CN113008826B - Method for determining flux amount of sulfur element in infrared absorption measurement sample - Google Patents
Method for determining flux amount of sulfur element in infrared absorption measurement sample 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 166
- 230000004907 flux Effects 0.000 title claims abstract description 124
- 238000005259 measurement Methods 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 64
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 230000035945 sensitivity Effects 0.000 claims description 6
- 239000006184 cosolvent Substances 0.000 claims description 2
- 238000012795 verification Methods 0.000 claims description 2
- 238000000921 elemental analysis Methods 0.000 abstract description 2
- 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
- 229910000601 superalloy Inorganic materials 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 239000007769 metal material Substances 0.000 description 10
- 229910000976 Electrical steel Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910000531 Co alloy Inorganic materials 0.000 description 5
- AWXLLPFZAKTUCQ-UHFFFAOYSA-N [Sn].[W] Chemical compound [Sn].[W] AWXLLPFZAKTUCQ-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- RMOBRDQVMQCHCG-UHFFFAOYSA-N [Sn].[W].[Fe] Chemical compound [Sn].[W].[Fe] RMOBRDQVMQCHCG-UHFFFAOYSA-N 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229910001145 Ferrotungsten Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 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
- 239000012159 carrier gas Substances 0.000 description 2
- 238000009614 chemical analysis method Methods 0.000 description 2
- 238000002485 combustion reaction 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
- -1 etc. Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 238000012360 testing method Methods 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005674 electromagnetic induction Effects 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
- 238000002386 leaching Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal 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
- 238000002360 preparation method 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
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
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- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention belongs to the elemental analysis technology, and particularly relates to a method for determining the flux amount of sulfur element in a measurement sample by an infrared absorption method. Too much flux is used, the measurement results are higher than the actual values, and the measurement cost is increased. Too little flux is used and the measurement result is lower than the actual value. The invention sets up the increasing mass to weigh the flux according to the fixed interval, and cover on each sample separately, corresponding to flux measuring point under each flux mass, calculate and get the sulfur growth rate under the n+1th flux measuring point, regard flux mass corresponding to maximum sulfur growth rate as the basic flux consumption; an incremental mass is added as a suitable flux amount based on the basic flux amount. The proper flux dosage can be judged, so that the complete release of sulfur can be ensured, the influence of blank in the flux can be reduced to the greatest extent, the measuring accuracy and precision are improved, and the measuring cost is reduced.
Description
Technical Field
The invention belongs to the elemental 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
Basic principle of measuring sulfur element by high-frequency induction heating infrared absorption method:
the sulfur-containing sample (solid) is melted and burned under the oxygen-enriched environment in a high-frequency furnace by the aid of fluxing agent, wherein sulfur and oxygen are combined to generate sulfur dioxide
S+O 2 ＝SO 2
The gaseous sulfur dioxide leaves the sample and is released to enter the detection system. The whole analysis process is usually automated by a carbon sulfur analyzer, and finally sulfur measurement values are output in percentage units.
The carbon-sulfur analyzer measures sulfur content in a sample by an infrared absorption method, and a fluxing agent is needed in the analysis process. The role of the fluxing agent in sulfur analysis is: assisting in melting combustion of the sample, lowering the melting point of the sample, providing partial heat, improving melt fluidity, ensuring complete oxidation of sulfur to SO 2 Released, etc., and the chemical components of the flux are usually metals such as tungsten, iron, tin, etc., and non-metals such as vanadium pentoxide, etc. The sulfur element impurities in the flux are also released during sulfur analysis to form a sulfur blank value, and of course, the lower the sulfur blank value, the better.
At present, no fluxing agent with a sulfur blank value of zero exists, and the sulfur blank value S is generally less than or equal to 0.0005%. Some flux species may be marked with a lower sulfur blank value. Compared with auxiliary materials such as a crucible, oxygen and the like, the price of the fluxing agent constitutes a larger cost for measurement.
At present, in all domestic and foreign measuring methods, the requirement on the addition amount of the fluxing agent is only an ambiguous rule. For example, part 6 of the high frequency induction combustion-infrared absorption method for determination of sulfur content (HB 5220.6-2008) of superalloy chemical analysis method 7.4.1 was added with a scoop (about 1.2 g) of flux. 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), 7.6 fluxing agent varieties and adding amounts are determined by the characteristics of instrument and equipment and the types of samples, and the adding amount is represented by adding 2g of copper, or 2-3 g of tungsten, or 1g of copper and 1g of pure iron.
The influence of the blank value of sulfur in the fluxing agent has a multiplication bad effect, because the mass of a sample is generally 0.500 g, the measurement result of the sample is calculated based on the mass of the sample, and 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 which is 2 to 6 times. The common flux sulfur blank value S is approximately equal to 0.0005%, and then the multiplication bad effect of 4 times is equal to 0.0020%. I.e. the flux affects the measurement result by 0.0020%.
The flux is used in too much amount, the multiplication bad effect of the flux sulfur blank and the sulfur blank of the crucible are obviously increased, the measurement result is higher than the actual value, and the measurement cost is increased. The amount of 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 a plurality of influencing factors, and the measurement results cannot be completely consistent, namely, certain uncertainty exists in the measurement results. The measurement is considered accurate as long as the measurement results are at an acceptable level. This acceptable level is the allowable difference, which is different for different measurement ranges.
The allowable differences of the sulfur content (HB 5220.6-2008) measured by the high-frequency induction combustion-infrared absorption method in section 6 of the chemical analysis method of superalloy are shown in Table 1.
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 a word, although the sulfur analysis methods at home and abroad at present have the ambiguous rule of flux consumption, the problem of proper flux consumption does exist in the analysis process.
Therefore, in the analysis process, it is necessary to judge the proper amount of the flux as accurately as possible to ensure complete release of sulfur, and the measurement result is within the allowable range even if the flux is slightly excessive. The multiplication bad effect of the fluxing agent is reduced as much as possible, the best measurement effect is achieved, and the measurement cost is effectively controlled.
Disclosure of Invention
The invention provides a method for determining the flux amount of sulfur element in a measurement sample by an infrared absorption method. The problems of the prior art that the flux is bad in multiplication effect, the measurement cost is high and the like are solved.
In one aspect, the present invention provides a method for determining the amount of flux for measuring elemental sulfur in a sample by infrared absorption, the method comprising the steps of:
1.1, determining the mass of a measured sample, and taking a plurality of samples to be respectively placed in respective crucibles;
1.2, setting incremental mass weighing fluxing agents according to fixed intervals, and respectively covering the fluxing agents on each sample, wherein the incremental mass weighing fluxing agents correspond to 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 and obtaining sulfur measurement values of all the samples by using a carbon-sulfur analyzer;
1.5 calculating the sulfur growth rate at the n+1th flux measurement point according to the following formula (n+1) ：
Sulfur growth rate (n+1) ＝(C n+1 -C n )/C n ×100％
Wherein C is n+1 Sulfur measurement at the n+1th flux measurement point, C n Sulfur measurements that are the nth flux measurement point;
1.6, taking the mass of the fluxing agent corresponding to the maximum sulfur increase rate as the basic fluxing agent dosage;
1.7 adding an incremental mass to the basic flux as the appropriate flux.
Advantageously or alternatively, the measurement samples and the flux are prepared in two or more groups, the measurement samples, the number of samples, and the weights of the flux and the flux in each group are identical, sulfur measurement values of the respective groups of samples are measured separately, sulfur measurement values of the respective groups of samples at the same flux measurement points are taken to calculate an average value of the sulfur measurement values, and the sulfur increase rate at the respective flux measurement points is calculated based on the result (n+1) 。
Advantageously or alternatively, the fixed interval is set according to the material properties for samples of different materials.
Advantageously or alternatively, for the measurement of new materials, firstly, the flux is weighed at a relatively large fixed interval, and the application range of the flux is rapidly determined; and then gradually reducing the fixed interval, and precisely determining the proper flux amount.
Advantageously or alternatively, the fixed interval is 0.10 or 0.20 grams.
Advantageously or alternatively, the carbon sulfur analyzer uses an enhanced sensitivity mode to determine sulfur content.
Advantageously or alternatively, if the resulting flux level does not meet the relevant criteria after actual verification, the fixed interval is narrowed to redefine the flux level.
Advantageously or alternatively, a backing crucible is used.
Advantageously or alternatively, after the crucible has been filled with the sample and flux, the crucible is capped at the crucible mouth.
The beneficial effects are that: the method for determining the flux amount of the sulfur element in the measurement sample by using the infrared absorption method can judge the proper flux amount, can ensure complete release of sulfur, can reduce the influence of blank in the flux to the greatest 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 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 invention when read in conjunction with the accompanying drawings, wherein:
FIG. 1 is a graph of flux mass versus sulfur measurement during a measurement for a sample of an embodiment, where the abscissa is flux mass and the ordinate is sulfur measurement.
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 test design scheme is as follows: in the process of measuring sulfur by an infrared absorption method, a carbon-sulfur analyzer is used for respectively analyzing and obtaining sulfur measurement values, and the sulfur measurement values are continuously increased along with the continuous increment of the mass of a fluxing agent.
For example, the standard substance nickel-base superalloy GBW 01641, standard value of sulfur is s=0.0046% and fixed mass is 0.500 g. As the amount of the multi-component fluxing agent increased, sulfur measurements were obtained by analysis using a carbon sulfur analyzer, respectively, as shown in table 2.
TABLE 2 flux mass-sulfur measurement-sulfur growth rate Table for nickel-base superalloy GBW 01641
FIG. 1 is a graph of flux mass versus sulfur measurement made based on the measurement results, and it can be seen that the sulfur measurement slowly increases as the flux mass increases from 0.40 grams to 1.00 grams. This indicates that the amount of flux is small, the sulfur in the sample is not substantially released, and the sulfur measurement S is less than or equal to 0.0007% and much lower than the standard (s=0.0046%).
As the flux mass increased from 1.00 grams to 1.10 grams, the sulfur measurement increased rapidly from 0.0007% to 0.0045%. Sulfur measurement 0.0045% indicates that most of the sulfur in the nickel-base superalloy GBW 01641 has been released.
As the flux mass continues to increase from 1.10 grams to 1.20 grams, the sulfur measurement increases from 0.0045% to 0.0047%. This stage ensures complete release of sulfur from the sample, and even if the flux release sulfur increase and crucible leaching sulfur increase are all accounted for in the sample sulfur measurement, the sulfur measurement is within the allowable range of Table 1 (0.0005%).
To facilitate practical work, the map is replaced with a fill flux mass-sulfur measurement-sulfur growth rate table.
TABLE 3 flux mass-sulfur measurement-sulfur growth rate Table
Definition: sulfur increase rate (%) at n+1 point was calculated as:
sulfur increase rate (%) = (C n+1 -C n )/C n ×100％
At a mass of 1.10 grams of the multi-component fluxing agent,
sulfur increase rate (%) = (0.0045-0.0007)/0.0007×100% = 543%
The sulfur growth rate of other points is calculated by the same method. The calculation results are shown in Table 2.
The maximum point of sulfur increase (1.10 g) is the maximum release of sulfur from the sample; the first point (1.20 g) after the maximum point, 0.10 g of flux was added to ensure a sufficient release of sulfur. The corresponding flux mass is a proper amount, which indicates that sulfur in the sample is fully released.
For increasing flux mass, the sulfur content increases rapidly by measuring and calculating the position of the maximum sulfur growth rate, and a substantial portion of the sulfur in the sample is released. The first measurement point after this maximum position, i.e. the measurement point at which 0.10 g of flux is added, ensures a complete release of sulfur from the sample. At the same time, 0.10 g of flux was added, wherein the sulfur released by the flux and the increase in sulfur leached from the crucible were all accounted for by the sample sulfur content, and the sulfur measurement was also within the allowable range. I.e. the mass of the fluxing agent corresponding to the first measurement point after the position of the maximum value of the sulfur increase rate (1.20 g) is a suitable amount.
After which the flux mass was increased from 1.20 g to 1.90 g and the sulfur measurement was slowly increased. 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 sample burns in a high frequency induction furnace under fluxing by a certain mass of flux, and sulfur therein is completely released. The addition amount of the fluxing agent is 1-3 g.
The invention selects the cosolvent mass increment interval of 0.10 g to be proper, has proper workload and is also sufficient for judging the sulfur release condition. Therefore, when the incremental mass of the flux is less than 0.10 g, the flux mass and the corresponding sulfur measurement value are counted into a flux mass-sulfur measurement value-sulfur growth rate table at intervals of 0.10 g, and the flux mass corresponding to the first sulfur growth rate after the maximum sulfur growth rate is used as a proper amount.
To reduce the effort, the flux mass spacing can be relaxed to 0.20 grams. Even though the flux released sulfur increased and the crucible leached sulfur increased the total sulfur content of the sample, the sulfur measurement was within the allowable range. Then the flux mass corresponding to the first point after the maximum sulfur increase rate is the appropriate amount.
For some unknown new materials, the initial screening can be carried out by selecting the incremental mass of the fluxing agent of more than 0.10 g, and the range of the proper dosage is locked. The appropriate flux level was then determined in the same step with an increment of 0.10 g.
The same incremental flux was weighed in duplicate and sulfur content was measured using a carbon sulfur analyzer, respectively, and a flux mass-sulfur measurement-sulfur growth rate table was calculated. The determination method has the advantages that the workload of weighing and measuring is obviously increased, the sulfur measurement value is averaged, and the influence of accidental factors on the sulfur content measurement is eliminated.
For particularly refractory materials such as ceramics, where a mass of the coupon requires more flux, the fixed value of the coupon mass can be chosen to be less than conventional (0.10 to 1.00 grams) to avoid too large a flux dose to be accommodated by the crucible.
For samples with smaller density, such as titanium alloy and aluminum alloy, the burning process of the samples is easy to cause splash and damage the quartz tube in the burning zone of the carbon-sulfur analyzer, so after the samples and the fluxing agent are added into the crucible, the crucible cover is covered on the crucible opening to protect the quartz tube.
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. It is known that the blank of the backing crucible is significantly reduced, which is advantageous for ultra-low sulfur measurements.
The typical measurement modes of carbon sulfur analyzers are: the carrier gas flow rate was 3.0 liters/minute and one analysis procedure took approximately 1.5 minutes. A part of carbon-sulfur analyzer, aiming at the measurement of ultralow sulfur in a sample, has an enhanced sensitivity measurement mode: carrier gas flow < 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 (5) measuring the monocrystal superalloy DD6, and quantitatively judging the proper dosage of the tungsten-tin-iron fluxing agent.
(1) The single crystal superalloy DD6 is fixedly weighed, and 0.350 g of the single crystal superalloy DD6 is placed in a bottoming crucible;
(2) The mass of the tungsten-tin-iron fluxing agent shown in the table 4 is weighed and added into 0.350 g of single crystal superalloy DD 6;
(3) Sulfur measurements were made using a carbon sulfur analyzer using an enhanced sensitivity mode, as listed in table 4;
(4) The sulfur growth rate of each point was calculated at intervals of 0.10 g of flux mass and shown in Table 4;
TABLE 4 Single Crystal superalloy DD6 flux quality-sulfur measurement-sulfur growth rate Table
In Table 4, the maximum point 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 addition, ensures complete release of sulfur in the sample. At the same time, the addition of 0.10 g of flux, even if the flux released sulfur increased and the crucible leached sulfur increased all of the sulfur content of the sample, the allowable difference of the sulfur measurement result of Table 1 was 0.0003%, and the sulfur measurement result was also within the allowable difference range. The mass of the flux corresponding to the first point after the maximum point is 1.00 g.
Namely, 0.350 g of a single crystal superalloy DD6 sulfur-measuring sample is selected, and the proper dosage of the tungsten-tin-iron fluxing agent is 1.00 g.
Example 3
And (5) measuring the silicon steel and the tungsten-tin fluxing agent, and quantitatively judging the proper dosage of the silicon steel and the tungsten-tin fluxing agent.
(1) Fixedly weighing 0.250 g of silicon steel;
(2) Weighing the mass of the tungsten-tin fluxing agent shown in table 5, and adding the tungsten-tin fluxing agent into 0.250 g of silicon steel;
(3) Sulfur measurements were made using a carbon sulfur analyzer and are listed in table 5;
(4) The sulfur growth rate of each point was calculated at intervals of 0.10 g of flux mass and shown in Table 5;
TABLE 5 silicon steel flux mass-sulfur measurement-sulfur growth rate table
In Table 5, the maximum point 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 addition, ensures complete release of sulfur in the sample. At the same time, the addition of 0.10 g of flux, even though the flux released sulfur increased and the crucible leached sulfur increased all of the sulfur content of the sample, the allowable difference of the sulfur measurement result of Table 1 was 0.0005%, and the sulfur measurement result was within the allowable difference range. The mass of the fluxing agent corresponding to the first point after the maximum point is 1.30 g.
Namely, a silicon steel sulfur test sample is selected to be 0.250 g, and the proper dosage of the tungsten-tin fluxing agent is 1.30 g.
Example 4
And (5) measuring the cobalt-based alloy, and quantitatively judging the proper dosage of the ferrotungsten fluxing agent.
(1) Fixedly weighing 1.000 g of cobalt-based alloy;
(2) The ferrotungsten flux mass as in Table 6 was weighed and added to 1.000 grams of cobalt-based alloy;
(3) Sulfur measurements were made using a carbon sulfur analyzer and are listed in table 6;
(4) The sulfur growth rate of each point was calculated with 0.20 g flux mass as interval, and shown in Table 6;
TABLE 6 cobalt-based alloy flux mass-sulfur measurement-sulfur growth rate Table
In Table 6, the maximum point 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 addition, ensures complete release of sulfur in the sample. At the same time, 0.20 g of flux was added, and even if the flux released sulfur was increased and the crucible leached sulfur was increased by all of the sulfur content of the sample, the allowable difference was 0.001% by table 1 sulfur measurement, and the sulfur measurement was within the allowable difference range. The mass of the fluxing agent corresponding to the first point after the maximum point is 3.80 g.
Namely, a cobalt-based alloy sulfur measurement sample is selected to be 1.000 g, and the proper dosage of the ferrotungsten fluxing agent is 3.80 g.
Example 5
Silicon carbide continuous fiber reinforced metallic materials have been successfully used in aerospace planning. The sulfur element is also a control element, and measurement is required by a carbon-sulfur analyzer. Because silicon carbide is a nonmetallic material, the silicon carbide continuous reinforced metallic material belongs to a low electromagnetic induction material, and is difficult to generate larger vortex, SO that SO is caused 2 Release is difficult and therefore a fixed mass of 0.050 grams is selected that is 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, which has not been analyzed before, and does not know how much fluxing agent is needed. Therefore, the flux mass interval was first selected to be 0.50 grams.
The sulfur content of the silicon carbide continuous fiber reinforced metal material is measured by using a special fluxing agent, and the special fluxing agent is suitable for quantitative judgment of the dosage.
(1) Fixedly weighing 0.050 g of silicon carbide continuous fiber reinforced metal material;
(2) Weighing the special fluxing agent mass shown in Table 7, and adding the special fluxing agent mass into 0.050 g of silicon carbide continuous fiber reinforced metal material;
(3) Sulfur measurements were made using a carbon sulfur analyzer and are listed in table 7;
(4) The sulfur growth rate of each point was calculated with 0.50 g of flux mass as interval, and shown in Table 7;
TABLE 7 mass-sulfur measurement-sulfur growth rate Table for silicon carbide continuous fiber reinforced metal fluxing agent
In Table 7, the maximum point of the sulfur growth rate was 2.50 g, and the sulfur content was measured by using a carbon-sulfur analyzer by adding flux of increasing mass to the sample at intervals of 0.10 g in the range of the interval between the front and rear of the maximum point of the sulfur growth rate (2.00 to 3.00 g).
(1) Fixedly weighing 0.050 g of silicon carbide continuous fiber reinforced metal material;
(2) Weighing the special fluxing agent mass shown in Table 8, and adding the special fluxing agent mass into 0.050 g of silicon carbide continuous fiber reinforced metal material;
(3) Sulfur measurements were made using a carbon sulfur analyzer and are listed in table 8;
(4) The sulfur growth rate of each point was calculated with 0.10 g of flux mass as interval, and is shown in Table 8;
TABLE 8 mass-sulfur measurement-sulfur growth rate Table for silicon carbide continuous fiber reinforced metal fluxing agent
In Table 8, the maximum point of sulfur increase (2.30 g) is the maximum release of sulfur from the sample, and the first point after the maximum point, i.e., 2.40 g after 0.10 g of flux addition, ensures complete release of sulfur from the sample. At the same time, the addition of 0.10 g of flux, even if the flux released sulfur increased and the crucible leached sulfur increased all of the sulfur content of the sample, the allowable difference of the sulfur measurement result of Table 1 was 0.002%, and the sulfur measurement result was also within the allowable difference range. The mass of the flux corresponding to the first point after the maximum point is 2.40 g of the proper amount.
Namely 0.050 g of silicon carbide continuous fiber reinforced metal material sulfur measurement sample, and 2.40 g of special fluxing agent.
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 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 (8)
1. A method for determining the flux amount of sulfur element in a measurement sample by an infrared absorption method is characterized by comprising the following steps:
1.1 preparing two or more groups of measurement samples and fluxing agents, wherein the weight of the measurement samples, the number of the samples, the fluxing agents and the cosolvents in each group are identical, determining the mass of the measured samples, and taking a plurality of samples to be respectively placed in respective crucibles;
1.2, setting incremental mass weighing fluxing agents according to fixed intervals, and respectively covering the fluxing agents on each sample, wherein the incremental mass weighing fluxing agents correspond to 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 and obtaining sulfur measurement values of all the samples by using a carbon-sulfur analyzer;
1.5 calculating the sulfur increase rate at the n+1th fluxing agent measuring point according to the following formula (n+1) ：
Sulfur growth rate (n+1) ＝(C n+1 -C n )/C n ×100％
Wherein C is n+1 Sulfur measurement at the n+1th flux measurement point, C n Sulfur measurements that are the nth flux measurement point; measuring sulfur measurement values of each group of samples respectively, taking the sulfur measurement values of each group of samples at the same flux measurement point, calculating the average value of the sulfur measurement values, and calculating the sulfur increase rate at each flux measurement point based on the result (n+1) ；
1.6, taking the mass of the fluxing agent corresponding to the maximum sulfur increase rate as the basic fluxing agent dosage;
1.7 adding an incremental mass to the basic flux as the appropriate flux.
2. The flux amount determination method according to claim 1, wherein: the fixed interval is set according to the material characteristics for samples of different materials.
3. The flux amount determination method according to claim 1, wherein: for the measurement of new materials, firstly, weighing the fluxing agent at a larger fixed interval, and rapidly determining the application range of the fluxing agent; and then gradually reducing the fixed interval, and precisely determining the proper flux amount.
4. The flux amount determination method according to claim 1, wherein: the fixed interval is 0.10 or 0.20 grams.
5. The flux amount determination method according to claim 1, wherein: the carbon sulfur analyzer uses an enhanced sensitivity mode to determine sulfur content.
6. The flux amount determination method according to claim 1, wherein: if the finally obtained flux dose does not meet the relevant standard after the actual verification, the fixed interval is reduced to redetermine the flux dose.
7. The flux amount determination method according to claim 1, wherein: a backing crucible was used.
8. The flux amount determination method according to claim 1, wherein: after the crucible is filled with the sample and the fluxing agent, a crucible cover is covered on the crucible opening.
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