CN113008826A - Method for determining dosage of fluxing agent for measuring sulfur element in sample by infrared absorption method - Google Patents
Method for determining dosage of fluxing agent for measuring sulfur element in sample by infrared absorption method Download PDFInfo
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 185
- 239000011593 sulfur Substances 0.000 title claims abstract description 185
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 14
- 230000004907 flux Effects 0.000 claims abstract description 99
- 238000005259 measurement Methods 0.000 claims abstract description 90
- 238000005303 weighing Methods 0.000 claims abstract description 8
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 8
- 230000035945 sensitivity Effects 0.000 claims description 6
- 238000012795 verification Methods 0.000 claims description 2
- 238000012935 Averaging Methods 0.000 claims 1
- 238000004458 analytical method Methods 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 13
- 229910010271 silicon carbide Inorganic materials 0.000 description 13
- 239000000835 fiber Substances 0.000 description 11
- 239000007769 metal material Substances 0.000 description 11
- 229910000601 superalloy Inorganic materials 0.000 description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910000976 Electrical steel Inorganic materials 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910000531 Co alloy Inorganic materials 0.000 description 4
- 229910001145 Ferrotungsten Inorganic materials 0.000 description 4
- AWXLLPFZAKTUCQ-UHFFFAOYSA-N [Sn].[W] Chemical compound [Sn].[W] AWXLLPFZAKTUCQ-UHFFFAOYSA-N 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- RMOBRDQVMQCHCG-UHFFFAOYSA-N [Sn].[W].[Fe] Chemical compound [Sn].[W].[Fe] RMOBRDQVMQCHCG-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000009614 chemical analysis method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 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 an element analysis technology, and particularly relates to a method for determining the dosage of a fluxing agent for measuring sulfur element in a sample by an infrared absorption method. When the amount of the flux is too much, the measurement result is higher than the actual value, and the measurement cost is also increased. If the amount of the flux is too small, the measurement result is lower than the actual value. Weighing fluxing agents according to a fixed interval set incremental mass, respectively covering the fluxing agents on each sample, calculating a sulfur growth rate under an n +1 th fluxing agent measurement point corresponding to a fluxing agent measurement point under each fluxing agent mass, and taking the fluxing agent mass corresponding to the maximum sulfur growth rate as a basic fluxing agent dosage; an increasing mass is added on the basis of the basic flux amount as a suitable flux amount. The appropriate flux dosage can be judged, the sulfur can be ensured to be completely released, the influence of blank in the flux can be reduced to the greatest extent, the measurement accuracy and precision are improved, and the measurement cost is reduced.
Description
Technical Field
The invention belongs to an element analysis technology, and particularly relates to a method for determining the dosage of a fluxing agent for measuring sulfur element in a sample by an infrared absorption method.
Background
The basic principle of measuring sulfur element by a high-frequency induction heating infrared absorption method is as follows:
melting combustion of sulfur-containing samples (solids) is assisted by fluxing agents in an oxygen-rich environment in a high-frequency furnace, wherein sulfur combines with oxygen to form sulfur dioxide
S+O2＝SO2
Gaseous sulfur dioxide leaves the sample, is released and enters the detection system. The whole analysis process is usually automatically operated by a carbon sulfur analyzer, and finally sulfur measurement values are output in percentage units.
The carbon-sulfur analyzer measures the sulfur content in a sample by an infrared absorption method, and a fluxing agent is needed in the analysis process. The flux functions in sulfur analysis as follows: assisting the melting combustion of the sample, lowering the melting point of the sample, providing partial heat, increasing the fluidity of the melt, ensuring complete oxidation of sulphur to SO2And the chemical components of the fluxing agent are metals such as metal tungsten, iron and tin, and non-metals such as vanadium pentoxide. The sulfur impurities in the flux are also released during the sulfur analysis process, forming a sulfur blank value, and of course, the lower the sulfur blank value, the better.
At present, no fluxing agent with zero sulfur blank value exists, and the sulfur blank value S is less than or equal to 0.0005 percent under the general condition. Some flux varieties may be marked with lower sulfur blank values. The price of the flux constitutes a measurement cost that is greater than that of the auxiliary materials such as a crucible and oxygen.
At present, in all measurement methods at home and abroad, the requirement on the adding amount of the fluxing agent is only vague regulation. For example, in section 6 of the superalloy chemical analysis method, sulfur content (HB 5220.6-2008) determined by high frequency induction combustion-infrared absorption method, 7.4.1 a spoon (about 1.2 g) of flux was added. In the high-frequency combustion infrared absorption method for measuring the sulfur content of nickel, nickel-iron and nickel alloy (GB/T21931.2-2008/ISO 7526:1985), the variety and the adding amount of 7.6 fluxing agents are determined by the characteristics of instruments and equipment and the types of samples, and 2g of copper, 2g to 3g of tungsten or 1g of copper and 1g of pure iron are typically added.
The influence of the blank value of sulfur in the fluxing agent has a multiplied bad effect, because the mass of the sample is generally weighed to be 0.500 g, the measurement result of the sample is calculated based on the mass of the sample, the total mass of the actually added fluxing agent fluctuates between 1.0 g and 3.0 g, namely, the blank value in the fluxing agent influences the measurement result by a value of 2 to 6 times. The blank value S of the sulfur in the common fluxing agent is approximately equal to 0.0005 percent, and then the 4-fold multiplication bad effect is equivalent to 0.0020 percent. I.e. the flux affects the measurement results at 0.0020%.
When the flux is used in too much amount, the multiplication bad effect of flux sulfur blank and the crucible sulfur blank are obviously increased, the measurement result is higher than the actual value, and the measurement cost is also increased. When the amount of the flux is too small, sulfur in the sample cannot be released, and the measurement result is lower than the actual value.
All chemical analysis and determination have various influencing factors, and the complete consistency of the measurement result cannot be achieved, namely the measurement result has certain uncertainty. The measurement is considered accurate as long as the measurement result is at an acceptable level. This acceptable level is the allowed difference, which is different for different measurement ranges.
Table 1 shows the allowable differences in sulfur contents (HB 5220.6-2008) measured by high-frequency induction combustion-infrared absorption method, section 6 of chemical analysis method for superalloys.
TABLE 1 allowable Difference
From table 1, it can be seen that the allowable difference is different for different sulfur content ranges, and the measurement result is considered to be accurate as long as the measurement result is within the allowable difference range.
In conclusion, although the sulfur analysis method at home and abroad makes vague regulations on the dosage of the fluxing agent, the problem of proper dosage of the fluxing agent does exist in the analysis process.
Therefore, in the analysis process, it is necessary to judge the proper amount of flux as accurately as possible to ensure complete release of sulfur, and even if the flux is slightly excessive, the measurement result is within the allowable difference range. The flux multiplication bad effect is reduced as much as possible, the best measurement effect is achieved, and meanwhile, the measurement cost is effectively controlled.
Disclosure of Invention
The invention provides a method for determining the dosage of a fluxing agent for measuring sulfur element in a sample by an infrared absorption method. The problems of flux multiplication bad effect, high measurement cost and the like in the prior art are solved.
In one aspect of the present invention, there is provided a flux amount determining method for measuring elemental sulfur in a sample by an infrared absorption method, the method comprising the steps of:
1.1, determining the quality of a measured sample, and taking a plurality of samples to be respectively placed in respective crucibles;
1.2 weighting fluxing agents according to the set gradually-increased mass at fixed intervals, and respectively covering the fluxing agents on each sample, wherein the weighting points correspond to the fluxing agent measuring points under the mass of each fluxing agent;
1.3 placing each crucible at a position to be measured;
1.4, respectively measuring by using a carbon-sulfur analyzer to obtain sulfur measurement values of all samples;
1.5 calculating the sulfur growth rate of the n +1 th fluxing agent at the measuring point according to the following formula(n+1)：
Rate of sulfur increase(n+1)＝(Cn+1-Cn)/Cn×100％
Wherein C isn+1Measured value of sulfur as measured value of n + 1-th fluxnA sulfur measurement value for the nth flux measurement point;
1.6 taking the flux mass corresponding to the maximum sulfur growth rate as the basic flux dosage;
1.7 adding an incremental mass to the basic flux amount is used as a suitable flux amount.
Advantageously or alternatively, the measurement samples and the flux are prepared in two or more groups, the measurement samples and the number of the samples and the weights of the flux and the flux in each group are completely the same, the sulfur measurement values of the samples in each group are respectively measured, the sulfur measurement values of the samples in each group at the same flux measurement point are taken to calculate the average value of the sulfur measurement values, and the sulfur growth rate at each flux measurement point is calculated based on the result(n+1)。
Advantageously or alternatively, the fixed spacing is set in dependence on material properties for samples of different materials.
Advantageously or optionally, for the measurement of a new material, the fluxing agent is weighed at a larger fixed interval, and the application range of the fluxing agent is rapidly determined; the fixed interval is then gradually reduced to accurately determine the appropriate flux dosage.
Advantageously or alternatively, the fixed spacing is 0.10 or 0.20 grams.
Advantageously or alternatively, the carbon sulfur analyzer uses an enhanced sensitivity mode to determine the sulfur content.
Advantageously or alternatively, if the finally obtained flux usage does not meet the relevant standard after actual verification, the flux usage is re-determined by reducing the fixed interval.
Advantageously or alternatively, a bottomed crucible is used.
Advantageously or alternatively, the crucible is capped at the crucible opening after the sample and flux are added to the crucible.
Has the advantages that: the method for determining the flux dosage for measuring the sulfur element in the sample by using the infrared absorption method can judge the proper flux dosage, can ensure the complete release of sulfur, can reduce the influence of blank in the flux to the maximum extent, improves the accuracy and precision of measurement, and reduces the measurement cost.
The features, functions, and advantages that have been discussed can be achieved independently in various examples or may be combined in yet other examples. Further details of the examples can be seen with reference to the following description and the accompanying drawings.
Drawings
The illustrative examples, as well as a preferred mode of use, further objectives, and descriptions thereof, will best be understood by reference to the following detailed description of an example of the present invention when read in conjunction with the accompanying drawings, wherein:
fig. 1 is a graph showing a change in flux mass and sulfur measurement value in the process of measurement on a sample of an example, where the abscissa is flux mass and the ordinate is sulfur measurement value.
Detailed Description
The disclosed examples will be described more fully with reference to the accompanying drawings, in which some (but not all) of the disclosed examples are shown. Indeed, many different examples may be described and should not be construed as limited to the examples set forth herein. Rather, these examples are described so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
Example 1
The experimental design scheme is as follows: a plurality of groups of samples with uniform quality are provided, theoretically, the sulfur content in each group of samples is the same, cosolvents with different qualities are added into each group of samples, a carbon sulfur analyzer is used for analyzing and obtaining sulfur measurement values in the process of measuring sulfur by an infrared absorption method, and the sulfur measurement values can be seen to increase along with the continuous increase of the quality of the cosolvent.
For example, a standard substance of nickel-base superalloy GBW 01641 was measured, and the standard value of sulfur was 0.0046% and the fixed mass was 0.500 g. With the increasing amount of the flux, the measured values of sulfur were obtained by analyzing with a carbon-sulfur analyzer, respectively, as shown in table 2.
TABLE 2 flux quality-Sulfur measurement-Sulfur growth Table for Nickel-base superalloys GBW 01641
FIG. 1 is a graph of flux mass versus sulfur measurement based on measurements, and it can be seen that the sulfur measurement increases slowly as the flux mass increases from 0.40 grams to 1.00 grams. This indicates that the flux is used in a small amount, sulfur in the sample is not released, and the measured sulfur value S is less than or equal to 0.0007%, which is far below the standard (S is 0.0046%).
The sulfur measurement increased rapidly from 0.0007% to 0.0045% as the flux mass increased from 1.00 to 1.10 grams. The sulfur measurement, 0.0045%, indicates that most of the sulfur in the nickel-base superalloy GBW 01641 has been released.
As flux mass continues to increase from 1.10 grams by 1.20 grams, sulfur measurements increase from 0.0045% to 0.0047%. Complete release of sulfur from the sample was ensured at this stage, and even though the flux-released sulfur increase and the crucible-leached sulfur increase were all taken into the sample sulfur measurement, the sulfur measurement was within the tolerance of table 1 (0.0005%).
For practical purposes, the filling flux mass-sulfur measurement-sulfur growth table is used instead of the plot.
TABLE 3 fluxing agent quality-Sulfur measurement-Sulfur growth Table
Defining: sulfur growth rate (%) at n +1 point:
sulfur growth rate (%) ═ Cn+1-Cn)/Cn×100％
At a mass of 1.10 grams of the multicomponent flux,
sulfur growth rate (%) (0.0045-0.0007)/0.0007 × 100%: 543%
The sulfur growth rate calculation method is the same for each point. The calculation results are shown in Table 2.
The maximum point of sulfur growth rate (1.10 g) is the maximum release of sulfur in the sample; the first point (1.20 g) after the maximum point, i.e. 0.10 g of flux was added, ensuring a sufficient release of sulphur. The corresponding mass of flux is the appropriate amount, indicating that sulfur is sufficiently released from the sample.
For increasing flux mass, the sulfur content rapidly increases at the position of the maximum value of the sulfur growth rate obtained by measurement and calculation, and most of the sulfur in the sample is released. The first measurement point after this maximum, i.e. the measurement point at which 0.10 g of flux is added, ensures that the sulfur in the sample is completely released. At the same time, the addition of 0.10 grams of flux, with the sulfur released by the flux and the increase in crucible leached sulfur, all taken into account in the sample sulfur content, also sulfur measurements were within the tolerance range. I.e. the flux mass (1.20 g) corresponding to the first measurement point after the position of the maximum value of the sulfur growth rate, is the appropriate amount.
After which the flux mass increased from 1.20 grams to 1.90 grams and the sulfur measurement increased slowly. The sulfur release in the sample was fixed, except that the flux released sulfur increased and the crucible leached sulfur increased.
It is known that a certain amount of a sample is fluxed under the flux of a certain mass of flux in a high-frequency induction furnace, the sample is burned and the sulfur therein is completely released. The adding amount of the fluxing agent is 1-3 g.
The invention selects the mass increment interval of 0.10 g of the cosolvent appropriately, has proper workload and is also enough to judge the release condition of the sulfur. Thus, when the flux mass is less than 0.10 grams, still at 0.10 gram intervals, the flux mass and corresponding sulfur measurements are taken into the flux mass-sulfur measurement-sulfur growth table, with the flux mass corresponding to the first sulfur growth rate after the maximum sulfur growth rate being the appropriate amount.
To reduce the effort, the flux mass spacing can be relaxed to 0.20 grams. Even though the increase in flux-released sulfur and the increase in crucible-leached sulfur were all taken into account for the sample sulfur content, the sulfur measurements were within the allowable difference. The flux mass corresponding to the first point after the maximum sulfur growth rate is then the appropriate amount.
For some unknown new materials, the flux with the mass increasing more than 0.10 g can be selected for preliminary screening, and the range of proper dosage is locked. The appropriate amount of flux was then determined in the same procedure in increments of 0.10 grams.
The same increasing flux is weighed in parallel, and the sulfur content is measured by using a carbon sulfur analyzer respectively, and the flux mass-sulfur measurement value-sulfur growth rate table is counted. The significance of the determination method is that the workload of weighing and measuring is obviously increased, but the sulfur measurement value is averaged, and the influence of accidental factors on the sulfur content measurement is eliminated.
For a certain mass of a sample made of a particularly refractory material such as ceramic, more fluxing agent is needed, and the mass fixed value of the sample can be selected to be smaller than the conventional value (0.10-1.00 g) so as to avoid the situation that the quantity of the fluxing agent is too large and the crucible cannot accommodate the fluxing agent.
For samples with low density, such as titanium alloy and aluminum alloy, the sample combustion process is easy to cause splashing and damage the quartz tube in the combustion area of the carbon-sulfur analyzer, so that after the sample and the fluxing agent are added into the crucible, a crucible cover is covered on the opening of the crucible to protect the quartz tube.
Preparing a bottoming crucible: and 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. As is well known, the blank of the bottoming crucible is obviously reduced, and the measurement of ultralow sulfur is facilitated.
The common measurement modes of the carbon sulfur analyzer are: the carrier gas flow rate was 3.0 liters/min, and one analysis run took approximately 1.5 minutes. The partial carbon sulfur analyzer aims at the measurement of ultra-low sulfur in a sample and has a measurement mode of enhanced sensitivity: the carrier gas flow rate is less than 1.0 liter/min. The sensitivity mode measurement is enhanced, the sensitivity is increased, and the method is suitable for ultra-low sulfur measurement, but the time consumption is increased by more than three times.
Example 2
And (4) measuring the single crystal superalloy DD6 and quantitatively judging the proper dosage of the tungsten-tin-iron fluxing agent.
(1) The mass of the single crystal superalloy DD6 is fixedly weighed, 0.350 g is placed in a bottoming crucible;
(2) weighing the mass of the ferrotungsten-tin flux shown in the table 4, and adding the weighed mass into 0.350 g of single crystal superalloy DD 6;
(3) the sulfur measurement was measured by the carbon sulfur analyzer using the enhanced sensitivity mode, and is listed in table 4;
(4) calculating the growth rate of sulfur at each point at intervals of 0.10 g of the mass of the fluxing agent, and listing the growth rates in table 4;
TABLE 4 melting flux quality-sulfur measurement-sulfur growth rate table for single crystal superalloy DD6
In table 4, the point of maximum rate of sulfur increase (0.90 g) is the maximum release of sulfur in the sample, and the first point after the maximum point, i.e., 1.00 g after 0.10 g of flux is added, ensures complete release of sulfur in the sample. Meanwhile, 0.10 g of fluxing agent is added, and even if the sulfur content of the test sample is totally counted by the increase of the sulfur released by the fluxing agent and the increase of the sulfur leached from the crucible, the allowable difference of the sulfur measurement result of the table lookup 1 is 0.0003%, and the sulfur measurement result is also in the allowable difference range. The mass of the fluxing agent corresponding to the first point after the maximum point is 1.00 g.
Namely, the sulfur test sample of the single crystal superalloy DD6 is selected to be 0.350 g, and the proper dosage of the tungsten tin iron fluxing agent is 1.00 g.
Example 3
And measuring the appropriate dosage of silicon steel and tungsten-tin fluxing agent and carrying out quantitative judgment.
(1) The mass of the silicon steel is fixedly weighed and is 0.250 g;
(2) weighing the mass of the tungsten-tin fluxing agent shown in the table 5, and adding the tungsten-tin fluxing agent into 0.250 g of silicon steel;
(3) sulfur measurements were taken using a carbon sulfur analyzer and are listed in table 5;
(4) calculating the growth rate of sulfur at each point at intervals of 0.10 g of the mass of the fluxing agent, and listing the growth rates in table 5;
TABLE 5 silicon steel flux quality-Sulfur measurement-Sulfur growth Rate Table
In table 5, the point of maximum rate of sulfur increase (1.20 g) is the maximum release of sulfur in the sample, and the first point after the maximum point, i.e., 1.30 g after 0.10 g of flux is added, ensures complete release of sulfur in the sample. Meanwhile, 0.10 g of fluxing agent is added, even if the sulfur content of the test sample is totally counted by the increase of the sulfur released by the fluxing agent and the increase of the sulfur leached from the crucible, the allowable difference of the sulfur measurement result in the table lookup 1 is 0.0005%, and the sulfur measurement result is in the allowable difference range. The mass of the fluxing agent corresponding to the first point after the maximum point is 1.30 g.
Namely, the sulfur test sample of the silicon steel is selected to be 0.250 g, and the proper dosage of the tungsten-tin fluxing agent is 1.30 g.
Example 4
And measuring the appropriate dosage of the cobalt-based alloy and the ferrotungsten fluxing agent, and carrying out quantitative judgment.
(1) The mass of the cobalt-based alloy is fixedly weighed to be 1.000 g;
(2) weighing the ferrotungsten fluxing agent in the mass shown in the table 6, and adding the ferrotungsten fluxing agent into 1.000 g of cobalt-based alloy;
(3) sulfur measurements using a carbon sulfur analyzer are shown in table 6;
(4) calculating the growth rate of sulfur at each point at intervals of 0.20 g of the mass of the fluxing agent, and listing the growth rates in table 6;
TABLE 6 table of Co-based alloy flux quality-Sulfur measurement-Sulfur growth Table
In table 6, the point of maximum rate of sulfur increase (3.60 g) is the maximum release of sulfur in the sample, and the first point after the maximum point, i.e., 3.80 g after 0.20 g of flux is added, ensures complete release of sulfur in the sample. Meanwhile, 0.20 g of fluxing agent is added, even if the sulfur content of the test sample is totally counted by the increase of the sulfur released by the fluxing agent and the increase of the sulfur leached from the crucible, the allowable difference of the sulfur measurement result in the table lookup 1 is 0.001%, and the sulfur measurement result is in the allowable difference range. The mass of the flux corresponding to the first point after the maximum point is 3.80 g.
Namely, the cobalt-based alloy sulfur test sample is selected to be 1.000 g, and the appropriate dosage of the ferrotungsten fluxing agent is 3.80 g.
Example 5
Silicon carbide continuous fiber reinforced metal materials have been successfully used in aerospace planning. The sulfur element is also a control element and needs to be measured by a carbon-sulfur analyzer. Because the silicon carbide is a non-metal material, the silicon carbide continuously reinforced metal material belongs to a low electromagnetic induction material, and is difficult to generate larger eddy current, SO2Release was difficult and therefore a fixed mass of 0.050 grams was chosen, less than the conventional mass (0.10 grams to 1.0 grams). Tungsten is properly supplemented in the common tungsten tin iron fluxing agent to form the special fluxing agent for measuring the silicon carbide continuous fiber reinforced metal material. Meanwhile, the silicon carbide continuous fiber reinforced metal material is a novel material, and the analysis is not carried out before, and how much fluxing agent is needed is not known. Thus, a flux mass interval of 0.50 grams was first selected.
The sulfur content of the silicon carbide continuous fiber reinforced metal material is measured by using a special fluxing agent, and the proper dosage of the special fluxing agent is quantitatively judged.
(1) The mass of the silicon carbide continuous fiber reinforced metal material is fixed and weighed, and is 0.050 g;
(2) weighing the mass of the special fluxing agent shown in the table 8, and adding the special fluxing agent into 0.050 g of silicon carbide continuous fiber reinforced metal material;
(3) sulfur measurements using a carbon sulfur analyzer are shown in table 8;
(4) calculating the growth rate of sulfur at each point at intervals of 0.50 g of the mass of the fluxing agent, and listing the growth rates in Table 8;
TABLE 7 quality of silicon carbide continuous fiber reinforced metal flux-sulfur measurement-sulfur growth rate table
In table 7, the maximum sulfur growth rate point is 2.50 g, and fluxes with increasing mass are added to the samples at intervals of 0.10 g in the range of intervals (2.00 to 3.00 g) before and after the maximum sulfur growth rate point, respectively, and the sulfur content is measured using a carbon-sulfur analyzer.
(1) The mass of the silicon carbide continuous fiber reinforced metal material is fixed and weighed, and is 0.050 g;
(2) weighing the mass of the special fluxing agent shown in the table 9, and adding the special fluxing agent into 0.050 g of silicon carbide continuous fiber reinforced metal material;
(3) sulfur measurements using a carbon sulfur analyzer are shown in table 9;
(4) calculating the growth rate of sulfur at each point at intervals of 0.10 g of the mass of the fluxing agent, and listing the growth rates in Table 8;
TABLE 8 quality of silicon carbide continuous fiber reinforced metal flux-sulfur measurement-sulfur growth rate table
In table 8, the point of maximum rate of sulfur increase (2.30 g) is the maximum release of sulfur in the sample, and the first point after the maximum point, i.e., 2.40 g after 0.10 g of flux is added, ensures complete release of sulfur in the sample. Meanwhile, 0.10 g of fluxing agent is added, even if the sulfur content of the test sample is totally counted by the increase of the sulfur released by the fluxing agent and the increase of the sulfur leached from the crucible, the allowable difference of the sulfur measurement result in the table lookup 1 is 0.002%, and the sulfur measurement result is also in the allowable difference range. The mass of the fluxing agent corresponding to the first point after the maximum point is 2.40 g.
Namely, the sample for measuring sulfur of the silicon carbide continuous fiber reinforced metal material is 0.050 g, and the proper dosage of the special fluxing agent is 2.40 g.
The description of the different advantageous arrangements has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the examples in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. Additionally, the different advantageous examples may describe different advantages as compared to other advantageous examples. The example or examples selected are chosen and described in order to best explain the principles of the examples, the practical application, and to enable others of ordinary skill in the art to understand the disclosure for various examples with various modifications as are suited to the particular use contemplated.
Claims (9)
1. A method for determining the dosage of a fluxing agent for measuring sulfur element in a sample by an infrared absorption method is characterized by comprising the following steps:
1.1, determining the quality of a measured sample, and taking a plurality of samples to be respectively placed in respective crucibles;
1.2 weighting fluxing agents according to the set gradually-increased mass at fixed intervals, and respectively covering the fluxing agents on each sample, wherein the weighting points correspond to the fluxing agent measuring points under the mass of each fluxing agent;
1.3 placing each crucible at a position to be measured;
1.4, respectively measuring by using a carbon-sulfur analyzer to obtain sulfur measurement values of all samples;
1.5 calculating the sulfur growth rate of the n +1 th fluxing agent at the measuring point according to the following formula(n+1)：
Rate of sulfur increase(n+1)＝(Cn+1-Cn)/Cn×100％
Wherein C isn+1Measured value of sulfur as measured value of n + 1-th fluxnA sulfur measurement value for the nth flux measurement point;
1.6 taking the flux mass corresponding to the maximum sulfur growth rate as the basic flux dosage;
1.7 adding an incremental mass to the basic flux amount is used as a suitable flux amount.
2. A flux amount determining method according to claim 1, characterized in that: preparing measurement samples and fluxing agents in two or more groups, wherein the measurement samples and the number of the samples and the weights of the fluxing agents and the fluxing agents in each group are completely the same, and respectively measuring the test samples and the fluxing agents in each groupMeasuring sulfur values of the samples, averaging the sulfur values measured at the same flux measurement point for each group of samples, and calculating the sulfur growth rate at each flux measurement point based on the average sulfur value(n+1)。
3. A flux amount determining method according to claim 1, characterized in that: for samples of different materials, the fixed spacing is set according to the material properties.
4. A flux amount determining method according to claim 1, characterized in that: for the measurement of a new material, firstly, weighing the fluxing agent at a larger fixed interval, and quickly determining the application range of the fluxing agent; the fixed interval is then gradually reduced to accurately determine the appropriate flux dosage.
5. A flux amount determining method according to claim 1, characterized in that: the fixed spacing is 0.10 or 0.20 grams.
6. A flux amount determining method according to claim 1, characterized in that: the carbon sulfur analyzer uses an enhanced sensitivity mode to determine sulfur content.
7. A flux amount determining method according to claim 1, characterized in that: and if the finally obtained flux dosage does not meet the relevant standard after actual verification, reducing the fixed interval and re-determining the flux dosage.
8. A flux amount determining method according to claim 1, characterized in that: a bottomed crucible was used.
9. A flux amount determining method according to claim 1, characterized in that: after the sample and the flux are added into the crucible, a crucible cover is covered on the opening of the crucible.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013057120A (en) * | 2011-08-12 | 2013-03-28 | Jfe Steel Corp | Method for desulfurizing molten steel and method for manufacturing molten steel |
| CN106932355A (en) * | 2015-12-31 | 2017-07-07 | 中核北方核燃料元件有限公司 | Carbon element content analysis method in WABA pellets |
| CN111122493A (en) * | 2020-01-06 | 2020-05-08 | 包头钢铁（集团）有限责任公司 | Method for measuring carbon and sulfur in dust mud by infrared absorption method-renewable resource different-standard correction |
-
2021
- 2021-04-02 CN CN202110360665.3A patent/CN113008826B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013057120A (en) * | 2011-08-12 | 2013-03-28 | Jfe Steel Corp | Method for desulfurizing molten steel and method for manufacturing molten steel |
| CN106932355A (en) * | 2015-12-31 | 2017-07-07 | 中核北方核燃料元件有限公司 | Carbon element content analysis method in WABA pellets |
| CN111122493A (en) * | 2020-01-06 | 2020-05-08 | 包头钢铁（集团）有限责任公司 | Method for measuring carbon and sulfur in dust mud by infrared absorption method-renewable resource different-standard correction |
Non-Patent Citations (7)
| Title |
|---|
| 晏高华 等: "高频燃烧-红外吸收法测定增碳剂中的硫", 《兵器材料科学与工程》, vol. 32, no. 05, 30 September 2009 (2009-09-30), pages 91 - 92 * |
| 柳轶男 等: "CS-800红外碳硫分析仪测定合金钢中的碳和硫", 《光谱实验室》, vol. 28, no. 04, 31 July 2011 (2011-07-31), pages 1958 - 1962 * |
| 武映梅 等: "高频燃烧炉红外吸收法测定铁矿石中的硫含量", 《南方金属》, no. 03, 30 June 2011 (2011-06-30), pages 21 - 24 * |
| 纪新华 等: "测定钽中碳的红外吸收方法研究", 《原子能科学技术》, vol. 38, 31 July 2004 (2004-07-31), pages 179 - 181 * |
| 纪新华 等: "铀铌合金中微量硫的测定", 《中国核科技报告》, 31 December 2002 (2002-12-31), pages 42 - 50 * |
| 纪新华 等: "高频加热红外吸收法测定铍中碳量", 《稀有金属与硬质合金》, vol. 40, no. 03, 30 June 2012 (2012-06-30), pages 63 - 66 * |
| 蒙益林 等: "高频感应燃烧红外线吸收法测定镍钛铌记忆合金中碳含量", 《化学分析计量》, vol. 25, no. 05, 30 September 2016 (2016-09-30), pages 45 - 48 * |
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