CN115586175A - Method for measuring contents of 19 elements in titanium sponge and titanium alloy by inductively coupled plasma emission spectrometry - Google Patents
Method for measuring contents of 19 elements in titanium sponge and titanium alloy by inductively coupled plasma emission spectrometry Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 50
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 44
- 238000009616 inductively coupled plasma Methods 0.000 title claims abstract description 31
- 238000004993 emission spectroscopy Methods 0.000 title claims abstract description 19
- 238000001514 detection method Methods 0.000 claims abstract description 57
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 33
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 27
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000120 microwave digestion Methods 0.000 claims abstract description 17
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 15
- 239000011651 chromium Substances 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 15
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 15
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 14
- 239000010955 niobium Substances 0.000 claims abstract description 14
- 229910052718 tin Inorganic materials 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010937 tungsten Substances 0.000 claims abstract description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000004698 Polyethylene Substances 0.000 claims description 18
- -1 polyethylene Polymers 0.000 claims description 18
- 229920000573 polyethylene Polymers 0.000 claims description 18
- 230000029087 digestion Effects 0.000 claims description 11
- 238000002133 sample digestion Methods 0.000 claims description 9
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000012086 standard solution Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000011002 quantification Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 37
- 238000002156 mixing Methods 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000001636 atomic emission spectroscopy Methods 0.000 description 2
- 238000009614 chemical analysis method Methods 0.000 description 2
- 238000000248 direct current plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000005375 photometry Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000368 spark atomic emission spectrometry Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001675 atomic spectrum Methods 0.000 description 1
- 238000003705 background correction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a method for measuring the content of 19 elements in titanium sponge and titanium alloy by using an inductively coupled plasma emission spectrometry, belonging to the technical field of detection of non-ferrous metal materials. The method takes hydrochloric acid, hydrofluoric acid, nitric acid and perchloric acid as solvents, adopts a microwave digestion technology to process a sample, takes an Ar420.073 line as an internal standard, takes high-purity titanium (titanium is more than or equal to 99.98%) as a matrix for matching, combines MSF, adopts a standard curve method for quantification, specifically eliminates the mutual influence of the matrix and each detection element by optimizing equipment parameters, and establishes a method for determining the contents of 19 elements (iron, silicon, manganese, molybdenum, boron, aluminum, tin, chromium, vanadium, zirconium, magnesium, niobium, palladium, nickel, tantalum, tungsten, neodymium, ruthenium and copper) in sponge titanium and titanium alloy by an inductively coupled plasma emission spectrometry.
Description
Technical Field
The invention belongs to the technical field of non-ferrous metal material detection, and particularly relates to a method for measuring the content of 19 trace elements in titanium sponge and titanium alloy by using an inductively coupled plasma emission spectrometry.
Background
At present, the domestic demand for high-end titanium sponge and titanium materials is increased explosively, and the market demand for domestic general industrial titanium sponge and titanium materials is in a fatigue current situation abroad.
The reason why the quality of the titanium sponge and the titanium material is not high in China is that besides the factors of technological innovation, technical process and the like, accurate and efficient detection technical means are also one of important factors. Firstly, because the detection efficiency is not high due to the excessive dispersion of the detection standards, in the currently used standard detection method (GB/T4698.1-28) for titanium sponge and titanium alloy in China, 18 detection method standards are provided for the detection of 19 chemical components of iron, silicon, manganese, molybdenum, boron, aluminum, tin, chromium, vanadium, zirconium, magnesium, niobium, palladium, nickel, tantalum, tungsten, neodymium, ruthenium and copper, if a plurality of elements are measured simultaneously, a large amount of time is consumed, the detection period is long, and the detection method is contradictory to the requirements of efficient and rapid detection for producing high-quality titanium sponge and titanium alloy at the present stage. Secondly, part of element detection standards do not meet the detection requirements of the industry at the present stage. For example, according to the requirements of the new national standard (GB/T2524-2019) of the titanium sponge, the quality grade in the standard is 0 A The impurity silicon element of the sponge titanium is specified to be less than or equal to 0.01 percent, and the lower limit of the determination in GB/T4698.3-2017 silicon amount determination by molybdenum blue photometry of chemical analysis methods of the sponge titanium, the titanium and the titanium alloy is 0.010 percent, so that the new standard inspection requirements can not be met. GB/T4698.21 adopts direct current arc atomic emission spectrometry (DCP-AES) to detect 10 chemical components of manganese, chromium, nickel, aluminum, molybdenum, tin, vanadium, yttrium, copper and zirconium in titanium alloy, the detection element range is 0.001-0.2%, the problems existing in the method mainly have two aspects, firstly, the detection method adopts a sample in a powder state to be injected, the sample in a cut shape needs to be acidified, carbonized with graphite powder in a high-temperature state and then ground into a powder sample for detection, the treatment process is complex, a certain amount of impurities are brought in, and the uncertain factors of the detection result are more; secondly, the detection method is lack of more added elements for detection, for example, the detection of vanadium and aluminum in the titanium alloy TC4 is not applicable.
SN/T3910-2014 inductively coupled plasma emission spectrometry for measuring manganese, chromium, nickel, aluminum, molybdenum, tin, vanadium and copper in titanium sponge, titanium and titanium alloy, the standard can simultaneously measure 8 elements such as manganese, chromium, nickel and the like in titanium alloy, although the detection efficiency can be improved to a certain extent compared with GB/T4698 series, elements such as silicon, boron and the like with higher detection difficulty are not included in the detection range of the method. Although the YS/T1262-2018 Standard of inductively coupled plasma atomic emission spectrometry for measuring the contents of multiple elements in the chemical analysis method of titanium sponge, titanium and titanium alloy can measure multiple elements simultaneously, neodymium in the titanium alloy cannot be measured, and in addition, in the standard, the neodymium is dissolved in an open beaker for sample pretreatment, the dissolving temperature is required to be not higher than 70 ℃, the temperature is not easy to control, and in the open beaker, hydrochloric acid and hydrofluoric acid are added to react with a titanium alloy sample violently, the solution temperature is quickly increased, and silicon loss is easily caused.
At present, foreign countries, the advanced countries of the titanium industrial technology generally adopt the ICP-AES method for detecting impurity metal elements in titanium sponge, but except the photometry and atomic spectrum absorption method standard methods, the standard methods and patents for measuring 19 elements such as silicon, boron, zirconium, yttrium, niobium, tantalum, ruthenium, neodymium, tungsten and the like in titanium sponge and titanium alloy by the ICP-AES method of related countries are not found, so the detailed operation process is not clear. ASTM E2994-16 issued in the United states analyzes 11 elements in titanium and titanium alloy by Spark atomic emission spectrometry (Spark-AES) and glow discharge atomic emission spectrometry (GD-AES), but does not relate to elements such as niobium, tantalum, boron, tungsten and the like, and ASTM E2371-21 standard provides a method for measuring 19 elements in titanium and titanium alloy by ICP-AES or DCP-AES, the standard adopts hydrochloric acid + hydrofluoric acid + nitric acid mixed acid dissolved sample, pure titanium is taken as a substrate, reference analysis lines, linear ranges and detection mean values and accuracies of a plurality of laboratories are given for each element, but the method cannot detect neodymium (Nd) because of F-and Nd 3+ Form a hardly soluble HCl and HNO 3 NdF (b) of 3 The Nd detection result is lowered.
Disclosure of Invention
The invention aims to provide a method for accurately and quickly detecting 19 medium and trace elements in titanium sponge and titanium alloy.
The technical scheme adopted by the invention for solving the technical problem is as follows: the method for measuring the contents of 19 elements in the titanium sponge and the titanium alloy by using the inductively coupled plasma emission spectrometry comprises the following steps:
a. sample digestion: weighing 0.20g +/-0.0001 g of sample, placing the sample in a microwave digestion tank, adding 15.0mL of hydrochloric acid, 5.0mL of hydrofluoric acid, 2.0mL of nitric acid and 0.5mL of perchloric acid, placing the digestion tank in a microwave digestion instrument, digesting according to set conditions, taking out the sample after digestion, and cooling the sample to room temperature;
b. and (3) volume fixing: b, fixing the volume of the solution treated in the step a to 100mL by using pure water to obtain a solution 1 for measuring elements with the content of less than or equal to 1.0%; taking 10mL of solution 1, and fixing the volume to 100mL by using pure water to obtain solution 2 for measuring elements with the content of more than 1.0%;
c. drawing a standard curve: respectively preparing standard curve solutions with the element content of less than or equal to 1.0% and the element content of more than 1.0%, introducing the standard curve solutions into an inductively coupled plasma spectrometer, measuring according to instrument detection conditions, and drawing a standard curve;
d. the establishment of the detection method comprises the following steps: reasonably selecting the detection conditions of the instrument according to an instrument operation manual, selecting an Ar420.073 line as an internal standard, and establishing an instrument detection method;
e. and (3) sample detection: and c, respectively introducing the solution 1 and the solution 2 obtained in the step b into an inductively coupled plasma spectrometer to test according to instrument detection conditions, and determining the content of 19 elements of iron, silicon, manganese, molybdenum, boron, aluminum, tin, chromium, vanadium, zirconium, magnesium, niobium, palladium, nickel, tantalum, tungsten, neodymium, ruthenium and copper in the titanium sponge and the titanium alloy according to a standard curve.
In the step a, the hydrochloric acid is a 1: 1 hydrochloric acid solution, the hydrofluoric acid is a 1: 1 hydrofluoric acid solution, the nitric acid is a 1: 1 nitric acid solution, and the perchloric acid is a perchloric acid solution with a concentration of 70%.
In the step a, the set conditions are that the initial temperature is 40 ℃, the temperature is kept for 5min, the temperature is increased to 120 ℃ at the speed of 8 ℃/min, and the temperature is kept for 15min.
In the step b, the volume is determined by using a 100mL polyethylene volumetric flask.
In the step c, the preparation method of the standard curve solution with the element content less than or equal to 1.0 percent comprises the following steps: respectively taking 6 parts of pure titanium (0.20 g +/-0.0001 g of each part), digesting according to the sample digestion procedure in the step a, transferring to a 100mL polyethylene volumetric flask, adding the element corresponding single element standard solution according to the standard curve point concentration, and then fixing the volume to 100mL by using pure water to obtain the standard curve solution with the element content being less than or equal to 1.0%.
In the step c, the preparation method of the standard curve solution with the element content of more than 1.0 percent comprises the following steps: taking 0.20g +/-0.0001 g of pure titanium, digesting according to the sample digestion procedure in the step a, transferring the sample to a 100mL polyethylene volumetric flask, using pure water to fix the volume to 100mL, respectively taking 10mL from the sample, adding the sample to 6 100mL polyethylene volumetric flasks, adding the corresponding element standard solution according to the concentration of the standard curve point, and then using pure water to fix the volume to 100mL to obtain the standard curve solution with the element content being more than 1.0%.
In the steps c, d and e, the conditions are set as follows: the analysis power is 1300W, the pump speed is 1.5mL/min, the plasma flow is 15L/min, the auxiliary gas flow is 0.2L/min, the atomizer flow is 0.55L/min, and the observation distance is 15mm.
The beneficial effects of the invention are: the impurity element content in the titanium sponge is generally low (0.01-0.30%), while the content difference of each element in the titanium alloy is large (0.01-47.0%), and the standard curve ranges are different due to the large content difference, so that the national standard is respectively used for measurement. The inductively coupled plasma emission spectrometer adopted by the invention has high sensitivity (meeting the detection requirement of low-content elements), the observation mode can select a proper observation mode (meeting the detection requirement of high-content elements) according to different contents of the elements to be detected, and the simultaneous detection of different content ranges of 19 elements is well solved by optimizing method parameters such as selecting proper sample amount, analyzing spectral lines, properly diluting high-concentration elements (meeting the detection of high-content elements without influencing the detection sensitivity of low-content elements) and proper background correction technology.
At present, silicon in titanium sponge and titanium alloy is subjected to a silicon-molybdenum-blue spectrophotometry, and an inductively coupled plasma emission spectrometry is not adopted, because titanium alloy is generally dissolved by hydrofluoric acid, silicon in a sample reacts with hydrofluoric acid to easily generate silicon tetrafluoride (gas is easily volatilized from the solution), and silicon loss is caused. The invention adopts the low-temperature microwave digestion technology to effectively solve the loss of silicon in a hydrofluoric acid solvent and realizes the detection of silicon by an inductively coupled plasma emission spectrometry.
The invention takes hydrochloric acid, hydrofluoric acid, nitric acid and perchloric acid as solvents, adopts a microwave digestion technology to process a sample, takes an Ar420.073 line as an internal standard, takes high-purity titanium (titanium is more than or equal to 99.98%) as a matrix for matching, combines an MSF (multi-spectrum fitting technology), adopts a standard curve method for quantification, and establishes a method for measuring the contents of 19 elements (iron, silicon, manganese, molybdenum, boron, aluminum, tin, chromium, vanadium, zirconium, magnesium, niobium, palladium, nickel, tantalum, tungsten, neodymium, ruthenium and copper) in titanium sponge and titanium alloy by optimizing equipment parameters and pertinently eliminating the mutual influence of the matrix and all detected elements.
Detailed Description
The technical solution of the present invention can be specifically implemented in the following manner.
The method for measuring the contents of 19 elements in the titanium sponge and the titanium alloy by using the inductively coupled plasma emission spectroscopy comprises the following steps:
a. sample digestion: weighing 0.20g +/-0.0001 g of sample, placing the sample in a microwave digestion tank, adding 15.0mL of hydrochloric acid, 5.0mL of hydrofluoric acid, 2.0mL of nitric acid and 0.5mL of perchloric acid, placing the digestion tank in a microwave digestion instrument, digesting according to set conditions, taking out the sample after digestion is finished, and cooling the sample to room temperature;
b. and (3) volume fixing: b, fixing the volume of the solution treated in the step a to 100mL by pure water to obtain a solution 1 for measuring elements with the content less than or equal to 1.0%; taking 10mL of solution 1, and fixing the volume to 100mL by using pure water to obtain solution 2 for measuring elements with the content of more than 1.0%;
c. drawing a standard curve: respectively preparing standard curve solutions with the element content of less than or equal to 1.0% and the element content of more than 1.0%, measuring by using an inductively coupled plasma spectrometer, and drawing a standard curve;
d. the establishment of the detection method comprises the following steps: reasonably selecting the detection conditions of the instrument according to an instrument operation manual, selecting an Ar420.073 line as an internal standard, and establishing an instrument detection method;
e. and (3) detecting a sample: and c, respectively introducing the solution 1 and the solution 2 obtained in the step b into an inductively coupled plasma spectrometer for testing according to set conditions, and determining the content of 19 elements of iron, silicon, manganese, molybdenum, boron, aluminum, tin, chromium, vanadium, zirconium, magnesium, niobium, palladium, nickel, tantalum, tungsten, neodymium, ruthenium and copper in the titanium sponge and the titanium alloy according to a standard curve.
In the step a, the hydrochloric acid is a 1: 1 hydrochloric acid solution, the hydrofluoric acid is a 1: 1 hydrofluoric acid solution, the nitric acid is a 1: 1 nitric acid solution, and the perchloric acid is a perchloric acid solution with a concentration of 70%.
The 1: 1 solution is formed by mixing solute and water in a volume ratio of 1: 1.
In the step a, the set conditions are that the initial temperature is 40 ℃, the temperature is kept for 5min, the temperature is increased to 120 ℃ at the speed of 8 ℃/min, and the temperature is kept for 15min.
In the step b, the volume is determined by using a 100mL polyethylene volumetric flask.
In the step c, the preparation method of the standard curve solution with the element content less than or equal to 1.0 percent comprises the following steps: respectively taking 6 parts of pure titanium (0.20 g +/-0.0001 g of each part), digesting according to the sample digestion procedure in the step a, transferring the sample to a 100mL polyethylene volumetric flask, adding the element corresponding single element standard solution according to the standard curve point concentration, and then fixing the volume to 100mL by using pure water to obtain the standard curve solution with the element content less than or equal to 1.0%, wherein the standard curve point concentration is shown in Table 1.
TABLE 1 Standard Curve Point concentration (μ g/mL) with element content ≤ 1.0%
| Standard point | Measuring element | Concentration of |
| Standard Point 0 | Fe,Si,Mn,Mo,B,Al,Sn,Cr,V,Zr,Mg,Nb,Pd,Ni,Ta,W,Nd,Ru,Cu | 0 |
| Standard Point 1 | Fe,Si,Mn,Mo,B,Al,Sn,Cr,V,Zr,Mg,Nb,Pd,Ni,Ta,W,Nd,Ru,Cu | 0.2 |
| Standard Point 2 | Fe,Si,Mn,Mo,B,Al,Sn,Cr,V,Zr,Mg,Nb,Pd,Ni,Ta,W,Nd,Ru,Cu | 0.5 |
| Standard Point 3 | Fe,Si,Mn,Mo,B,Al,Sn,Cr,V,Zr,Mg,Nb,Pd,Ni,Ta,W,Nd,Ru,Cu | 2.0 |
| Standard Point 4 | Fe,Si,Mn,Mo,B,Al,Sn,Cr,V,Zr,Mg,Nb,Pd,Ni,Ta,W,Nd,Ru,Cu | 8.0 |
| Standard Point 5 | Fe,Si,Mn,Mo,B,Al,Sn,Cr,V,Zr,Mg,Nb,Pd,Ni,Ta,W,Nd,Ru,Cu | 20.0 |
In the step c, the preparation method of the standard curve solution with the element content being more than 1.0 percent comprises the following steps: taking 0.20g +/-0.0001 g of pure titanium, digesting according to the sample digestion procedure in the step a, transferring the sample to a 100mL polyethylene volumetric flask, using pure water to fix the volume to 100mL, respectively taking 10mL of pure titanium, adding the sample to 6 100mL polyethylene volumetric flasks, adding the corresponding element standard solution according to the standard curve point concentration, then using pure water to fix the volume to 100mL, and obtaining the standard curve solution with the element content being more than 1.0%, wherein the standard curve point concentration is shown in Table 2.
TABLE 2 Standard Curve Point concentrations (μ g/mL) for element content > 1.0%
In the above steps c, d, e, the setting conditions are: the analysis power is 1300W, the pump speed is 1.5mL/min, the plasma flow is 15L/min, the auxiliary gas flow is 0.2L/min, the atomizer flow is 0.55L/min, and the observation distance is 15mm.
Preferably, in step d, the set conditions in the inductively coupled plasma spectrometer are as shown in table 3.
TABLE 3 measurement conditions of respective elements in titanium sponge and titanium alloy
The inductively coupled plasma emission spectrometry has the advantages of simultaneous measurement of multiple elements and high sensitivity; the method comprises the following steps of (1) totally 19 elements according to the product standards and the brands of the current titanium sponge (GB/T2425-2019) and titanium alloy (GB/T3620.1-2016); at present, the 19 elements in titanium sponge and titanium alloy can be detected by 18 detection methods, and if a plurality of elements in titanium alloy are detected simultaneously, a large amount of labor cost, material cost and time cost are consumed. The method can simultaneously detect 19 elements of the titanium sponge and the titanium alloy, not only improves the detection efficiency, but also greatly saves the labor and material cost.
The inductively coupled plasma emission spectrometer has two optional vertical and horizontal observation modes (the vertical observation mode has less interference, smaller matrix effect and interference, particularly on organic samples, and has good detection limit on complex matrixes); at present, the elements in the titanium alloy measured by national standards (GB/T4698 series and YS/T1262-2018) are dissolved in a sample by adopting an open beaker, and in an open environment, a blank is easily polluted by foreign impurities and is uncontrollable; according to the method, the sample is digested in the closed environment of the microwave digestion tank (the microwave digestion technology is applied to the field of titanium sponge and titanium alloy detection for the first time), the blank of the sample is low and controllable (according to a detection limit calculation formula, DL (detection limit) =3 xRSD (relative standard deviation of blank intensity of an element to be detected) × BEC (background equivalent concentration of the element to be detected), the lower the blank of the sample is, the lower the RSD and BEC are, and the lower the calculated element detection limit is).
It can be understood by those skilled in the art that the method for measuring the contents of 19 elements in titanium sponge and titanium alloy by inductively coupled plasma emission spectroscopy according to the present invention uses quantitative values to express each process value in the claims, in order to ensure the clarity and conciseness of the technical solution. On the basis of the technical scheme of the invention, the technical scheme of the invention is also equivalent to the technical scheme of the invention that the technical parameters are proportionally increased or reduced by a person skilled in the art, so that the technical effect of the invention can be achieved, and the technical effect also belongs to the protection scope of the invention.
The technical solution and effects of the present invention will be further described below by way of practical examples.
Examples
Example 1
1. Accurately weighing 0.20 +/-0.0001 g of sample;
2. placing a sample in a microwave digestion tank, adding 15.0mL of hydrochloric acid (1 + 1), 5.0mL of hydrofluoric acid (1 + 1), 2.0mL of nitric acid (1 + 1) and 0.5mL of perchloric acid, placing the digestion tank in a microwave digestion instrument for digestion according to the following temperature-rising program: the initial temperature is 40 ℃, the temperature is kept for 5min, the temperature is increased to 120 ℃ at the speed of 8 ℃/min, the temperature is kept for 15min, then the temperature is cooled to room temperature, the solution is taken out and transferred into a 100mL polyethylene measuring flask, pure water is used for constant volume and uniform mixing for standby (solution 1), and for elements with the content less than or equal to 1.0 percent, the solution 1 is directly used for machine measurement; for elements with the content of more than 1.0%, 10mL to 100mL of polyethylene solution bottles are taken from the solution 1, pure water is used for constant volume and uniform mixing for standby application (solution 2), and high-purity titanium is used as a blank along with a sample;
3. selecting an analysis method for the prepared sample solution, and measuring by an inductively coupled plasma spectrometer;
4. the results are shown in Table 4.
TABLE 4 statistical table/% of the results of the measurements of four different titanium alloy standard samples according to the method of the invention
Example 2
1. Accurately weighing 0.20 + -0.0001 g of sample (IARM 337A) (comparing results of different laboratories);
2. placing a sample in a microwave digestion tank, adding 15.0mL of hydrochloric acid (1 + 1), 5.0mL of hydrofluoric acid (1 + 1), 2.0mL of nitric acid (1 + 1) and 0.5mL of perchloric acid, placing the digestion tank in a microwave digestion instrument for digestion according to the following temperature-rising program: the initial temperature is 40 ℃, the temperature is kept for 5min, the temperature is raised to 120 ℃ at the speed of 8 ℃/min, the temperature is kept for 15min, then the temperature is cooled to room temperature, the temperature is taken out and transferred into a 100mL polyethylene measuring flask, pure water is used for constant volume and uniform mixing for standby (solution 1), and for elements with the content less than or equal to 1.0 percent, the solution 1 is directly used for measuring on a machine; for elements with the content of more than 1.0%, taking 10mL to 100mL polyethylene solution bottles from the solution 1, using pure water to fix the volume and uniformly mixing for standby (solution 2), and using high-purity titanium as a blank along with a sample;
3. selecting an analysis method for the prepared sample solution, and measuring by an inductively coupled plasma spectrometer;
4. the results are shown in Table 5:
TABLE 5 statistical table/% of the results of the different laboratory comparison measurements
Example 3
1. Accurately weighing 0.20 +/-0.0001 g of samples (IARM 269B and IARM 300B) (comparing different detection methods);
2. placing the sample in a microwave digestion tank, adding 15.0mL hydrochloric acid (1 + 1), 5.0mL hydrofluoric acid (1 + 1), 2.0mL nitric acid (1 + 1) and 0.5mL perchloric acid, placing the digestion tank in a microwave digestion instrument, and digesting according to the following temperature-raising program: the initial temperature is 40 ℃, the temperature is kept for 5min, the temperature is raised to 120 ℃ at the speed of 8 ℃/min, the temperature is kept for 15min, then the temperature is cooled to room temperature, the temperature is taken out and transferred into a 100mL polyethylene measuring flask, pure water is used for constant volume and uniform mixing for standby (solution 1), and for elements with the content less than or equal to 1.0 percent, the solution 1 is directly used for measuring on a machine; for elements with the content of more than 1.0%, 10mL to 100mL of polyethylene solution bottles are taken from the solution 1, pure water is used for constant volume and uniform mixing for standby application (solution 2), and high-purity titanium is used as a blank along with a sample;
3. selecting an analysis method for the prepared sample solution, and measuring by an inductively coupled plasma spectrometer;
4. the results are shown in Table 6:
TABLE 6 statistical table of comparison data of different detection methods
Claims (7)
1. The method for measuring the contents of 19 elements in the titanium sponge and the titanium alloy by using the inductively coupled plasma emission spectrometry is characterized by comprising the following steps of:
a. sample digestion: weighing 0.20g +/-0.0001 g of sample, placing the sample in a microwave digestion tank, adding 15.0mL of hydrochloric acid, 5.0mL of hydrofluoric acid, 2.0mL of nitric acid and 0.5mL of perchloric acid, placing the digestion tank in a microwave digestion instrument, digesting according to set conditions, taking out the sample after digestion is finished, and cooling the sample to room temperature;
b. and (3) volume fixing: b, fixing the volume of the solution treated in the step a to 100mL by using pure water to obtain a solution 1 for measuring elements with the content of less than or equal to 1.0%; taking 10mL of the solution 1, and fixing the volume to 100mL by pure water to obtain a solution 2 for measuring elements with the content of more than 1.0%;
c. drawing a standard curve: respectively preparing standard curve solutions with the element content of less than or equal to 1.0% and the element content of more than 1.0%, introducing the standard curve solutions into an inductively coupled plasma spectrometer, measuring according to instrument detection conditions, and drawing a standard curve;
d. the detection method is established as follows: reasonably selecting the detection conditions of the instrument according to an instrument operation manual, selecting an Ar420.073 line as an internal standard, and establishing an instrument detection method;
e. and (3) sample detection: and c, respectively introducing the solution 1 and the solution 2 obtained in the step b into an inductively coupled plasma spectrometer to test according to instrument detection conditions, and determining the content of 19 elements of iron, silicon, manganese, molybdenum, boron, aluminum, tin, chromium, vanadium, zirconium, magnesium, niobium, palladium, nickel, tantalum, tungsten, neodymium, ruthenium and copper in the titanium sponge and the titanium alloy according to a standard curve.
2. The method for measuring the contents of 19 elements in titanium sponge and titanium alloy by using the inductively coupled plasma emission spectroscopy method as claimed in claim 1, wherein the method comprises the following steps: in the step a, the hydrochloric acid is a 1: 1 hydrochloric acid solution, the hydrofluoric acid is a 1: 1 hydrofluoric acid solution, the nitric acid is a 1: 1 nitric acid solution, and the perchloric acid is a perchloric acid solution with the concentration of 70%.
3. The method for measuring the contents of 19 elements in titanium sponge and titanium alloy by using the inductively coupled plasma emission spectroscopy method as claimed in claim 1, wherein the method comprises the following steps: in the step a, the set conditions are that the initial temperature is 40 ℃, the temperature is kept for 5min, the temperature is increased to 120 ℃ at the speed of 8 ℃/min, and the temperature is kept for 15min.
4. The method for measuring the contents of 19 elements in titanium sponge and titanium alloy by using the inductively coupled plasma emission spectroscopy method as claimed in claim 1, wherein the method comprises the following steps: in the step b, a 100mL polyethylene volumetric flask is adopted for constant volume.
5. The method for measuring the contents of 19 elements in titanium sponge and titanium alloy by using the inductively coupled plasma emission spectroscopy method as claimed in claim 1, wherein the method comprises the following steps: in the step c, the preparation method of the standard curve solution with the element content less than or equal to 1.0 percent comprises the following steps: respectively taking 6 parts of 0.20g +/-0.0001 g of pure titanium, digesting according to the sample digestion procedure in the step a, transferring to a 100mL polyethylene volumetric flask, adding the element corresponding single element standard solution according to the standard curve point concentration, and then using pure water to fix the volume to 100mL to obtain the standard curve solution with the element content being less than or equal to 1.0%.
6. The method for measuring the contents of 19 elements in titanium sponge and titanium alloy by using the inductively coupled plasma emission spectroscopy method as claimed in claim 1, wherein the method comprises the following steps: in the step c, the preparation method of the standard curve solution with the element content of more than 1.0 percent comprises the following steps: taking 0.20g +/-0.0001 g of pure titanium, digesting according to the sample digestion procedure in the step a, transferring the sample to a 100mL polyethylene volumetric flask, using pure water to fix the volume to 100mL, respectively taking 10mL from the sample, adding the sample to 6 100mL polyethylene volumetric flasks, adding the corresponding element standard solution according to the concentration of the standard curve point, and then using pure water to fix the volume to 100mL to obtain the standard curve solution with the element content being more than 1.0%.
7. The method for measuring the contents of 19 elements in titanium sponge and titanium alloy by using the inductively coupled plasma emission spectroscopy method as claimed in claim 1, wherein the method comprises the following steps: in the steps c, d and e, the detection conditions of the instrument are as follows: the analysis power is 1300W, the pump speed is 1.5mL/min, the plasma flow is 15L/min, the auxiliary gas flow is 0.2L/min, the atomizer flow is 0.55L/min, and the observation distance is 15mm.
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