CN108414470B - Method for measuring ultralow sulfur content in wrought superalloy - Google Patents
Method for measuring ultralow sulfur content in wrought superalloy Download PDFInfo
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 205
- 239000011593 sulfur Substances 0.000 title claims abstract description 205
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 42
- 239000000126 substance Substances 0.000 claims abstract description 70
- 238000004458 analytical method Methods 0.000 claims abstract description 37
- 239000000956 alloy Substances 0.000 claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 114
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 112
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 98
- 238000005259 measurement Methods 0.000 claims description 85
- 229910052742 iron Inorganic materials 0.000 claims description 56
- AWXLLPFZAKTUCQ-UHFFFAOYSA-N [Sn].[W] Chemical compound [Sn].[W] AWXLLPFZAKTUCQ-UHFFFAOYSA-N 0.000 claims description 52
- 239000002245 particle Substances 0.000 claims description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 238000005303 weighing Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004364 calculation method Methods 0.000 claims description 6
- 230000004907 flux Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 23
- 238000003723 Smelting Methods 0.000 abstract description 11
- 238000003908 quality control method Methods 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 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 12
- 239000000919 ceramic Substances 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 239000002274 desiccant Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005242 forging Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004164 analytical calibration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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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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Abstract
The invention belongs to the field of alloy trace element analysis, and relates to a method for measuring ultralow sulfur content in a wrought superalloy, which comprises the following steps: reducing and stabilizing the blank value, measuring the total blank value of the sulfur content by using a high-sulfur standard substance calibration instrument, measuring the total blank value of the sulfur content through three calibration processes, measuring the low-sulfur standard substance, confirming that the measured value is within the allowable difference range of the standard substance, and finally measuring the ultralow sulfur content in the deformed high-temperature alloy sample to be measured. The invention improves the accuracy of the measuring result and provides reliable technical guarantee for the smelting and quality control of the deformed high-temperature alloy.
Description
Technical Field
The invention belongs to the alloy trace element analysis technology, and relates to a method for measuring the content of ultralow sulfur (0.00008% -0.0010%) in a deformed high-temperature alloy.
Background
The wrought superalloy is widely used for manufacturing important parts such as a high-pressure turbine disc, a sealing disc, a turbine shaft, a casing, a fastener and the like in an aircraft engine, and is a superalloy material with the largest use amount, the widest application range and the most complete product types and specifications in the engine. With the development of high-performance engines, the high-purity requirement is put forward for the deformed high-temperature alloy material in order to improve the oxidation resistance and corrosion resistance of the deformed high-temperature alloy material, and to have higher yield strength and welding forming performance. High purity is mainly manifested by a significant reduction in the impurity content of the finished ingot. The impurity element sulfur contained in the material affects the performance of the material because of easy aggregation. Therefore, controlling the sulfur content is an important indicator. In order to meet the requirement of high purity, the smelting process is improved from the original duplex smelting process to the duplex smelting process, so that the content of sulfur can be reduced to 0.0003 percent and even 0.00008 percent, and an innovative sulfur detection method is urgently needed to meet the requirement brought by smelting progress.
A high-frequency infrared carbon-sulfur analyzer is generally adopted for analyzing the sulfur content in the material, and a corresponding analysis method is established on the basis of the high-frequency infrared carbon-sulfur analyzer. In the prior art, for example, CN103543122A discloses a method for determining the ultra-low sulfur content in a single crystal superalloy, but the method can only measure the single crystal superalloy with the sulfur content of 0.0002% -0.0020%, and cannot accurately measure the sulfur content of less than 0.0002%. CN101975760B discloses a method for determining sulfur content in powdered superalloy, which can only determine powdered superalloy with minimum sulfur content of 0.0008%, and cannot accurately determine superalloy with sulfur content less than 0.0008%. In addition, in the two methods, the blank value and the blank display value are not distinguished in the test process, so that the measurement result is inaccurate, and the steps are complicated.
It is well known to those skilled in the art that wrought superalloys differ significantly from powdered superalloys, and single crystal superalloys. The deformed high-temperature alloy is cast into an ingot through processes such as vacuum smelting and the like, then is made into sections such as cake blanks, rods, plates, pipes and the like through thermal deformation such as forging, rolling, cogging and the like, finally is die-forged into blanks such as turbine discs, blades and the like, and is processed into parts such as turbine discs, turbine blades and the like after thermal treatment. The smelting process mostly adopts a duplex smelting process (vacuum induction smelting and vacuum consumable remelting), and a small number adopts a duplex process (vacuum induction smelting, protective atmosphere electroslag remelting and vacuum consumable remelting). The triple process can reduce the content of impurity sulfur to be about 0.0001 percent. Sulfur is one of recognized harmful elements in the high-temperature alloy, and the plasticity, the durability and the like of the high-temperature alloy material are obviously influenced by the content of the sulfur. The sulfur is easy to be deviated to the grain boundary in the high-temperature alloy, the endurance life of the alloy is directly related to the content of the sulfur in the grain boundary, and when the sulfur is deviated to the grain boundary in an atomic state, the grain boundary strength can be weakened. In particular, the wrought superalloy needs to be subjected to a thermal deformation process such as forging, rolling, cogging and the like, so that the as-cast structure of the alloy becomes uneven, the segregation becomes more serious, and the precipitation of harmful phases is accompanied, thereby seriously influencing the cogging and forging processing of the alloy. The deformed high-temperature alloy has a plurality of deformation processing links, and the influence of sulfur accumulation harm is obvious, so the control requirement on ultra-low sulfur is stricter. In the aspect of measurement, the alloy components are complex, the high-melting point alloy elements are more, and the content is higher, so that the difficulty is brought to the complete release of ultralow sulfur in the melting process of the sample.
Therefore, the method standard for accurately detecting the content of the ultralow sulfur (0.00008% -0.0010%) in the deformed high-temperature alloy does not exist in the field at present. Therefore, how to accurately measure the content of ultra-low sulfur (0.00008% -0.0010%) in the wrought superalloy is a difficult problem.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for measuring the content of ultralow sulfur (0.00008% -0.0010%) in a wrought superalloy with high efficiency, accuracy and simple and convenient operation, so that the problem of measuring the content of ultralow sulfur (0.00008% -0.0010%) in the wrought superalloy can be solved.
The object of the present invention and the solution of the technical problem are achieved by the following technical means. The technical scheme of the invention is as follows: a method for measuring the content of ultra-low sulfur (0.00008% -0.0010%) in a wrought superalloy comprises the following steps: preparing a bottoming crucible; reducing and stabilizing the blank value; calibrating a high-frequency infrared carbon-sulfur analyzer; measuring a total blank value of the sulfur content; measuring a blank display value; calculating a blank influence value; and (4) carrying out inspection measurement on the low-content sulfur standard substance and measurement on a sample to be measured.
In an embodiment of the present invention, the method for measuring the ultra low sulfur content in a wrought superalloy comprises the steps of:
1. a method for measuring the ultra-low sulfur content in a wrought superalloy is characterized by comprising the following steps:
1.1 preparation of a bottoming crucible: adding a high-purity iron fluxing agent into the crucible, putting the crucible into a high-frequency infrared carbon-sulfur analyzer, burning, and cooling to obtain the bottoming crucible;
1.2 calibrating a high-frequency infrared carbon and sulfur analyzer and measuring a total blank value of sulfur content, comprising the following steps of:
calibrating a high-frequency infrared carbon-sulfur analyzer for the first time:
weighing a high-sulfur standard substance, putting the high-sulfur standard substance into the bottoming crucible, inputting the weighed mass into the high-frequency infrared carbon-sulfur analyzer, adding 2g +/-0.5 g of high-purity tungsten tin particle fluxing agent and 0.5g +/-0.2 g of high-purity iron fluxing agent into the bottoming crucible, putting the bottoming crucible into the high-frequency infrared carbon-sulfur analyzer for analysis to obtain a first measured value of the high-sulfur standard substance, and performing first calibration on the high-frequency infrared carbon-sulfur analyzer according to a standard value of sulfur in the high-sulfur standard substance;
1.2.1, measuring the first average blank value
Adding 2g +/-0.5 g of high-purity tungsten tin particle fluxing agent and 0.5g +/-0.2 g of high-purity iron fluxing agent into the bottoming crucible, and then adding the materialsInputting the nominal mass into the high-frequency infrared carbon and sulfur analyzer, returning the blank item of the high-frequency infrared carbon and sulfur analyzer to zero, putting the bottoming crucible into the high-frequency infrared carbon and sulfur analyzer for analyzing for at least 3 times to obtain a blank value, and calculating an average value to obtain a first average blank value
1.2.2. And (3) calibrating the high-frequency infrared carbon-sulfur analyzer for the second time:
weighing high-sulfur standard substances, putting the standard substances into the bottoming crucible, inputting the weighed mass into the high-frequency infrared carbon-sulfur analyzer, and taking the first average blank value
Inputting the data into a blank item of the high-frequency infrared carbon-sulfur analyzer, automatically deducting the data by the high-frequency infrared carbon-sulfur analyzer, adding high-purity tungsten tin particle fluxing agent and high-purity iron fluxing agent into the bottoming crucible, putting the bottoming crucible into the high-frequency infrared carbon-sulfur analyzer, analyzing to obtain a second measured value of the high-sulfur standard substance, and performing second calibration on the high-frequency infrared carbon-sulfur analyzer according to a standard value of sulfur in the high-sulfur standard substance;
1.2.3, measuring the second average blank value
Adding 2g +/-0.5 g of high-purity tungsten tin particle fluxing agent and 0.5g +/-0.2 g of high-purity iron fluxing agent into the bottoming crucible, inputting the nominal mass of the high-purity tungsten tin particle fluxing agent and the high-purity iron fluxing agent into the high-frequency infrared carbon-sulfur analyzer, enabling blank items of the high-frequency infrared carbon-sulfur analyzer to be zero, putting the bottoming crucible into the high-frequency infrared carbon-sulfur analyzer, analyzing for at least 3 times, calculating an average value, and obtaining a second average blank value
1.2.4 calibrating the high-frequency infrared carbon-sulfur analyzer for the third time:
weighing high-sulfur standard substance, putting into the bottoming crucible, and transferring the weighed massEntering the high-frequency infrared carbon and sulfur analyzer to obtain the second average blank value
Inputting the measured value into a blank item of the high-frequency infrared carbon-sulfur analyzer, automatically deducting the blank value by the analyzer, adding a high-purity tungsten-tin particle fluxing agent and a high-purity iron fluxing agent into the bottoming crucible, putting the bottoming crucible into the high-frequency infrared carbon-sulfur analyzer for analysis to obtain a third measured value of the high-sulfur standard substance, and carrying out third calibration on the high-frequency infrared carbon-sulfur analyzer according to the standard value of sulfur in the high-sulfur standard substance;
1.2.5 measurement of third average blank value:
adding 2g +/-0.5 g of high-purity tungsten tin particle fluxing agent and 0.5g +/-0.2 g of high-purity iron fluxing agent into the bottoming crucible, inputting nominal mass into the high-frequency infrared carbon-sulfur analyzer, enabling blank items of the high-frequency infrared carbon-sulfur analyzer to be zero, analyzing to obtain blank values, analyzing for at least 3 times, calculating an average value, and obtaining a third average blank value
The blank value is the total blank value of the sulfur content;
1.2.6 measurement of blank display value
Adding 2g +/-0.5 g of high-purity tungsten tin particle fluxing agent and 0.5g +/-0.2 g of high-purity iron fluxing agent into the bottoming crucible, inputting the nominal mass of the high-purity tungsten tin particle fluxing agent and the high-purity iron fluxing agent into the high-frequency infrared carbon-sulfur analyzer, and adding the third average blank value
Inputting blank items of the high-frequency infrared carbon and sulfur analyzer, and analyzing for at least 3 times to obtain at least 3 blank display values;
1.2.7. calculation of blank impact value:
the measurement range limited by the method is 0.00008% -0.0010%, and the blank influence value is less than one tenth of the lower limit of the measurement range, namely
0.00008％÷10＝0.000008％
Calculating an average value for at least 3 blank display values
And standard deviation, and calculating the blank impact value according to the following formula:
when the blank influence value is less than or equal to 0.000008 percent, the test sample can be measured.
1.3. Measurement of low sulfur standard:
weighing a low-sulfur standard substance, putting the low-sulfur standard substance into the bottoming crucible, inputting the weighed mass into the high-frequency infrared carbon-sulfur analyzer, adding 2g +/-0.5 g of high-purity tungsten tin particle fluxing agent and 0.5g +/-0.2 g of high-purity iron fluxing agent into the bottoming crucible, and putting the bottoming crucible into the high-frequency infrared carbon-sulfur analyzer for analysis to obtain a measured value of the sulfur content of the low-sulfur standard substance.
1.4 measurement of Sulfur content in wrought superalloy specimens
Weighing a deformed high-temperature alloy sample, placing the sample in the bottoming crucible, inputting the mass of the sample into the high-frequency infrared carbon-sulfur analyzer, adding 2g of high-purity tungsten-tin particle fluxing agent and 0.5g of high-purity iron fluxing agent into the bottoming crucible, and mixing the high-purity tungsten-tin particle fluxing agent and the high-purity iron fluxing agent with the sample to form a sample; and (3) placing the bottoming crucible containing the sample into the high-frequency infrared carbon-sulfur analyzer, and measuring to obtain a measured value. The analysis was performed at least 2 times. And the average value of the measured values is the sulfur content of the deformed superalloy sample.
Before a crucible containing a flux or a sample is placed in the high-frequency infrared carbon-sulfur analyzer, the crucible is heated.
The weighing in the first calibration measurement, steps 1.2.2, 1.2.4, 1.3 and 1.4 has an accuracy of 0.0001 g.
In the step 1.3, if the measured value of the sulfur content of the low-sulfur standard substance does not fall within the allowable difference range of the low-sulfur standard substance, repeating the steps 1.2-1.3 until the measured value of the sulfur content of the low-sulfur standard substance falls within the allowable difference range of the low-sulfur standard substance.
The analysis was performed 5 times while measuring the first, second, and third average blank values.
The heating treatment is performed using a microwave oven.
In said step 1.2.6, the blank display value is measured 5 times.
Compared with the prior art, the invention has obvious beneficial technical effects. According to the technical scheme, the blank value and the blank display value are distinguished, the blank value is reduced and stabilized, and the blank value is accurately measured for three times, so that the blank influence value is lower than one tenth of the lower limit of the measurement range, the accuracy of the measurement result is improved, the measurement problem of the deformed high-temperature alloy is solved, reliable technical guarantee is provided for the smelting and quality control of the deformed high-temperature alloy, the step of preparing a sulfur calibration sample, which is indispensable to the measurement methods of the two patent documents, is omitted in the measurement process, the process is reduced, and the material consumption in the measurement process is reduced.
Detailed Description
Nominal mass in the process means: the high-frequency infrared carbon-sulfur analyzer must have a quality value when calculating the sulfur content; when the sample is measured, the mass value corresponds to the mass of the sample; for blank value measurement, the blank is of no quality, but the calculation must be performed by giving a quality value to the high frequency infrared carbon sulfur analyzer, which must be given as a nominal quality, typically 1.0000.
The blank impact value in the method refers to: the blank level after three instrument calibrations by the method represents the influence degree of the blank on the measurement and is closely related to the blank display value.
The existence of the blank can affect the measurement of sulfur in the sample. The influence of blank on the measurement of the sample can be reduced as much as possible, and the blank display value is a variable value and cannot be directly used for representing the blank level, but the blank display value is closely related to the blank level.
The blank impact values are: calculating an average value for at least 3 blank display values
And the standard deviation of the measured values,
the measurement range limited by the method is 0.00008% -0.0010%, and the blank influence value is less than one tenth of the lower limit of the measurement range, namely
0.00008％÷10＝0.000008％
When the blank influence value is less than or equal to 0.000008 percent, the test sample can be measured.
In the method of the present invention, in performing the first, second and third calibrations, the measured value of the high-sulfur content standard substance is measured at least 2 times or more for each calibration, the average value thereof is calculated, preferably 5 times in consideration of the accuracy and efficiency of the measurement, and the high-frequency infrared carbon-sulfur analyzer is sequentially calibrated according to the standard value of sulfur in the high-sulfur content standard substance.
In the method according to the invention, wherein in step 1.2.6, the blank display value may be measured 3, 4, 5, 6, 7, 8, 9, 10, 11 etc., preferably 5 times. The efficiency can be ensured under the condition of ensuring the measurement accuracy.
In the method according to the invention, wherein in step 1.4, 2, 3, 4, 5, 6, 7, 8 etc. times, preferably 2 times, can be measured. Therefore, the efficiency can be ensured under the condition of ensuring the measurement accuracy.
In the method, a high-frequency infrared carbon-sulfur analyzer is adopted for measurement, the lower limit of the sensitivity of the analyzer is +/-0.0000005%, and the working conditions are as follows: measuring the flow rate at 3.0 +/-0.2L/min, the pressure at 40 +/-2 psi, the power gas pressure at 40 +/-2 psi and the minimum analysis time at 40 s; the environmental conditions were: the indoor relative humidity is not more than 60%.
In the process of the invention, the high sulfur standard may be, for example, AR-673 (0.0011. + -. 0.0002) in the United states, the sulfur content being: 0.0011% + -0.0002%.
In the method of the invention, the low-sulfur standard substance can be a standard sample YSBC20117c-2009 (0.00044 +/-0.00009), and the sulfur content is as follows: 0.00044% ± 0.00009%; JSS 003-6(0.00013 ± 0.00003) in japan, sulfur content: 0.00013% + -0.00003%.
In the method of the invention, the crucible may be a porcelain crucible, for example, of Al2O3 material, phi 25mm by 25 mm.
In the method, the S of the high-purity tungsten-tin particle fluxing agent is as follows: less than or equal to 0.00002%, for example 0.000018%, 0.000015%, 0.000010%, etc.
In the method, the S of the high-purity iron fluxing agent is less than or equal to 0.00005 percent.
In the process of the present invention, the oxygen content of the high purity oxygen gas is greater than 99.999%, and may be, for example, 99.9999%, 99.99999%, etc.
In the method, in order to reduce and stabilize the blank value, an effective drying agent needs to be replaced, so that the carrier gas is effectively purified, and the influence of water on the measurement is eliminated; cleaning a combustion furnace, a pipeline, a filter and the like, and ensuring the stability of the blank value of an instrument system; and heating the crucible (without sample when measuring blank) with the sample and flux in it by microwave oven, wherein the flux is slightly discolored.
Example one
In this example, the content of ultra-low sulfur (0.00008% -0.0010%) in wrought superalloy GH4169 was measured using a high frequency infrared carbon-sulfur analyzer. In the measuring process, the lower limit of the sensitivity of the high-frequency infrared carbon-sulfur analyzer is +/-0.0000005%, and the working conditions of the analyzer are as follows: measuring the flow rate at 3.0 +/-0.2L/min, the pressure at 40 +/-2 psi, the power gas pressure at 40 +/-2 psi and the minimum analysis time at 40 s; the environmental conditions were: the indoor relative humidity is not more than 60%. The materials used in the measurement were as follows:
high sulfur content standard: us AR-673(0.0011 ± 0.0002), sulfur content: 0.0011% + -0.0002%;
low sulfur standard: standard sample YSBC20117c-2009 (0.00044 +/-0.00009) has the sulfur content: 0.00044% ± 0.00009%;
a porcelain crucible: al2O3 material, phi 25mm is multiplied by 25 mm;
high-purity tungsten tin particle fluxing agent: s: less than or equal to 0.00002 percent;
high-purity iron fluxing agent: s is less than or equal to 0.00005 percent;
high purity oxygen: the content is more than 99.999 percent.
The measurement steps are as follows:
1.1, preparing a bottoming crucible: adding 2.0 g of high-purity iron fluxing agent into the ceramic crucible, putting the ceramic crucible into a high-frequency infrared carbon-sulfur analyzer, and burning and cooling the ceramic crucible to obtain the bottoming crucible.
1.2, calibrating a high-frequency infrared carbon and sulfur analyzer and measuring a total blank value of sulfur content, wherein the measuring steps are as follows:
calibrating a high-frequency infrared carbon-sulfur analyzer for the first time: weighing about 0.500 g of high-sulfur standard substance AR-673(0.0011 +/-0.0002) to 0.0001g, placing the high-sulfur standard substance into a bottoming crucible, and inputting the mass of the high-sulfur standard substance into a high-frequency infrared carbon-sulfur analyzer, wherein the blank item of the high-frequency infrared carbon-sulfur analyzer is 0.0000000. Adding 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent into a bottoming crucible, and analyzing to obtain a first measured value of a high-sulfur standard substance: 0.00123, 0.00134, 0.00118, 0.00133, 0.00145, with the average: 0.00131. according to the standard value of sulfur in the high-sulfur standard substance (S: 0.0011% + -0.0002%), the measured value of the high-sulfur standard substance is subjected to the first calibration as follows: 0.00104, 0.00113, 0.00099, 0.00112, 0.00122, with the average: 0.00110.
1.2.1, measuring first average blank value: 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. The nominal mass of the input high frequency infrared carbon and sulfur analyzer is 1.0000 grams, and the blank item of the high frequency infrared carbon and sulfur analyzer is 0.0000000. The analysis gave the first blank value. Five analyses were performed: 0.0000910, 0.0000895, 0.0000782, 0.0000933 and 0.0000759, and calculating the average value to be 0.0000856 to obtain the first average blank value
1.2.2, calibrating the high-frequency infrared carbon and sulfur analyzer for the second time: weighing high-sulfur standard substance AR-673 (S: 0.0011 + -0.0002) about 0.500 g to 0.0001g, placing into a bottoming crucible, inputting into a high-frequency infrared carbon-sulfur analyzer, and measuring the first average blank value
Inputting the data into a blank item of the high-frequency infrared carbon and sulfur analyzer, and automatically deducting the data by the high-frequency infrared carbon and sulfur analyzer. 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. And analyzing to obtain a second measured value of the high-sulfur standard substance: 0.00101, 0.00099, 0.00111, 0.00089, 0.00109, with an average value of 0.00102. According to the standard value of sulfur in the high-sulfur standard substance (S: 0.0011% + -0.0002%), the measured value of the high-sulfur standard substance is subjected to a second calibration as follows: 0.00109, 0.00107, 0.00120, 0.00096, 0.00118, with the average: 0.00110.
1.2.3, measuring the second average blank value: 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. The nominal mass of the input high frequency infrared carbon and sulfur analyzer is 1.0000 grams, and the blank item of the high frequency infrared carbon and sulfur analyzer is 0.0000000. And analyzing to obtain a second blank value. Five analyses were performed: 0.0000910, 0.0001005, 0.0001012, 0.0001103 and 0.0001290, calculating the average value to be 0.0001064 to obtain a second average blank value
1.2.4, calibrating the high-frequency infrared carbon-sulfur analyzer for the third time: weighing high-sulfur standard substance AR-673 (S: 0.0011 + -0.0002) about 0.500 g to 0.0001g, placing into a bottoming crucible, inputting into a high-frequency infrared carbon-sulfur analyzer, and measuring the second average blank value
Input into high-frequency infrared carbon-sulfur analyzerIn blank terms, it is automatically subtracted by the instrument. 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. Analysis, a third measurement of high sulfur standard was obtained: 0.00121, 0.00099, 0.00111, 0.00122, 0.00132, with an average value of 0.00117. According to the standard value of sulfur in the high-sulfur standard substance (S: 0.0011% + -0.0002%), the third calibration is carried out on the measured value of the high-sulfur standard substance, and comprises the following steps: 0.00114, 0.00093, 0.00104, 0.00115, 0.00124, with an average: 0.00110. the five calibration values fall within their allowable difference (0.00090-0.00130).
1.2.5, measuring third average blank value: 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. The nominal mass of the input high frequency infrared carbon and sulfur analyzer is 1.0000 grams, and the blank item of the high frequency infrared carbon and sulfur analyzer is 0.0000000. Analysis gave a third blank value. Five analyses were performed: 0.0001275, 0.0001151, 0.0001003, 0.0001053 and 0.0000880, calculating the average value and calculating the third average blank value
This blank value is the total sulfur content blank value.
1.2.6, measurement blank display value: 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. The nominal mass of the input high-frequency infrared carbon and sulfur analyzer is 1.0000 g, and the third average blank value
Inputting the data into a blank item of a high-frequency infrared carbon-sulfur analyzer. The analysis gave blank values. Five analyses were performed: 0.0000021, 0.0000042, 0.0000000, 0.0000031, 0.0000009, average: 0.00000206. obtaining blank display value
1.2.7, calculation of blank influence value:
the measurement range limited by the method is 0.00008% -0.0010%, and the blank influence value is less than one tenth of the lower limit of the measurement range, namely
0.00008％÷10＝0.000008％
For blank display values, calculate the average value as
The standard deviation is: 0.00000168.
blank impact value-mean +3 × standard deviation.
The blank influence value of this measurement is 0.00000206+3 × 0.00000168 0.00000709.
The blank influence value is less than or equal to 0.000008 percent, and subsequent measurement can be carried out.
1.3 test measurement of low-sulfur standard substance: weighing YSBC20117c-2009 (0.00044 +/-0.00009) with the mass m of 0.50g, accurately measuring the mass m to 0.001g, inputting the mass m of a sample into a high-frequency infrared carbon-sulfur analyzer, then placing the sample into a bottoming crucible, and then adding 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent; two measurements, measurement: 0.00046,0.00050. The two measurements fall within their tolerance (0.00035-0.00053).
1.4 measurement of Sulfur content in wrought superalloy specimens
Sampling and preparing samples: sampling and preparing the deformation superalloy to be detected provided by a customer according to the requirements of HB/Z205-.
Preparing a sample: weighing samples with the mass m of 0.5001g and 0.5010g from the prepared deformed superalloy sample to be detected, inputting the mass m of the sample into a high-frequency infrared carbon-sulfur analyzer, then placing the sample into a bottoming crucible, and then adding 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent.
Measuring the sulfur content in the deformed high-temperature alloy sample to be measured: and (3) putting the sample into a high-frequency infrared carbon-sulfur analyzer, and measuring the sulfur content twice according to the working conditions selected by the high-frequency infrared carbon-sulfur analyzer. The measured values were obtained: 0.00010, 0.00011, the average value of this measurement being: 0.00010 percent.
In the measuring process, in order to reduce and stabilize a blank value, an effective drying agent is replaced, carrier gas is effectively purified, the influence of water on the measurement is eliminated, a combustion furnace, a pipeline, a filter and the like are cleaned, the blank value of an instrument system is ensured to be stable, and meanwhile, a microwave oven is used for heating a bottoming crucible (without adding a sample when the blank is measured) already containing a sample and a fluxing agent, wherein the fluxing agent slightly discolors.
Example two
In this example, the content of ultra-low sulfur (0.00008% -0.0010%) in wrought superalloy GH4169 was measured using a high frequency infrared carbon-sulfur analyzer. In the measuring process, the lower limit of the sensitivity of the high-frequency infrared carbon-sulfur analyzer is +/-0.0000005%, and the working conditions of the analyzer are as follows: measuring the flow rate at 3.0 +/-0.2L/min, the pressure at 40 +/-2 psi, the power gas pressure at 40 +/-2 psi and the minimum analysis time at 40 s; the environmental conditions were: the indoor relative humidity is not more than 60%.
The materials used in the measurement were as follows:
high sulfur content standard: us AR-673(0.0011 ± 0.0002), sulfur content: 0.0011% + -0.0002%;
low sulfur standard: standard sample YSBC20117c-2009 (0.00044 +/-0.00009) has the sulfur content: 0.00044% ± 0.00009%;
a porcelain crucible: al2O3 material, phi 25mm is multiplied by 25 mm;
high-purity tungsten tin particle fluxing agent: s: less than or equal to 0.00002 percent;
high-purity iron fluxing agent: s is less than or equal to 0.00005 percent;
high purity oxygen: the content is more than 99.999 percent.
The specific measurement steps are as follows:
1.1 preparation of a bottoming crucible: adding 2.0 g of high-purity iron fluxing agent into the ceramic crucible, putting the ceramic crucible into a high-frequency infrared carbon-sulfur analyzer, burning and cooling to obtain the bottoming crucible.
1.2, calibrating a high-frequency infrared carbon and sulfur analyzer and measuring a total blank value of sulfur content, wherein the measuring steps are as follows:
calibrating a high-frequency infrared carbon-sulfur analyzer for the first time: high sulfur standard AR-673(0.0011 ± 0.0002), about 0.500 grams to 0.0001 grams, was weighed into a dummy crucible and the mass input into the instrument, which had a blank of 0.0000000. Adding 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent into a bottoming crucible, and analyzing to obtain a first measured value of a high-sulfur standard substance: 0.00132, 0.00124, 0.00128, 0.00130, 0.00150, with the average: 0.00133. according to the standard value of sulfur in the high-sulfur standard substance (S: 0.0011% + -0.0002%), the measured value of the high-sulfur standard substance is subjected to the first calibration as follows: 0.00109, 0.00103, 0.00106, 0.00108, 0.00124, with an average of: 0.00110.
1.2.1 measurement of first average blank value: 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. The nominal mass input to the high frequency infrared carbon sulfur analyzer was 1.0000 grams and the blank entry for the instrument was 0.0000000. The analysis gave the first blank value. Five analyses were performed: 0.0000890, 0.0000885, 0.0000762, 0.0000953 and 0.0000708, and calculating the average value to be 0.0000840 to obtain the first average blank value
1.2.2 calibrating the high-frequency infrared carbon-sulfur analyzer for the second time: weighing high-sulfur standard substance AR-673 (S: 0.0011 + -0.0002) about 0.500 g to 0.0001g, placing into a bottoming crucible, inputting into a high-frequency infrared carbon-sulfur analyzer, and measuring the first average blank value
Entered into the instrument blank entry, and automatically deducted by the instrument. 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. And analyzing to obtain a second measured value of the high-sulfur standard substance: 0.00101, 0.00086, 0.00107, 0.00098, 0.00100, with an average value of 0.00098. According to the standard value of sulfur in the high-sulfur standard substance (S: 0.0011% + -0.0002%), the measured value of the high-sulfur standard substance is subjected to a second calibration as follows: 0.00113, 0.00096, 0.00120, 0.00110, 0.00112 mean: 0.00110.
1.2.3 measurement of second average blank value: 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. The nominal mass input to the high frequency infrared carbon sulfur analyzer was 1.0000 grams and the blank entry for the instrument was 0.0000000. And analyzing to obtain a second blank value. Five analyses were performed: 0.0001010, 0.0000895, 0.0000992, 0.0001003 and 0.0001209, calculating the average value to be 0.0001022 to obtain a second average blank value
1.2.4 calibrating the high-frequency infrared carbon-sulfur analyzer for the third time: weighing high-sulfur standard substance AR-673 (S: 0.0011 + -0.0002) about 0.500 g to 0.0001g, placing into a bottoming crucible, inputting into a high-frequency infrared carbon-sulfur analyzer, and measuring the second average blank value
Inputting the data into a blank item of a high-frequency infrared carbon-sulfur analyzer, and automatically deducting the data by the analyzer. 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. Analysis, a third measurement of high sulfur standard was obtained: 0.00131, 0.00109, 0.00101, 0.00139, 0.00122, with an average of 0.00120. According to the standard value of sulfur in the high-sulfur standard substance (S: 0.0011% + -0.0002%), the third calibration is carried out on the measured value of the high-sulfur standard substance, and comprises the following steps: 0.00120, 0.00100, 0.00092, 0.00127, 0.00111, with the average: 0.00110. the five calibration values fall within their allowable difference (0.00090-0.00130).
1.2.5 measurement of third average blank value: 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. The nominal mass input to the high frequency infrared carbon sulfur analyzer was 1.0000 grams and the blank entry for the instrument was 0.0000000. Analysis gave a third blank value. Five analyses were performed: 0.0001105, 0.0000870, 0.0001093, 0.0000993 and 0.0001245, calculating the average value and calculating the third average blank value
This blank value is the total sulfur content blank value.
1.2.6 measurement blank display value: 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. The nominal mass of the input high-frequency infrared carbon and sulfur analyzer is 1.0000 g, and the third blank value
Entered into a blank entry of the instrument. The analysis gave blank values. Five analyses were performed: 0.0000021, 0.0000032, -0.0000001, -0.0000024, 0.0000010, average: 0.00000076. obtaining blank display value
1.2.7. Calculation of blank impact values
The measurement range limited by the method is 0.00008% -0.0010%, and the blank influence value is less than one tenth of the lower limit of the measurement range, namely
0.00008％÷10＝0.000008％
For blank display values, calculate the average value as
The standard deviation is: 0.00000215.
blank impact value-mean +3 × standard deviation.
The blank influence value of this measurement is 0.00000076+3 × 0.00000215 0.00000722.
The blank influence value is less than or equal to 0.000008 percent, and subsequent measurement can be carried out.
1.3 test measurement of low-sulfur standard substance: weighing YSBC20117c-2009 (0.00044 +/-0.00009) with the mass m of 0.50g, accurately measuring the mass m to 0.001g, inputting the mass m of a sample into a high-frequency infrared carbon-sulfur analyzer, then placing the sample into a bottoming crucible, and then adding 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent; two measurements, measurement: 0.00043,0.00039. The two measurements fall within their tolerance (0.00035-0.00053).
1.4 measurement of Sulfur content in wrought superalloy specimens
Sampling and preparing samples: sampling and preparing a to-be-detected deformation superalloy provided by a customer according to the requirements of HB/Z205-;
preparing a sample: weighing 0.5003g and 0.4995 g samples in mass m from the prepared deformed superalloy samples to be detected, inputting the mass m of the samples into a high-frequency infrared carbon-sulfur analyzer, then placing the samples into a bottoming crucible, and then adding 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent;
measuring the sulfur content in the deformed high-temperature alloy sample to be measured: and (3) putting the sample into a high-frequency infrared carbon-sulfur analyzer, and measuring the sulfur content twice according to the working conditions selected by the high-frequency infrared carbon-sulfur analyzer. The measured values were obtained: 0.00040, 0.00036, the mean value of this measurement being: 0.00038 percent.
In the measuring process, in order to reduce and stabilize a blank value, an effective drying agent is replaced, the carrier gas is effectively purified, the influence of water on the measurement is eliminated, a combustion furnace, a pipeline, a filter and the like are cleaned, the blank value of an instrument system is ensured to be stable, and in addition, a microwave oven is used for heating a bottoming crucible (without adding a sample when the blank value is measured) already containing a sample and a fluxing agent, and the limit is that the fluxing agent slightly changes color.
EXAMPLE III
In this example, the content of ultra-low sulfur (0.00008% -0.0010%) in wrought superalloy GH4169 was measured using a high frequency infrared carbon-sulfur analyzer. The lower limit of the sensitivity of the high-frequency infrared carbon and sulfur analyzer in the measurement process is +/-0.0000005%, and the working conditions of the analyzer are as follows: measuring the flow rate at 3.0 +/-0.2L/min, the pressure at 40 +/-2 psi, the power gas pressure at 40 +/-2 psi and the minimum analysis time at 40 s; the environmental conditions were: the indoor relative humidity is not more than 60%.
The materials used in the measurement were as follows:
high sulfur content standard: us AR-673(0.0011 ± 0.0002), sulfur content: 0.0011% + -0.0002%;
low sulfur standard: JSS 003-6(0.00013 ± 0.00003) in japan, sulfur content: 0.00013% ± 0.00003%;
a porcelain crucible: al2O3 material, phi 25mm is multiplied by 25 mm;
high-purity tungsten tin particle fluxing agent: s: less than or equal to 0.00002 percent;
high-purity iron fluxing agent: s is less than or equal to 0.00005 percent;
high purity oxygen: the content is more than 99.999 percent.
The specific measurement steps are as follows:
1.1 preparation of a bottoming crucible: adding 2.0 g of high-purity iron fluxing agent into the ceramic crucible, putting the ceramic crucible into a high-frequency infrared carbon-sulfur analyzer, burning and cooling to obtain the bottoming crucible.
1.2, calibrating a high-frequency infrared carbon and sulfur analyzer and measuring a total blank value of sulfur content, wherein the measuring steps are as follows:
calibrating a high-frequency infrared carbon-sulfur analyzer for the first time: high sulfur standard AR-673(0.0011 ± 0.0002), about 0.500 grams to 0.0001 grams, was weighed into a bottomed crucible and the mass was input into the instrument with a blank of 0.0000000. Adding 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent into a bottoming crucible, and analyzing to obtain a first measured value of a high-sulfur standard substance: 0.00122, 0.00124, 0.00148, 0.00110, 0.00158, with the average: 0.00132. according to the standard value of sulfur in the high-sulfur standard substance (S: 0.0011% + -0.0002%), the measured value of the high-sulfur standard substance is subjected to the first calibration as follows: 0.00101, 0.00103, 0.00123, 0.00091, 0.00131, with the average: 0.00110.
1.2.1 measurement of first average blank value: 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. The nominal mass input to the high frequency infrared carbon sulfur analyzer was 1.0000 grams and the blank entry for the instrument was 0.0000000. The analysis gave the first blank value. Five analyses were performed: 0.0000896, 0.0000925, 0.0000862, 0.0000853 and 0.0000908, and calculating the average value to be 0.0000889 to obtain the first average blank value
1.2.2 calibrating the high-frequency infrared carbon-sulfur analyzer for the second time: high sulfur content standard AR-673 (S: 0.0011. + -. 0.0002), about 0.500 g, to 0.0001g, was weighed into a bottomed crucible, the mass was transferred to the apparatus, the first average blank value was calculated
Entered into the instrument blank entry, and automatically deducted by the instrument. 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. And analyzing to obtain a second measured value of the high-sulfur standard substance: 0.00095, 0.00088, 0.00106, 0.00088, 0.00100, with an average value of 0.00095. According to the standard value of sulfur in the high-sulfur standard substance (S: 0.0011% + -0.0002%), the measured value of the high-sulfur standard substance is subjected to a second calibration as follows: 0.00110, 0.00101, 0.00122, 0.00101, 0.00115 have an average value: 0.00110.
1.2.3 measurement of second average blank value: 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. The nominal mass input to the high frequency infrared carbon sulfur analyzer was 1.0000 grams and the blank entry for the instrument was 0.0000000. And analyzing to obtain a second blank value. Five analyses were performed: 0.0001019, 0.0001225, 0.0000995, 0.0001063 and 0.0000972, calculating the average value to be 0.0001022 to obtain a second average blank value
1.2.4 calibrating the high-frequency infrared carbon-sulfur analyzer for the third time: high sulfur content standard AR-673 (S: 0.0011. + -. 0.0002), about 0.500 g, to 0.0001g, was weighed into a bottomed crucible, the mass was transferred to the instrument, the second average blank value was calculated
Entered into the instrument blank entry, and automatically deducted by the instrument. 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. Analyzing to obtain high-content sulfurThird measurement of standard substance: 0.00137, 0.00119, 0.00131, 0.00100, 0.00099, with an average of 0.00117. According to the standard value of sulfur in the high-sulfur standard substance (S: 0.0011% + -0.0002%), the third calibration is carried out on the measured value of the high-sulfur standard substance, and comprises the following steps: 0.00129, 0.00112, 0.00123, 0.00094 and 0.00093 have average values: 0.00110. the five calibration values fall within their allowable difference (0.00090-0.00130).
1.2.5 measurement of third average blank value: 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. The nominal mass input to the high frequency infrared carbon sulfur analyzer was 1.0000 grams and the blank entry for the instrument was 0.0000000. Analysis gave a third blank value. Five analyses were performed: 0.0001100, 0.0001010, 0.0000893, 0.0000983 and 0.0001205, calculating the average value and calculating the third average blank value
This blank value is the total sulfur content blank value.
1.2.6 measurement blank display value: 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent are added into the bottoming crucible. The nominal mass of the input high-frequency infrared carbon and sulfur analyzer is 1.0000 g, and the third average blank value
Entered into a blank entry of the instrument. The analysis gave blank values. Five analyses were performed: -0.0000011, 0.0000030, -0.0000011, -0.0000020, 0.0000015, average: 0.00000066. the blank display value X0 is 0.00000066.
1.2.7. Calculation of blank impact values
The measurement range limited by the method is 0.00008% -0.0010%, and the blank influence value is less than one tenth of the lower limit of the measurement range, namely
0.00008％÷10＝0.000008％
For blank display values, calculate the average value as
The standard deviation is: 0.00000211.
blank impact value-mean +3 × standard deviation.
The blank influence value of this measurement is 0.00000066+3 × 0.00000211 0.00000700.
The blank influence value is less than or equal to 0.000008 percent, and subsequent measurement can be carried out.
1.3 test measurement of low-sulfur standard substance: weighing JSS 003-6(0.00013 +/-0.00003) with the mass m of 0.50g and the precision of 0.001g, inputting the mass m of a sample into a high-frequency infrared carbon-sulfur analyzer, then placing the sample into a bottoming crucible, and then adding 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent; two measurements, measurement: 0.00013,0.00010. The two measurements fall within their tolerance (0.00010-0.00016).
1.4 measurement of Sulfur content in wrought superalloy specimens
Sampling and preparing samples: sampling and sample preparation are carried out on the deformation superalloy to be detected provided by a customer according to the requirements of HB/Z205-1991 sampling specification of samples for chemical analysis of steel and superalloy to obtain a deformation superalloy sample to be detected,
preparing a sample: weighing samples with mass m of 0.5009g and 0.4999g from the prepared deformed superalloy sample to be detected, inputting the mass m of the sample into a high-frequency infrared carbon-sulfur analyzer, then placing the sample into a bottoming crucible, and then adding 2.00 g of high-purity tungsten-tin particle fluxing agent and 0.500 g of high-purity iron fluxing agent.
Measuring the sulfur content in the deformed high-temperature alloy sample to be measured: and (3) putting the sample into a high-frequency infrared carbon-sulfur analyzer, and measuring the sulfur content twice according to the working conditions selected by the high-frequency infrared carbon-sulfur analyzer. The measured values were obtained: 0.00010, 0.00008, the average value of this measurement is: 0.00009%.
In the measuring process, in order to reduce and stabilize a blank value, an effective drying agent is replaced, the carrier gas is effectively purified, the influence of water on the measurement is eliminated, a combustion furnace, a pipeline, a filter and the like are cleaned, the blank value of an instrument system is ensured to be stable, and in addition, a microwave oven is used for heating a bottoming crucible (without adding a sample when the blank value is measured) already containing a sample and a fluxing agent, and the limit is that the fluxing agent slightly changes color.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. A method for measuring the ultra-low sulfur content in a wrought superalloy comprises the following steps:
1.1 preparing a bottoming crucible;
1.2, calibrating a high-frequency infrared carbon-sulfur analyzer and measuring a total blank value of sulfur content;
1.3. measuring a low-sulfur standard substance;
1.4 measuring the sulfur content in the deformed high-temperature alloy sample;
characterized in that, in step 1.2, after the first calibration measurement, the following steps are carried out:
1.2.1 measurement of the first average blank value:
adding 2 +/-0.5 g of high-purity tungsten tin particle fluxing agent and 0.5 +/-0.2 g of high-purity iron fluxing agent into the bottoming crucible, inputting the nominal mass of the high-purity tungsten tin particle fluxing agent and the high-purity iron fluxing agent into the high-frequency infrared carbon-sulfur analyzer, enabling blank items of the high-frequency infrared carbon-sulfur analyzer to be zero, putting the bottoming crucible into the high-frequency infrared carbon-sulfur analyzer, analyzing for at least 3 times to obtain blank values, calculating an average value, and obtaining a first average blank value
1.2.2. And (3) calibrating the high-frequency infrared carbon-sulfur analyzer for the second time:
weighing high-sulfur standard substances, putting the standard substances into the bottoming crucible, inputting the weighed mass into the high-frequency infrared carbon-sulfur analyzer, and leveling the mass for the first timeMean blank value
Inputting the measured values into a blank item of the high-frequency infrared carbon-sulfur analyzer, automatically deducting the measured values by the high-frequency infrared carbon-sulfur analyzer, adding 2 +/-0.5 g of high-purity tungsten tin particle fluxing agent and 0.5 +/-0.2 g of high-purity iron fluxing agent into the bottoming crucible, putting the bottoming crucible into the high-frequency infrared carbon-sulfur analyzer, analyzing to obtain a second measured value of the high-sulfur standard substance, and performing second calibration on the high-frequency infrared carbon-sulfur analyzer according to the standard value of sulfur in the high-sulfur standard substance;
1.2.3, measuring the second average blank value:
adding 2 +/-0.5 g of high-purity tungsten tin particle fluxing agent and 0.5 +/-0.2 g of high-purity iron fluxing agent into the bottoming crucible, inputting the nominal mass of the high-purity tungsten tin particle fluxing agent and the high-purity iron fluxing agent into the high-frequency infrared carbon-sulfur analyzer, enabling blank items of the high-frequency infrared carbon-sulfur analyzer to be zero, putting the bottoming crucible into the high-frequency infrared carbon-sulfur analyzer, analyzing for at least 3 times to obtain blank values, calculating an average value, and obtaining a second average blank value
1.2.4 calibrating the high-frequency infrared carbon-sulfur analyzer for the third time:
weighing high-sulfur standard substances, putting the standard substances into the bottoming crucible, inputting the weighed mass into the high-frequency infrared carbon-sulfur analyzer, and taking the second average blank value
Inputting the data into a blank item of the high-frequency infrared carbon-sulfur analyzer, automatically deducting the blank value by the high-frequency infrared carbon-sulfur analyzer, adding 2 +/-0.5 g of high-purity tungsten-tin particle fluxing agent and 0.5 +/-0.2 g of high-purity iron fluxing agent into the bottoming crucible, putting the bottoming crucible into the high-frequency infrared carbon-sulfur analyzer for analysis to obtain a third measured value of the high-sulfur standard substance, and obtaining a third measured value of the sulfur in the high-sulfur standard substance according to the content of sulfur in the high-sulfur standard substanceCalibrating the high-frequency infrared carbon and sulfur analyzer for the third time according to the standard value;
1.2.5 measurement of third average blank value:
adding 2 +/-0.5 g of high-purity tungsten-tin particle fluxing agent and 0.5 +/-0.2 g of high-purity iron fluxing agent into the bottoming crucible, inputting nominal mass into the high-frequency infrared carbon-sulfur analyzer, zeroing a blank item of the high-frequency infrared carbon-sulfur analyzer, analyzing for at least 3 times to obtain a blank value, calculating an average value, and obtaining a third average blank value
The blank value is the total blank value of the sulfur content;
1.2.6, measurement blank display value:
adding 2 +/-0.5 g of high-purity tungsten tin particle fluxing agent and 0.5 +/-0.2 g of high-purity iron fluxing agent into the bottoming crucible, inputting the nominal mass of the high-purity tungsten tin particle fluxing agent and the high-purity iron fluxing agent into the high-frequency infrared carbon-sulfur analyzer, and adding the third average blank value
Inputting blank items of the high-frequency infrared carbon and sulfur analyzer, and analyzing for at least 3 times to obtain at least 3 blank display values;
1.2.7 calculation of blank impact values:
the measurement range limited by the method is 0.00008% -0.0010%, and the blank influence value is less than one tenth of the lower limit of the measurement range, namely
0.00008％÷10＝0.000008％
Calculating an average value for at least 3 blank display values
And standard deviation, and calculating a blank impact value according to the following formula:
and when the blank influence value is less than or equal to 0.000008%, measuring the sample.
2. The method for measuring an ultra-low sulfur content in a wrought superalloy as in claim 1, wherein a heating process is performed on a bottomed crucible containing a flux or a sample before the bottomed crucible is placed in the high frequency infrared carbon-sulfur analyzer.
3. The method of measuring ultra low sulfur content in wrought superalloy according to claim 1, wherein in step 1.3, if the measured value of the sulfur content of the low sulfur standard does not fall within the allowable difference range of the low sulfur standard, steps 1.2-1.3 are repeated until the measured value of the sulfur content of the low sulfur standard falls within the allowable difference range thereof.
4. The method of measuring ultra low sulfur content in a wrought superalloy as in claim 1, wherein the analyzing is performed 5 times while measuring the first, second, and third average blank values.
5. The method for measuring ultra low sulfur content in wrought superalloy according to claim 2, wherein the heating process is performed using a microwave oven.
6. The method of measuring ultra low sulfur content in wrought superalloy according to claim 1, wherein in step 1.2.6, the blank value is measured 5 times.
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