；
It is characterized in that, being followed the steps below after first time calibration measurement in 1.2 step：
1.2.1 it carries out high frequency infrared ray carbon sulphur analyser to calibrate for the first time, the measurement of first time mean blank value：
High purity tungsten tin grain fluxing agent 2g ± 0.5, high purity iron fluxing agent 0.5g ± 0.2 are added in the bottomed crucible, by its name
In high frequency infrared ray carbon sulphur analyser described in adopted mass input, and the void item of the high frequency infrared ray carbon sulphur analyser is zeroed, it will
The bottomed crucible is put into analysis in the high frequency infrared ray carbon sulphur analyser and obtains blank value, analyzes at least 3 times, calculates average
Value, obtains first time mean blank value
1.2.2. second of calibration of high frequency infrared ray carbon sulphur analyser：
High-content sulphur standard substance is weighed, the bottomed crucible is put into, high frequency-infrared analysis of carbon and sulfur described in mass input will be weighed
In instrument, by the first time mean blank valueIt inputs in the void item of the high frequency infrared ray carbon sulphur analyser, by the high frequency
Infrared carbon sulfur analyzer deducts automatically, and addition high purity tungsten tin grain fluxing agent 2g ± 0.5, high purity iron are fluxing in the bottomed crucible
The bottomed crucible is put into the high frequency infrared ray carbon sulphur analyser by agent 0.5g ± 0.2, and analysis obtains the high-content sulphur mark
Second of measured value of quasi- substance, according to the standard value of sulphur in the high-content sulphur standard substance, to high frequency-infrared analysis of carbon and sulfur
Instrument carries out second and calibrates；
1.2.3 second of mean blank value, is measured：
High purity tungsten tin grain fluxing agent 2g ± 0.5, high purity iron fluxing agent 0.5g ± 0.2 are added in the bottomed crucible, by its name
In high frequency infrared ray carbon sulphur analyser described in adopted mass input, and the void item of the high frequency infrared ray carbon sulphur analyser is zeroed, and
The bottomed crucible is put into analysis in the high frequency infrared ray carbon sulphur analyser and obtains blank value, is analyzed at least 3 times, is calculated average
Value, obtains second of mean blank value
1.2.4 high frequency infrared ray carbon sulphur analyser third time is calibrated：
High-content sulphur standard substance is weighed, the bottomed crucible is put into, high frequency-infrared analysis of carbon and sulfur described in mass input will be weighed
In instrument, by second of mean blank valueIt inputs in the void item of the high frequency infrared ray carbon sulphur analyser, by the high frequency
Infrared carbon sulfur analyzer deducts the blank value automatically, and high purity tungsten tin grain high purity tungsten tin grain is added in the bottomed crucible and is helped
Flux 2g ± 0.5, high purity iron fluxing agent 0.5g ± 0.2, and the bottomed crucible is put into the high frequency infrared ray carbon sulphur analyser
Middle analysis obtains the high-content sulphur standard substance third time measured value, according to the mark of sulphur in the high-content sulphur standard substance
Quasi- value carries out third time calibration to high frequency infrared ray carbon sulphur analyser；
1.2.5 measuring third time mean blank value：
High-purity high purity tungsten tin grain fluxing agent 2g ± 0.5, high purity iron fluxing agent 0.5g ± 0.2 are added in the bottomed crucible, it will
Nominal mass inputs in the high frequency infrared ray carbon sulphur analyser, and the void item of the high frequency infrared ray carbon sulphur analyser is zeroed,
Analysis obtains blank value, analyzes at least 3 times, calculates average value, obtains third time mean blank valueThis blank value is that sulphur contains
Measure total blank value；
1.2.6 blank show value, is measured：
High purity tungsten tin grain fluxing agent 2g ± 0.5, high purity iron fluxing agent 0.5g ± 0.2 are added in the bottomed crucible, by its name
In high frequency infrared ray carbon sulphur analyser described in adopted mass input, and by third time mean blank valueInput the high frequency-infrared carbon
The void item of sulphur content analyzer is analyzed at least 3 times, obtains at least three blank show value；
1.2.7 the calculating of blank test effect value：
For the measurement range that this method limits as 0.00008%~0.0010%, blank test effect value should be less than measurement range lower limit
1/10th, i.e.,
0.00008% ÷ 10=0.000008%
Average value is calculated at least three blank show valueAnd standard deviation, and blank test effect value is calculated according to following formula：
When blank test effect value≤0.000008%, sample can be measured.
2. the method for measuring ultra-low sulfur in wrought superalloy as described in claim 1, which is characterized in that will contain and help
The bottomed crucible of flux or sample is put into before the high frequency infrared ray carbon sulphur analyser, is carried out at heating to the bottomed crucible
Reason.
3. the method for measuring ultra-low sulfur in wrought superalloy as claimed in claim 1 or 2, which is characterized in that the
The accuracy weighed described in primary calibration measurement, step 1.2.2,1.2.4,1.3 and 1.4 is 0.0001g.
4. the method for measuring ultra-low sulfur in wrought superalloy as described in claim 1, which is characterized in that the step
In 1.3, if the measured value of the low content sulphur standard substance sulfur content does not fall within the low content sulphur standard substance tolerance
In range, then repeatedly step 1.2~1.3, until the measured value of the low content sulphur standard substance sulfur content falls into its tolerance
Until in range.
5. the method for measuring ultra-low sulfur in wrought superalloy as described in claim 1, which is characterized in that wherein surveying
When measuring the first time, second, third time mean blank value, the analysis carries out 5 times.
6. the method for measuring ultra-low sulfur in wrought superalloy as claimed in claim 2, which is characterized in that the heating
Processing is carried out using micro-wave oven.
7. the method for measuring ultra-low sulfur in wrought superalloy as described in claim 1, which is characterized in that the step
1.2.6 in, blank show value measures 5 times.
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