CN113820289A - Method for simultaneously measuring oxygen and nitrogen contents in titanium material - Google Patents
Method for simultaneously measuring oxygen and nitrogen contents in titanium material Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 328
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 239000001301 oxygen Substances 0.000 title claims abstract description 166
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 166
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 164
- 239000000463 material Substances 0.000 title claims abstract description 87
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000010936 titanium Substances 0.000 title claims abstract description 83
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 80
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004458 analytical method Methods 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 32
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000012935 Averaging Methods 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 9
- 238000012937 correction Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000005259 measurement Methods 0.000 description 17
- 238000007872 degassing Methods 0.000 description 9
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000005303 weighing Methods 0.000 description 4
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 238000007750 plasma spraying Methods 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
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
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- General Health & Medical Sciences (AREA)
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Abstract
The invention provides a method for simultaneously measuring the contents of oxygen and nitrogen in a titanium material, which comprises the following steps: (1) respectively and independently establishing an oxygen standard curve and a nitrogen standard curve by adopting a multipoint calibration method; (2) wrapping a titanium material to be detected with a nickel material to form an inclusion; (3) placing the inclusion obtained in the step (2) in a graphite container, introducing inert gas, heating and melting the inclusion, and releasing carbon monoxide, carbon dioxide and nitrogen; (4) detecting the carbon monoxide and the carbon dioxide obtained in the step (3), and determining the oxygen content in the titanium material according to the oxygen standard curve obtained in the step (1); (5) detecting the nitrogen obtained in the step (3), and determining the nitrogen content in the titanium material according to the nitrogen standard curve obtained in the step (1); wherein, the step (4) and the step (5) are carried out simultaneously. The method provided by the invention is particularly suitable for measuring the oxygen and nitrogen elements with high content in the titanium material, and the analysis method is accurate and reliable and has stable analysis results.
Description
Technical Field
The invention belongs to the technical field of analysis and test, relates to a method for simultaneously determining the contents of oxygen and nitrogen, and particularly relates to a method for simultaneously determining high-content oxygen and nitrogen elements in a titanium material.
Background
The titanium material is one of the most popular new materials researched at present, and the titanium alloy has the advantages of light weight, high specific strength, wear resistance, combustion resistance, oxidation resistance and the like, has excellent high-temperature mechanical properties, can be used as materials for engines and machine bodies of aviation airplanes, automobile valves and rockers and the like, and has good application prospects in the fields of biomedicine, automobile industry and the like.
Because the oxygen and nitrogen elements have higher solubility in the preparation process of the titanium material, the oxygen and nitrogen elements become indispensable items of the titanium material. Generally, for measuring the oxygen and nitrogen contents in a titanium material, the instrumental method can be performed in accordance with GB/T4698.7, but in this method, the oxygen content is measured in a range of 0.01 wt% to 0.50 wt%, and the nitrogen content is measured in a range of 0.003 wt% to 0.11 wt%, and the method cannot be applied to the measurement of the oxygen and nitrogen contents exceeding this range. In addition, the chemical method has lagged equipment, complex operation and long test period, and is difficult to meet the requirements of modern industrial production.
For example, for the preparation of titanium coatings for surgical implants, oxygen and nitrogen are inevitably added during plasma spraying, and ISO:13179-1:2014 specifies that oxygen is less than or equal to 10 wt% and nitrogen is less than or equal to 5 wt%; in addition, the oxygen and nitrogen content in the titanium sintered and 3D printed samples is also beyond the measurement range of conventional analytical methods. However, there is no accurate analysis method for such a sample containing a high content of oxygen and nitrogen, and there is no standard sample containing a similar content, and if a conventional calibration method is directly used, the measurement result will be greatly deviated.
CN 109342500a discloses a method for simultaneously determining the contents of oxygen, nitrogen and hydrogen in a titanium alloy, which comprises the following steps: putting the titanium alloy into an oxygen nitrogen hydrogen analyzer based on an inert gas melting-infrared absorption and/or thermal conductivity method, and measuring by using metal nickel as a fluxing agent in a two-section heating mode, wherein the first-section heating temperature is 1050-1550 ℃, and the second-section heating temperature is 2700-3000 ℃; wherein the hydrogen content in the titanium alloy is 0.030-4.1% (w/w). Although the invention eliminates the interference of high hydrogen content on nitrogen determination and realizes the simultaneous determination of three elements, the invention still can not be applied to the analysis and determination of titanium materials with high oxygen content and high nitrogen content.
CN 106525757A discloses a method for determining trace oxygen and nitrogen elements in alloy steel, which comprises the following steps: preparing test conditions; step 2: preparing a sample; and step 3: blank test; and 4, step 4: calibrating an oxygen-nitrogen analyzer; 4.1: calibrating by using an oxygen and nitrogen content standard substance in steel; 4.2: determining and calibrating an oxygen and nitrogen content standard substance in the steel; and 5: and measuring the content of trace oxygen and nitrogen in the sample. However, the method is only suitable for measuring trace oxygen and nitrogen elements, the measuring range is limited, and the problem that the high-content oxygen and nitrogen elements cannot be accurately measured exists.
Therefore, how to provide a method for simultaneously measuring the contents of oxygen and nitrogen in a titanium material, which is particularly suitable for measuring oxygen and nitrogen elements with high content, has accurate and reliable analysis method and stable analysis result, meets the actual production requirement, and becomes a problem to be solved by technical personnel in the field at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for simultaneously measuring the contents of oxygen and nitrogen in a titanium material, the method is particularly suitable for measuring oxygen and nitrogen elements with high content in the titanium material, the analysis method is accurate and reliable, and the analysis result is stable.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for simultaneously measuring the contents of oxygen and nitrogen in a titanium material, which comprises the following steps:
(1) respectively and independently establishing an oxygen standard curve and a nitrogen standard curve by adopting a multipoint calibration method;
(2) wrapping a titanium material to be detected with a nickel material to form an inclusion;
(3) placing the inclusion obtained in the step (2) in a graphite container, introducing inert gas, heating and melting the inclusion, and releasing carbon monoxide, carbon dioxide and nitrogen;
(4) detecting the carbon monoxide and the carbon dioxide obtained in the step (3), and determining the oxygen content in the titanium material according to the oxygen standard curve obtained in the step (1);
(5) and (4) detecting the nitrogen obtained in the step (3), and determining the nitrogen content in the titanium material according to the nitrogen standard curve obtained in the step (1).
Wherein, the step (4) and the step (5) are carried out simultaneously.
Based on an instrument method, the invention firstly adopts a multipoint calibration method to respectively and independently establish an oxygen standard curve and a nitrogen standard curve, and then reduces the sample weighing of the titanium material to be measured, so that the quality of oxygen and nitrogen elements in the titanium material is in the range of the standard curve, thereby realizing the measurement of the oxygen and nitrogen elements with high content in the titanium material, improving the accuracy and stability of the measurement result, and overcoming the problem of larger deviation of the measurement result obtained by the conventional calibration method.
In the process of establishing an oxygen standard curve and a nitrogen standard curve, a titanium-based material (an oxygen standard sample) is wrapped by a nickel material to form an inclusion; for steel-based materials (nitrogen standards), the melting can be directly analyzed without adding a cosolvent.
In the present invention, the oxygen content of the titanium material to be measured in step (2) is 1-3 wt%, for example, 1 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.4 wt%, 2.6 wt%, 2.8 wt%, or 3 wt%, but is not limited to the recited values, and other unrecited values in the range of the recited values are also applicable.
In the present invention, the nitrogen content of the titanium material to be tested in step (2) is 0.5-1.5 wt%, for example, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, or 1.5 wt%, but is not limited to the recited values, and other unrecited values in the range of values are also applicable.
The method provided by the invention is carried out in a conventional oxygen-nitrogen analyzer, as long as the content of oxygen and nitrogen in the titanium material can be measured, so the specific model of the oxygen-nitrogen analyzer is not particularly limited, and for example, a ONH836 high-temperature oxygen-nitrogen analyzer manufactured by LECO company can be adopted.
Preferably, the method for establishing the oxygen standard curve in the step (1) comprises the following steps: selecting at least 3 first standard samples with different oxygen contents, analyzing the oxygen content of each first standard sample at least 3 times, and establishing an oxygen standard curve by using a multipoint calibration program after averaging.
Preferably, the correlation coefficient R of the oxygen standard curve in the step (1)2Not less than 0.99, for example 0.99, 0.995 or 0.999, but not limited to the enumerated values, and other non-enumerated values within the range are also applicable.
Preferably, the first standard sample is a titanium-based standard sample.
In the invention, the oxygen content of the titanium-based standard sample is in the measurement range of a conventional oxygen-nitrogen analyzer, as long as the accurate measurement of the oxygen content in the titanium material to be measured can be realized, so the specific type of the titanium-based standard sample is not particularly limited, and for example, the standard samples with the models of LECO 502-.
Preferably, the oxygen standard curve is also subjected to a first accuracy check after establishment.
Preferably, the specific process of the first accuracy test is as follows: and (3) determining a first standard sample of the intermediate oxygen content according to the oxygen standard curve, and when the analysis result is in an uncertainty range, indicating that the accuracy of the oxygen standard curve is good, otherwise, performing correction processing.
In the present invention, the first standard sample of the intermediate oxygen content is specifically a first standard sample having an oxygen content in the range of 0.1 to 0.5 wt% and not more than 0.1 wt% from the intermediate value of 0.3 wt%.
Preferably, the method for establishing the nitrogen standard curve in the step (1) comprises the following steps: selecting at least 3 second standard samples with different nitrogen contents, analyzing the nitrogen content of each second standard sample for at least 3 times, and establishing a nitrogen standard curve by using a multipoint calibration program after averaging.
Preferably, the correlation coefficient R of the nitrogen standard curve in the step (1)2Not less than 0.99, for example 0.99, 0.995 or 0.999, but not limited to the enumerated values, and other non-enumerated values within the rangeThe same applies.
Preferably, the second standard sample is a steel-based standard sample.
In the invention, the nitrogen content of the steel-based standard sample is in the measurement range of a conventional oxygen-nitrogen analyzer as long as the nitrogen content of the titanium material to be measured can be accurately measured, so the specific type of the steel-based standard sample is not particularly limited, and for example, the standard samples with the models of YSBC 11936-2012, GBW (E)020089, YSBC 11936-2012 or No. 68-2-1 can be adopted.
In the invention, the nitrogen content and the adjustment area in the titanium material to be measured are within the linear range of the steel-based standard sample, are higher by one order of magnitude than the titanium-based standard sample and exceed the quantitative range of the steel-based standard sample, so the steel-based standard sample is selected as the second standard sample to calculate the nitrogen content in the titanium material to be measured.
Preferably, the nitrogen standard curve is also subjected to a second accuracy test after establishment.
Preferably, the specific process of the second accuracy test is as follows: and (4) determining a second standard sample of the middle nitrogen content according to the nitrogen standard curve, and when the analysis result is in an uncertainty range, indicating that the accuracy of the nitrogen standard curve is good, otherwise, performing correction processing.
In the present invention, the second standard sample of the intermediate nitrogen content is specifically a second standard sample having a nitrogen content in the range of 0.05 to 0.3 wt% and not more than 0.1 wt% from the intermediate value of 0.175 wt%.
Preferably, the nickel material in step (2) comprises any one of a nickel basket, a nickel bag, a nickel foil or a nickel foil cup.
Preferably, the titanium material to be detected in the step (2) includes a titanium simple substance or a titanium alloy.
Preferably, the mass ratio of the nickel material to the titanium material to be measured in the step (2) is (7-17):1, and may be, for example, 7:1, 8:1, 10:1, 12:1, 14:1, 16:1 or 17:1, but is not limited to the enumerated values, and other unrecited value ranges in the numerical range are also applicable.
In the invention, the nickel material in the step (2) is used as a nickel cosolvent in the subsequent heating and melting process, so that the sufficient release of oxygen and nitrogen elements in the titanium material to be detected is ensured, and the mass ratio of the nickel material to the titanium material to be detected has a remarkable influence on the sufficient release of nitrogen and oxygen.
Preferably, the mass of the titanium material to be tested in step (2) is less than or equal to 87mg, for example, 10mg, 15mg, 20mg, 25mg, 30mg, 35mg, 40mg, 45mg, 50mg, 55mg, 60mg, 65mg, 70mg, 75mg, 80mg, 85mg or 87mg, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
In the invention, the quality of the titanium material to be tested has obvious influence on the test result. When the quality of the titanium material to be measured is higher than 87mg, the content of gas elements (elements such as oxygen, nitrogen and hydrogen) in the sample is higher, so that a large amount of gas is released instantly during heating and melting, a bulge is formed at the opening of the crucible, the release of the oxygen and nitrogen elements is blocked, and the measurement result is lower.
Preferably, the graphite container of step (3) comprises a graphite crucible.
In the invention, the graphite container in the step (3) is used as a carbon resistor, and can generate enough heat to melt the sample after being electrified, oxygen in the titanium material can be oxidized with carbon in the graphite container to generate carbon monoxide, and the obtained carbon monoxide can be reacted with the scorching copper oxide in the oxygen-nitrogen analyzer to generate carbon dioxide, so that the sufficient release of oxygen in the titanium material is realized.
Preferably, the inert gas in step (3) comprises helium or argon.
Preferably, the temperature for melting by heating in step (3) is 2200-.
Preferably, the heating of step (3) is melted until the oxygen and nitrogen elements in the titanium material are completely released.
Preferably, the detection in step (4) is performed by using an infrared detector.
Preferably, the detection in step (5) is performed by using a thermal conductivity detector.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) the method adopts a multipoint calibration method to respectively and independently establish an oxygen standard curve and a nitrogen standard curve, and comprises the following specific processes:
(a) selecting at least 3 first standard samples with different oxygen contents, analyzing the oxygen content of each first standard sample for at least 3 times, averaging, and establishing a correlation coefficient R by using a multipoint calibration program2An oxygen standard curve of 0.99 or more; determining a first standard sample of the intermediate oxygen content according to the oxygen standard curve, and when the analysis result is in an uncertainty range, indicating that the accuracy of the oxygen standard curve is good, otherwise, performing correction processing; the first standard sample is a titanium-based standard sample;
(b) selecting at least 3 second standard samples with different nitrogen contents, analyzing the nitrogen content of each second standard sample for at least 3 times, averaging, and establishing a correlation coefficient R by using a multipoint calibration program2A nitrogen standard curve of 0.99 or more; determining a second standard sample of the middle nitrogen content according to the nitrogen standard curve, and when the analysis result is in an uncertainty range, indicating that the accuracy of the nitrogen standard curve is good, otherwise, performing correction processing; the second standard sample is a steel-based standard sample;
(2) wrapping a titanium material to be measured by using a nickel material according to the mass ratio of (7-17) to 1 to form an inclusion; the nickel material comprises any one of a nickel basket, a nickel bag, a nickel foil or a nickel foil cup; the titanium material to be detected comprises a titanium simple substance or a titanium alloy, and the mass of the titanium material to be detected is less than or equal to 87 mg;
(3) placing the inclusion obtained in the step (2) in a graphite crucible, introducing helium or argon, and heating and melting the inclusion at 2200-;
(4) detecting the carbon monoxide and the carbon dioxide obtained in the step (3) by adopting an infrared detector, and determining the oxygen content in the titanium material according to the oxygen standard curve obtained in the step (1);
(5) and (4) detecting the nitrogen obtained in the step (3) by adopting a thermal conductivity detector, and determining the nitrogen content in the titanium material according to the nitrogen standard curve obtained in the step (1).
Wherein, the step (4) and the step (5) are carried out simultaneously.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) based on an instrument method, firstly, a multipoint calibration method is adopted to respectively and independently establish an oxygen standard curve and a nitrogen standard curve, and then the sample weighing of the titanium material to be measured is reduced to be below 87mg, so that the quality of oxygen and nitrogen elements of the titanium material is in the range of the standard curve; firstly, calculating the mass of an element to be measured according to the weight of a standard sample, and then establishing a calibration curve by taking the mass of the oxygen/nitrogen element as an abscissa and the response area as an ordinate, so as to ensure that the mass of the oxygen/nitrogen element of the sample to be measured is similar to that of the oxygen/nitrogen element of the standard sample, and improve the measurement accuracy to the greatest extent;
(2) the method provided by the invention increases the measuring range of the oxygen content to 1-5 wt%, and the measuring range of the nitrogen content to 0.5-5 wt%, so that the accuracy and stability of the measuring result are improved, and the problem of larger deviation of the measuring result obtained by the conventional calibration method is solved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a method for simultaneously measuring the contents of oxygen and nitrogen in a titanium material, which adopts an ONH836 model high-temperature nitrogen-oxygen analyzer manufactured by LECO company, and the oxygen detection range of the analyzer is as follows: 0.00005mg/g-50mg/g, and the nitrogen detection range is 0.00005mg/g-30 mg/g; the working conditions are as follows: degassing power 6000W, degassing time 20s, analytical power 5500W, oxygen analysis time 60s, nitrogen analysis time 60s, double degassing, flow 450mL/min, inlet pressure 22 psi.
In this embodiment, the method includes the steps of:
(1) the method adopts a multipoint calibration method to respectively and independently establish an oxygen standard curve and a nitrogen standard curve, and comprises the following specific processes:
(a) selecting 4 first standard samples with different oxygen contents, and referring to table 1, analyzing the oxygen content of each first standard sample for 3 times, averaging, and establishing an oxygen standard curve by using a multipoint calibration program, wherein the oxygen standard curve is referred to as formula 1; determining a first standard sample of the intermediate oxygen content according to the oxygen standard curve, wherein the analysis result is in an uncertainty range, which indicates that the accuracy of the oxygen standard curve is good;
(b) selecting 4 second standard samples with different nitrogen contents, and referring to table 2, analyzing the nitrogen content for 3 times by each second standard sample, and establishing a nitrogen standard curve by using a multipoint calibration program after taking an average value, wherein the nitrogen standard curve is referred to as formula 2; determining a second standard sample of the middle nitrogen content according to the nitrogen standard curve, wherein the analysis result is in an uncertainty range, which indicates that the accuracy of the nitrogen standard curve is good;
(2) wrapping 30mg of titanium alloy by using a nickel basket according to the mass ratio of 17:1 to form a wrapping body; in order to improve the accuracy of the measured sample, the oxygen element quality (note: not the sample quality) of the standard sample and the sample is ensured to be as close as possible;
(3) placing the inclusion obtained in the step (2) in a graphite crucible, introducing helium gas, and heating and melting the inclusion at 2250 ℃ until oxygen and nitrogen elements in the titanium alloy are respectively and independently released completely in the forms of carbon monoxide, carbon dioxide and nitrogen;
(4) detecting the carbon monoxide and the carbon dioxide obtained in the step (3) by using an infrared detector, and determining the oxygen content in the titanium alloy according to the oxygen standard curve of the formula 1;
(5) and (4) detecting the nitrogen obtained in the step (3) by adopting a thermal conductivity detector, and determining the nitrogen content in the titanium alloy according to the nitrogen standard curve of the formula 2.
Wherein, the step (4) and the step (5) are carried out simultaneously.
In this example, the oxygen content of the titanium alloy sample was measured to be 2.64 wt%, and the nitrogen content was measured to be 1.11 wt%.
TABLE 1
Oxygen standard curve: Y-1.01791404X-0.00001586 (1)
Coefficient of correlation R2＝0.9994。
TABLE 2
Nitrogen standard curve: Y-1.10000284X-0.00000431 (2)
Coefficient of correlation R2＝0.9997。
Example 2
The embodiment provides a method for simultaneously measuring the contents of oxygen and nitrogen in a titanium material, which adopts an ONH836 model high-temperature nitrogen-oxygen analyzer manufactured by LECO company, and the oxygen detection range of the analyzer is as follows: 0.00005mg/g-50mg/g, and the nitrogen detection range is 0.00005mg/g-30 mg/g; the working conditions are as follows: degassing power 6000W, degassing time 20s, analytical power 5500W, oxygen analysis time 60s, nitrogen analysis time 60s, double degassing, flow 450mL/min, inlet pressure 22 psi.
In this embodiment, the method includes the steps of:
(1) the method adopts a multipoint calibration method to respectively and independently establish an oxygen standard curve and a nitrogen standard curve, and comprises the following specific processes:
(a) selecting 3 first standard samples with different oxygen contents, and referring to table 3, analyzing the oxygen content of each first standard sample for 3 times, and establishing an oxygen standard curve by using a multipoint calibration program after taking an average value, wherein the oxygen standard curve is referred to as formula 3; determining a first standard sample of the intermediate oxygen content according to the oxygen standard curve, wherein the analysis result is in an uncertainty range, which indicates that the accuracy of the oxygen standard curve is good;
(b) the method and result for establishing the nitrogen standard curve in this embodiment are the same as those in embodiment 1, and therefore are not described herein again;
(2) wrapping 30mg of titanium alloy by using a nickel bag according to the mass ratio of 13:1 to form an inclusion; in order to improve the accuracy of the measured sample, the oxygen element quality (note: not the sample quality) of the standard sample and the sample is ensured to be as close as possible;
(3) placing the inclusion obtained in the step (2) in a graphite crucible, introducing argon gas, and heating and melting the inclusion at 2300 ℃ until oxygen and nitrogen elements in the titanium alloy are respectively and independently released completely in the forms of carbon monoxide, carbon dioxide and nitrogen;
(4) detecting the carbon monoxide and the carbon dioxide obtained in the step (3) by using an infrared detector, and determining the oxygen content in the titanium alloy according to an oxygen standard curve of a formula 3;
(5) and (4) detecting the nitrogen obtained in the step (3) by adopting a thermal conductivity detector, and determining the nitrogen content in the titanium alloy according to the nitrogen standard curve of the formula 2.
Wherein, the step (4) and the step (5) are carried out simultaneously.
In this example, the oxygen content of the titanium alloy sample was measured to be 2.68 wt%, and the nitrogen content was measured to be 1.10 wt%.
TABLE 3
Oxygen standard curve: Y-1.00151014X-0.00001521 (3)
Coefficient of correlation R2＝0.9991。
Example 3
The embodiment provides a method for simultaneously measuring the contents of oxygen and nitrogen in a titanium material, which adopts an ONH836 model high-temperature nitrogen-oxygen analyzer manufactured by LECO company, and the oxygen detection range of the analyzer is as follows: 0.00005mg/g-50mg/g, and the nitrogen detection range is 0.00005mg/g-30 mg/g; the working conditions are as follows: degassing power 6000W, degassing time 20s, analytical power 5500W, oxygen analysis time 60s, nitrogen analysis time 60s, double degassing, flow 450mL/min, inlet pressure 22 psi.
In this embodiment, the method includes the steps of:
(1) the method adopts a multipoint calibration method to respectively and independently establish an oxygen standard curve and a nitrogen standard curve, and comprises the following specific processes:
(a) selecting 3 first standard samples with different oxygen contents, and referring to table 4, analyzing the oxygen content for 3 times by each first standard sample, and establishing an oxygen standard curve by using a multipoint calibration program after taking an average value, wherein the oxygen standard curve is referred to as formula 4; determining a first standard sample of the intermediate oxygen content according to the oxygen standard curve, wherein the analysis result is in an uncertainty range, which indicates that the accuracy of the oxygen standard curve is good;
(b) the method and result for establishing the nitrogen standard curve in this embodiment are the same as those in embodiment 1, and therefore are not described herein again;
(2) wrapping 30mg of titanium alloy by using a nickel bag according to the mass ratio of 8:1 to form an inclusion; in order to improve the accuracy of the measured sample, the oxygen element quality (note: not the sample quality) of the standard sample and the sample is ensured to be as close as possible;
(3) placing the inclusion obtained in the step (2) in a graphite crucible, introducing helium, and heating and melting the inclusion at 2200 ℃ until oxygen and nitrogen elements in the titanium alloy are respectively and independently released completely in the forms of carbon monoxide, carbon dioxide and nitrogen;
(4) detecting the carbon monoxide and the carbon dioxide obtained in the step (3) by using an infrared detector, and determining the oxygen content in the titanium alloy according to an oxygen standard curve of a formula 4;
(5) and (4) detecting the nitrogen obtained in the step (3) by adopting a thermal conductivity detector, and determining the nitrogen content in the titanium alloy according to the nitrogen standard curve of the formula 2.
Wherein, the step (4) and the step (5) are carried out simultaneously.
In this example, the oxygen content of the titanium alloy sample was measured to be 2.66 wt%, and the nitrogen content was measured to be 1.11 wt%.
TABLE 4
Oxygen standard curve: Y-1.02009680X-0.00002291 (4)
Coefficient of correlation R2＝0.9984。
Example 4
This example provides a method for simultaneously determining the oxygen and nitrogen contents in a titanium material, which is the same as example 1 except that the mass of the titanium alloy sample in step (2) is changed to 28mg, and therefore, the detailed description thereof is omitted here.
In this example, the oxygen content of the titanium alloy specimen was measured to be 2.74 wt%, and the nitrogen content was measured to be 1.11 wt%.
Example 5
This example provides a method for simultaneously determining the oxygen and nitrogen contents in a titanium material, which is the same as example 1 except that the mass of the titanium alloy sample in step (2) is changed to 58mg, and therefore, the detailed description thereof is omitted here.
In this example, the oxygen content of the titanium alloy specimen was measured to be 2.78 wt% and the nitrogen content was measured to be 1.08 wt%.
Example 6
This example provides a method for simultaneously determining the oxygen and nitrogen contents in a titanium material, which is the same as example 1 except that the mass of the titanium alloy sample in step (2) is changed to 87mg, and therefore, the detailed description thereof is omitted here.
In this example, the oxygen content of the titanium alloy specimen was measured to be 2.77 wt%, and the nitrogen content was measured to be 1.05 wt%.
Example 7
This example provides a method for simultaneously determining the oxygen and nitrogen contents in a titanium material, which is the same as example 1 except that the mass of the titanium alloy sample in step (2) is changed to 100mg, and therefore, the detailed description thereof is omitted here.
In this example, the oxygen content of the titanium alloy specimen was measured to be 1.79 wt%, and the nitrogen content was measured to be 0.214 wt%.
Compared with example 1, in this embodiment, since the sample weighing amount of the titanium alloy is too high, the content of gas elements (elements such as oxygen, nitrogen, and hydrogen) in the sample is high, a large amount of gas is released instantaneously during heating and melting, a bulge is formed at the crucible opening, the release of oxygen and nitrogen elements is hindered, and the measurement result is low.
Therefore, based on an instrument method, the oxygen standard curve and the nitrogen standard curve are respectively and independently established by adopting a multipoint calibration method, and then the sample weighing of the titanium material to be measured is reduced to be below 87mg, so that the quality of oxygen and nitrogen elements of the titanium material is in the range of the standard curve; the mass of the element to be measured is calculated according to the weight of the standard sample, and then a calibration curve is established by taking the mass of the oxygen/nitrogen element as an abscissa and the response area as an ordinate, so that the mass of the oxygen/nitrogen element of the sample to be measured is close to that of the oxygen/nitrogen element of the standard sample, and the measurement accuracy is improved to the maximum extent. In addition, the method provided by the invention increases the measurement range of the oxygen content to 1-5 wt%, and the measurement range of the nitrogen content to 0.5-5 wt%, so that the accuracy and stability of the measurement result are improved, and the problem of large deviation of the measurement result obtained by the conventional calibration method is solved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for simultaneously measuring the contents of oxygen and nitrogen in a titanium material is characterized by comprising the following steps:
(1) respectively and independently establishing an oxygen standard curve and a nitrogen standard curve by adopting a multipoint calibration method;
(2) wrapping a titanium material to be detected with a nickel material to form an inclusion;
(3) placing the inclusion obtained in the step (2) in a graphite container, introducing inert gas, heating and melting the inclusion, and releasing carbon monoxide, carbon dioxide and nitrogen;
(4) detecting the carbon monoxide and the carbon dioxide obtained in the step (3), and determining the oxygen content in the titanium material according to the oxygen standard curve obtained in the step (1);
(5) detecting the nitrogen obtained in the step (3), and determining the nitrogen content in the titanium material according to the nitrogen standard curve obtained in the step (1);
wherein, the step (4) and the step (5) are carried out simultaneously.
2. The method according to claim 1, wherein the oxygen standard curve in step (1) is established by: selecting at least 3 first standard samples with different oxygen contents, analyzing the oxygen content of each first standard sample for at least 3 times, and establishing an oxygen standard curve by using a multipoint calibration program after averaging;
preferably, the correlation coefficient R of the oxygen standard curve in the step (1)2≥0.99。
3. The method of claim 2, wherein the first standard is a titanium-based standard;
preferably, the oxygen standard curve is also subjected to a first accuracy test after being established;
preferably, the specific process of the first accuracy test is as follows: and (3) determining a first standard sample of the intermediate oxygen content according to the oxygen standard curve, and when the analysis result is in an uncertainty range, indicating that the accuracy of the oxygen standard curve is good, otherwise, performing correction processing.
4. The method according to any one of claims 1 to 3, wherein the nitrogen standard curve in step (1) is established by: selecting at least 3 second standard samples with different nitrogen contents, analyzing the nitrogen content of each second standard sample for at least 3 times, and establishing a nitrogen standard curve by using a multipoint calibration program after averaging;
preferably, the correlation coefficient R of the nitrogen standard curve in the step (1)2≥0.99。
5. The method according to claim 4, characterized in that the second standard sample is a steel-based standard sample;
preferably, the nitrogen standard curve is also subjected to a second accuracy test after being established;
preferably, the specific process of the second accuracy test is as follows: and (4) determining a second standard sample of the middle nitrogen content according to the nitrogen standard curve, and when the analysis result is in an uncertainty range, indicating that the accuracy of the nitrogen standard curve is good, otherwise, performing correction processing.
6. The method of any one of claims 1-5, wherein the nickel material of step (2) comprises any one of a nickel basket, a nickel pouch, a nickel foil, or a nickel foil cup;
preferably, the titanium material to be detected in the step (2) comprises a titanium simple substance or a titanium alloy;
preferably, the mass ratio of the nickel material to the titanium material to be detected in the step (2) is (7-17) to 1;
preferably, the mass of the titanium material to be detected in the step (2) is less than or equal to 87 mg.
7. The method of any one of claims 1-6, wherein the graphite container of step (3) comprises a graphite crucible;
preferably, the inert gas of step (3) comprises helium or argon;
preferably, the temperature for heating and melting in the step (3) is 2200-;
preferably, the heating of step (3) is melted until the oxygen and nitrogen elements in the titanium material are completely released.
8. The method according to any one of claims 1 to 7, wherein the detection of step (4) is performed using an infrared detector.
9. The method of any one of claims 1-8, wherein said detecting of step (5) is performed using a thermal conductivity detector.
10. Method according to any of claims 1-9, characterized in that the method comprises the steps of:
(1) the method adopts a multipoint calibration method to respectively and independently establish an oxygen standard curve and a nitrogen standard curve, and comprises the following specific processes:
(a) selecting at least 3 first standard samples with different oxygen contents, analyzing the oxygen content of each first standard sample for at least 3 times, averaging, and establishing a correlation coefficient R by using a multipoint calibration program2An oxygen standard curve of 0.99 or more; determining a first standard sample of the intermediate oxygen content according to the oxygen standard curve, and when the analysis result is in an uncertainty range, indicating that the accuracy of the oxygen standard curve is good, otherwise, performing correction processing; the first standard sample is a titanium-based standard sample;
(b) selecting at least 3 second standard samples with different nitrogen contents, analyzing the nitrogen content of each second standard sample for at least 3 times, averaging, and establishing a correlation coefficient R by using a multipoint calibration program2A nitrogen standard curve of 0.99 or more; determining a second standard sample of the middle nitrogen content according to the nitrogen standard curve, and when the analysis result is in an uncertainty range, indicating that the accuracy of the nitrogen standard curve is good, otherwise, performing correction processing; the second standard sample is a steel-based standard sample;
(2) wrapping a titanium material to be measured by using a nickel material according to the mass ratio of (7-17) to 1 to form an inclusion; the nickel material comprises any one of a nickel basket, a nickel bag, a nickel foil or a nickel foil cup; the titanium material to be detected comprises a titanium simple substance or a titanium alloy, and the mass of the titanium material to be detected is less than or equal to 87 mg;
(3) placing the inclusion obtained in the step (2) in a graphite crucible, introducing helium or argon, and heating and melting the inclusion at 2200-;
(4) detecting the carbon monoxide and the carbon dioxide obtained in the step (3) by adopting an infrared detector, and determining the oxygen content in the titanium material according to the oxygen standard curve obtained in the step (1);
(5) detecting the nitrogen obtained in the step (3) by using a thermal conductivity detector, and determining the nitrogen content in the titanium material according to the nitrogen standard curve obtained in the step (1);
wherein, the step (4) and the step (5) are carried out simultaneously.
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