CN116558935A - Method for measuring trace impurity elements in high-purity tantalum - Google Patents
Method for measuring trace impurity elements in high-purity tantalum Download PDFInfo
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- 239000012535 impurity Substances 0.000 title claims abstract description 145
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000012360 testing method Methods 0.000 claims abstract description 62
- 238000009616 inductively coupled plasma Methods 0.000 claims abstract description 30
- 239000012488 sample solution Substances 0.000 claims abstract description 23
- 238000005259 measurement Methods 0.000 claims abstract description 15
- 239000000523 sample Substances 0.000 claims description 54
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- 239000011550 stock solution Substances 0.000 claims description 24
- 238000001514 detection method Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 11
- 239000012086 standard solution Substances 0.000 claims description 6
- 238000012795 verification Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000889 atomisation Methods 0.000 claims description 4
- 238000004441 surface measurement Methods 0.000 claims description 4
- 239000012085 test solution Substances 0.000 claims description 4
- 238000012937 correction Methods 0.000 claims description 3
- 238000002372 labelling Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 10
- 238000001819 mass spectrum Methods 0.000 abstract description 5
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000005464 sample preparation method Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013100 final test Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water 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
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4044—Concentrating samples by chemical techniques; Digestion; Chemical decomposition
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The application provides a method for measuring trace impurity elements in high-purity tantalum, which comprises the following steps: preparing a tantalum sample solution to be tested; respectively establishing standard curves of impurity elements to be detected; placing a tantalum sample solution to be tested in an inductively coupled plasma mass spectrometer, and respectively testing to obtain the signal intensity of impurity elements to be tested; and respectively calculating to obtain the concentration content value of the impurity element to be detected in the tantalum sample solution to be detected according to the signal intensity of the impurity element to be detected and the standard curve of the impurity element to be detected. The method can finish the content measurement of 9 chemical impurity elements required to be measured in the high-purity tantalum powder at one time, greatly shortens the test duration and effectively improves the test efficiency. The method enhances the controllability of the mass spectrum testing process and improves the stability of the testing result between parallel samples, thereby greatly improving the accuracy of impurity element determination.
Description
Technical Field
The application relates to the technical field of impurity detection, in particular to a method for measuring trace impurity elements in high-purity tantalum.
Background
The content of chemical impurities is an important index of tantalum powder for capacitors, and the content of the chemical impurities directly influences the leakage current of the capacitors, the voltage of flash voltage and the reliability and the service life of products, so that accurate and efficient determination of the chemical impurities in the tantalum powder is particularly important.
The purity of the high-purity tantalum base is extremely high, the content of other chemical impurity elements is extremely low, and the impurity content ranges from 1 ppm to 30 ppm. The traditional test method is adopted as a water sample preparation method, the content of the sample is low, the sample is easily influenced by the external factors such as equipment state, the purity of the reagent and water used, the instrument and vessel used for the test and the like, the sample preparation process is overlong, and the residual HF and HNO are required to be removed during the sample dissolution in order to eliminate the matrix effect 3 The gas is kept warm for more than 2 hours, so that the invasion of impurities is easy to cause; in addition, the test stability of the parallel sample in the test process is poor, so that the test result is difficult to judge, and finally the test efficiency is low.
Disclosure of Invention
The method can be used for measuring the content of 9 chemical impurity elements required to be measured in the high-purity tantalum powder at one time, so that the testing time is greatly shortened, and the testing efficiency is effectively improved. The method enhances the controllability of the mass spectrum testing process and improves the stability of the testing result between parallel samples, thereby greatly improving the accuracy of impurity element determination.
The application provides a method for measuring trace impurity elements in high-purity tantalum, which comprises the following steps:
preparing a tantalum sample solution to be tested;
respectively establishing standard curves of impurity elements to be detected;
placing the tantalum sample solution to be tested in an inductively coupled plasma mass spectrometer, and respectively testing to obtain the signal intensity of the impurity element to be tested;
and respectively calculating the concentration content value of the impurity element to be detected in the tantalum sample solution to be detected according to the signal intensity of the impurity element to be detected and the standard curve of the impurity element to be detected.
In one embodiment, the preparing a tantalum sample solution to be tested includes:
weighing a tantalum sample with preset mass, and adding nitric acid with preset capacity;
after the tantalum sample is fully infiltrated, dropwise adding hydrofluoric acid to fully dissolve the tantalum sample, and adopting graphite to digest for a preset time;
and preparing the tantalum sample to-be-measured solution after the tantalum sample is fully dissolved, and fixing the volume in a volumetric flask.
In one embodiment, before the preparing the tantalum sample solution to be tested, the method further comprises:
and dissolving high-purity tantalum by using nitric acid and hydrofluoric acid, and digesting by using graphite to prepare a stock solution with preset concentration, wherein the purity of the high-purity tantalum is more than 99.8%.
In an embodiment, the establishing standard curves of the impurity elements to be measured respectively includes:
adding current impurity elements to be detected with different preset concentrations into the stock solution according to the concentration range of each impurity element to be detected;
respectively testing the corresponding signal intensity of the impurity element to be tested at each preset concentration by the inductively coupled plasma mass spectrometer;
and establishing a standard curve of each impurity element to be detected according to different preset concentrations and the corresponding signal intensity of the current impurity element to be detected under each preset concentration.
In one embodiment, after the placing the tantalum sample solution to be tested in an inductively coupled plasma mass spectrometer, the method further comprises:
and determining preset detection conditions according to the full-axis scanning surface measurement setting interface, wherein the preset detection conditions comprise preset radio frequency power, preset cooling air flow, preset atomization air flow, preset pump speed, preset sample lifting rate, preset measurement mode and preset scanning times.
In an embodiment, an abscissa of the standard curve of the impurity element to be measured represents a concentration content value of the impurity element to be measured, an ordinate of the standard curve of the impurity element to be measured represents a signal intensity of the impurity element to be measured, and the concentration content value of the impurity element to be measured in the tantalum sample to be measured is calculated according to the signal intensity of the impurity element to be measured and the standard curve of the impurity element to be measured, respectively, including:
substituting the signal intensity of the impurity element to be detected into the standard curve of the impurity element to be detected, and respectively calculating to obtain the concentration content value of the impurity element to be detected in the tantalum sample solution to be detected.
In one embodiment, the method further comprises:
selecting target detection tantalum powder, and performing a labeling recovery verification test;
and determining the recovery rate of the target detection tantalum powder according to the test result.
In one embodiment, the predetermined concentration is 0ppb, 1ppb, 5ppb, 20ppb, 100ppb.
In one embodiment, the method further comprises: an internal standard solution was prepared for concentration correction treatment.
In one embodiment, the isotopes selected from the impurity elements to be detected are 24Mg, 48Ti, 52Cr, 55Mn, 56Fe, 60Ni, 93Nb, 95Mo, 184W.
In the scheme, the ICP-MS measuring method special for the high-purity tantalum-based chemical impurities uses a standard curve stock solution sample preparation method, so that the matrix effect influence caused by high-purity tantalum metal base effect can be effectively eliminated, the established standard curve is simple and higher in accuracy, and the measuring reliability of impurity elements is improved.
According to the method, the ICP-MS equipment is used for completing the content measurement of 9 chemical impurity elements required to be measured in the high-purity tantalum powder at one time, so that the test duration is greatly shortened, and the test efficiency is effectively improved. The method enhances the controllability of the mass spectrum testing process and improves the stability of the testing result between parallel samples, thereby greatly improving the accuracy of impurity element determination.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly explain the drawings that are required to be used in the embodiments of the present application.
FIG. 1 is a schematic diagram of the configuration of an inductively coupled plasma mass spectrometer of the present application;
FIG. 2 is a schematic flow chart of a method for determining trace impurity elements in high purity tantalum according to an embodiment of the present application;
FIG. 3 is a schematic representation of device sensitivity characterization in STD mode according to one embodiment of the present application;
FIG. 4 is a standard curve of 24Mg impurity element provided in one embodiment of the present application;
FIG. 5 is a standard curve of 48Ti impurity elements according to one embodiment of the present application;
FIG. 6 is a standard curve of a 52Cr impurity element according to an embodiment of the present application;
FIG. 7 is a standard curve of a 55Mn impurity element according to an embodiment of the present application;
FIG. 8 is a standard curve of the impurity element 56Fe according to one embodiment of the present application;
FIG. 9 is a standard curve of a 60Ni impurity element according to an embodiment of the present application;
FIG. 10 is a standard curve of 93Nb impurity element provided in an embodiment of the present application;
FIG. 11 is a standard curve of a 95Mo impurity element provided in one embodiment of the present application;
fig. 12 is a standard curve of 184W impurity element provided in an embodiment of the present application.
Detailed Description
The terms "first," "second," "third," and the like are used merely for distinguishing between descriptions and not for indicating a sequence number, nor are they to be construed as indicating or implying relative importance.
The technical solutions of the present application will be described below with reference to the accompanying drawings.
Inductively coupled plasma mass spectrometry (hereinafter referred to as ICP-MS) is one of the most rapidly developed trace element analysis techniques. ICP-MS has been widely used in various fields worldwide since the eighties' commercialization. This technique enables rapid measurements of multiple elements at ultra trace levels. Has the advantages of extremely low detection limit, less interference, overwhelming isotope analysis and the like. A four-stage rod inductively coupled plasma mass spectrometer used in the present application is shown in fig. 1. The content of impurity elements in the high-purity tantalum sample can be detected simultaneously by on-line detection of the inductively coupled plasma mass spectrometer, and the method is simple in process, high in anti-interference performance and high in precision.
Referring to fig. 2, a flow chart of a method for determining trace impurity elements in high purity tantalum is provided, and the method includes steps S210-S240:
step S210: and preparing a tantalum sample solution to be tested.
Because the tantalum sample used in the application is high-purity tantalum, the purity of the high-purity tantalum is more than 99.8%, the background of a high-purity tantalum matrix is high, and the matrix effect greatly influences the test result. Therefore, in order to effectively eliminate the influence of tantalum-based impurities, high purity tantalum needs to be treated to prepare a stock solution with a certain concentration.
In one embodiment, prior to step S210, high purity tantalum is dissolved using nitric acid and hydrofluoric acid and digested with graphite to prepare a stock solution of a predetermined concentration.
Exemplary, 0.6 to 1g of high purity tantalum (Ta (OH) is weighed 5 ) Drying, using 6ml of ultra-pure nitric acid HNO 3 And 70 drops of ultrapure hydrofluoric acid HF are dissolved, graphite is digested for 10min, and then the solution is fixed in a 50ml pipette to serve as a stock solution for standby. The dilution factor is 30-50 times.
Next, a tantalum sample test solution is prepared. The tantalum powder is prepared from high-purity nitric acid HNO 3 (nitric acid concentration > 99%) and hydrofluoric acid HF (hydrofluoric acid concentration > 99%) are completed together. The tantalum sample solution is more stable under the acidic environment, and the vigorous formation during the addition of HF can be inhibited to a certain extent in the presence of liquidAnd the chemical reaction reduces the process loss in the sample dissolving process and improves the detection accuracy.
In one embodiment, the step S210 specifically includes: step S211 to step S213.
Step S211: a tantalum sample with preset mass is weighed, and nitric acid with preset capacity is added.
Illustratively, the tantalum sample has a mass of 0.1 to 0.3g. Added high-purity nitric acid HNO 3 The amount of (2) is 0.5-3 ml.
Step S212: after the tantalum sample is fully infiltrated, dropwise adding hydrofluoric acid to fully dissolve the tantalum sample, and adopting graphite to digest for a preset time.
Illustratively, the HF hydrofluoric acid is added in an amount of 12-20 drops and the graphite digestion time is 0.3-1h.
Step S213: and preparing a tantalum sample solution to be measured after the tantalum sample is fully dissolved, and fixing the volume in a volumetric flask.
Because the sample to be tested of the inductively coupled plasma mass spectrometer needs to be liquid and the tantalum powder sample is solid, the tantalum powder is required to be dissolved in advance, so that the tantalum powder is processed into a liquid solution to be tested. In the dissolving process, in the embodiment, the sequence of adding the high-purity acid solution is changed, namely, the high-purity nitric acid HNO is added first 3 After the sample is fully infiltrated, adding hydrofluoric acid HF for fully dissolving, and carrying out graphite digestion to obtain the solution to be measured.
Step S220: and respectively establishing standard curves of impurity elements to be detected.
The isotopes selected from impurity elements to be detected in the tantalum sample in the application are 9 kinds of 24Mg, 48Ti, 52Cr, 55Mn, 56Fe, 60Ni, 93Nb, 95Mo and 184W. In testing the content of these 9 impurity elements, it is necessary to prepare a standard curve for each impurity element to be measured separately.
In one embodiment, the step S220 specifically includes step S221 to step S223:
step S221: and adding the current impurity elements to be detected with different preset concentrations into the stock solution according to the concentration range of each impurity element to be detected.
In one embodiment, the predetermined concentration is 0ppb, 1ppb, 5ppb, 20ppb, 100ppb.
In this embodiment, when a standard curve of the impurity element to be measured is established, the selected solution is the stock solution described above, and the concentration gradient of the standard curve may be set to 0ppb (blank), 1ppb, 5ppb, 20ppb, 100ppb. The national standard substance is used to prepare the standard curve for standby.
Illustratively, taking the 24Mg element as an example, 0ppb of 24Mg, 1ppb of 24Mg, 5ppb of 24Mg, 20ppb of 24Mg, and 100ppb of 24Mg are added to the stock solution.
Taking 48Ti as an example, 0ppb of 48Ti, 1ppb of 48Ti, 5ppb of 48Ti, 20ppb of 48Ti, and 100ppb of 48Ti are added to the stock solution.
The concentration of the standard curves of 52Cr, 55Mn, 56Fe, 60Ni, 93Nb, 95Mo, 184W was prepared by the same method.
In one embodiment, the concentration calibration process may be performed by preparing the internal standard solution at the same time when the standard curve is established.
Illustratively, the internal standard elements selected can be 7Li, 45Sc, 73Ge, 89Y, 103Rh, 115In and 209Bi, and the internal standard solution enters the inductively coupled plasma mass spectrometer along with the stock solution, so that concentration correction can be performed, and the final test accuracy is improved.
Step S222: and respectively testing the corresponding signal intensity of the impurity element to be tested at each preset concentration by an inductively coupled plasma mass spectrometer.
The working principle of the inductively coupled plasma mass spectrometer is as follows: the atomizer sends the solution sample into the plasma light source, gasifies under high temperature, dissociates the ionized gas, the ion collected by the copper or nickel sampling cone forms the molecular beam under the pressure of 133.322Pa of low vacuum, then enters the quadrupole mass analyzer through the intercepting plate with the diameter of 1-2 mm, and reaches the ion detector after the mass separation of the mass filter, and the content or isotope ratio of the element can be measured according to the proportional relation of the count and the concentration of the detector.
After the concentration configuration of the standard curves of the 9 impurity elements to be tested is completed, the signal intensity of the impurity element to be tested corresponding to each concentration is tested through an inductively coupled plasma mass spectrometer.
Before testing, the inductively coupled plasma mass spectrometer needs to be tuned for device sensitivity, and detection conditions are set.
Specifically, a preset detection condition is determined according to a full-axis scanning surface measurement setting interface, wherein the preset detection condition comprises preset radio frequency power, preset cooling air flow, preset atomization air flow, preset pump speed, preset sample lifting rate, preset measurement mode and preset scanning times. After tuning of the device and setting of detection conditions are completed, the signal intensity test of the impurity element to be detected can be performed.
Taking 24Mg as an example, after 0ppb of 24Mg is prepared, placing a stock solution into an inductively coupled plasma mass spectrometer, testing after testing parameters are adjusted, and outputting the signal intensity of the 24Mg under 0ppb on the instrument for recording; then placing the prepared 24Mg stock solution with the concentration of 1ppb into an inductively coupled plasma mass spectrometer, and continuously testing, wherein the instrument outputs the signal intensity of 24Mg element with the concentration of 1ppb, and the like, so as to respectively test the signal intensity of 24Mg with the concentration of 5ppb, 24Mg with the concentration of 20ppb and 24Mg with the concentration of 100ppb.
Step S223: and establishing a standard curve of each impurity element to be detected according to different preset concentrations and the corresponding signal intensity of the current impurity element to be detected under each preset concentration.
The abscissa of the standard curve of the impurity element to be measured represents the concentration content value of the impurity element to be measured, and the ordinate of the standard curve of the impurity element to be measured represents the signal intensity of the impurity element to be measured.
Since step S221 to step S222 determine the signal intensities of the impurity elements to be measured at the concentrations corresponding to the abscissa of 0ppb, 1ppb, 5ppb, 20ppb, 100ppb, respectively, the ordinate of the abscissa, a straight line equation, that is, the standard curve described in this step can be established. In the same manner, a standard curve of 9 impurity elements to be measured was established.
When the standard curve is established, 0ppb, 1ppb, 5p are selected from the abscissaFive points data of pb, 20ppb and 100ppb, it is necessary to ensure the linear correlation coefficient R of the standard curve 2 More than 0.9994, the error of the final test result can be ensured to be smaller. If the standard curve is established, 1 point with more deviated standard curves exists in the 5 points, the rest 3 or 4 points can be selected and removed, and the rest 3 or 4 points are reserved as the selected points of the standard curve.
Step S230: and placing the tantalum sample solution to be tested in an inductively coupled plasma mass spectrometer, and respectively testing to obtain the signal intensity of the impurity element to be tested.
And placing the prepared tantalum sample to-be-detected solution in an inductively coupled plasma mass spectrometer, selecting a standard curve corresponding to the impurity element to be tested, and then testing to obtain the signal intensity response value of the impurity element.
Step S240: and respectively calculating to obtain the concentration content value of the impurity element to be detected in the tantalum sample solution to be detected according to the signal intensity of the impurity element to be detected and the standard curve of the impurity element to be detected.
Substituting the signal intensity of the impurity element to be tested (namely, the value of the ordinate in the standard curve corresponding to the impurity element to be tested) into the standard curve of the impurity element to be tested, and calculating to obtain the concentration content value of the impurity element to be tested in the tantalum sample to be tested (namely, the value of the abscissa in the standard curve corresponding to the impurity element to be tested).
According to the same method, concentration content values of 9 impurity elements to be detected are respectively calculated.
In order to verify the accuracy of the above measurement method, the method of the present application further comprises a labeled recovery test verification test. Specifically, selecting target detection tantalum powder, performing a labeling recovery verification test, and determining the recovery rate of the target detection tantalum powder according to a test result. And (3) monitoring tantalum powder through each element standard curve and targets of different powder types, and verifying the accuracy of the method by a labeled recovery test.
According to the above procedure, the present application conducted a full experiment. The experimental equipment adopts an ICP-MS inductively coupled plasma mass spectrometer as Thermo Fisher ICAPQ-ICPMS. Device temperature: 18-22 ℃; humidity: 40% -50%; the reagent used in the experimental procedure was ultrapure water, and the resistivity was 18.25 M.OMEGA.cm.
Embodiment one:
step 1: preparing a stock solution. 0.75g of high-purity tantalum (purity more than 99.8%) is weighed, dried, dissolved by using 6ml of ultrapure nitric acid and 70 drops of ultrapure hydrofluoric acid, and digested by graphite for 10 minutes, and then fixed to a volume in a 50ml pipette as a stock solution for standby, thereby eliminating the influence of tantalum base effect.
Step 2: and preparing a tantalum sample solution to be tested. Three batches of A, B, C, D four powder tantalum powders (high, medium, and low pressure tantalum powders were capped) were weighed, respectively, and three parallel samples were weighed for each batch, as shown in table 1, for a total of 12 parts. The weight of each tantalum sample is 0.1200+/-0.0010 g. 1.2ml HNO is added into each sample 3 After the sample is fully infiltrated, adding 20 drops of HF for fully dissolving, digesting graphite for 20min, and fixing the volume in a 50ml pipette to be used as a solution to be measured.
TABLE 1 Relative Standard Deviation (RSD) of impurity element test results and parallel samples in tantalum sample A, B, C, D
Step 3: sensitivity tuning of the inductively coupled plasma mass spectrometer apparatus is performed. The equipment has the sensitivity of 238U reaching more than or equal to 300000 cps count after tuning, 115In more than or equal to 200000 cps count, 59Co more than or equal to 100000 cps count, 7Li more than or equal to 50000 cps count, and double charges less than or equal to 0.03 after tuning by the automatic tuning parameter under the STD mode.
And determining preset detection conditions according to a full-axis scanning surface measurement setting interface (Survey scan settings), wherein the preset detection conditions comprise preset radio frequency power, preset cooling air flow, preset atomization air flow, preset pump speed, preset sample lifting rate, preset measurement mode and preset scanning times.
Wherein, preset radio frequency power L kW, preset cooling air flow 12+ -1L/min, preset atomizing air flow 0.90+ -0.05L/min, preset peristaltic pump speed 40+ -1, preset sample lifting rate 0.95+ -0.05 mL/min, preset Measurement mode (Measurement mode) select KED (Kinetic Energy Discrimination, collision cell technology), preset scanning times are set to 30 times. See in particular fig. 3.
Step 4: and respectively establishing standard curves of impurity elements to be detected. According to the concentration range of impurity elements to be measured in the tantalum sample solution to be measured, setting the concentration gradient of a standard curve to be 0ppb (blank), 1ppb, 5ppb, 20ppb and 100ppb, and configuring the standard curve for standby by using national standard substances. Preparing the GNM-M081395-2013-8 element specific standard substance into an internal standard solution with the same matching concentration for later use.
Taking Mg as an example, adding 0ppb of 24Mg, 1ppb of 24Mg, 5ppb of 24Mg, 20ppb of 24Mg and 100ppb of 24Mg into a stock solution, placing the 24Mg stock solution containing 0ppb into an inductively coupled plasma mass spectrometer for testing, and recording the signal intensity of the 24Mg element under 0ppb output on the instrument; then placing the prepared 24Mg stock solution with the concentration of 1ppb into an inductively coupled plasma mass spectrometer, and continuously testing, wherein the instrument outputs the signal intensity of 24Mg element with the concentration of 1ppb, and the like, so as to respectively test the signal intensity of 24Mg with the concentration of 5ppb, 24Mg with the concentration of 20ppb and 24Mg with the concentration of 100ppb.
The signal intensity of 24Mg of the impurity element to be measured at the concentrations of 0ppb, 1ppb, 5ppb, 20ppb, 100ppb on the abscissa and 0ppb, 1ppb, 5ppb, 20ppb, 100ppb on the ordinate can be established by establishing a straight line equation of 24Mg element, that is, establishing a standard curve of 24Mg element described in this step, as shown in fig. 4. The standard linear equation corresponding to the 24Mg element is f (x) =166.2729×x+425.4632, and the correlation coefficient R is 2 =0.9999, bec=2.559 ppb, lod=0.0933 ppb. Where BEC represents the background equivalent concentration, can be used to evaluate the cleanliness of the system and the degree of interference of mass spectra. LoD (limit of detection) the lowest concentration (amount) of the component to be detected in the sample, referred to as the detection limit, i.e., the sample at which the signal (peak height) is generated k times the standard deviation of the baseline noiseThe product concentration is generally the concentration at a signal to noise ratio (S/N) of 2:1 or 3:1.
Then, a standard curve of 48Ti element is prepared, 0ppb of 48Ti, 1ppb of 48Ti, 5ppb of 48Ti, 20ppb of 48Ti and 100ppb of 48Ti are added into the stock solution, after the preparation, the stock solution containing 0ppb of 48Ti is placed into an inductively coupled plasma mass spectrometer for testing, and at this time, the signal intensity of 48Ti element under 0ppb is output on the instrument for recording; then, the prepared 48Ti stock solution with the concentration of 1ppb is placed in an inductively coupled plasma mass spectrometer, and the test is continued, wherein the signal intensity of 48Ti element with the concentration of 1ppb is output on the instrument, and the signal intensity of 48Ti element with the concentration of 5ppb, 48Ti element with the concentration of 20ppb and 48Ti element with the concentration of 100ppb are respectively tested by analogy.
The signal intensity of 48Ti of the impurity element to be measured at the concentrations of 0ppb, 1ppb, 5ppb, 20ppb, 100ppb on the abscissa and 0ppb, 1ppb, 5ppb, 20ppb, 100ppb on the ordinate can be established by establishing a linear equation of 48Ti element, namely, establishing a standard curve of 48Ti element described in this step, as shown in FIG. 5. The standard linear equation corresponding to 48Ti element is f (x) =804.1138xx+272.1753, and the correlation coefficient R 2 ＝0.9998，BEC＝0.338ppb，LoD＝0.0507ppb。
Similarly, standard curves of 9 kinds of impurity elements, 52Cr, 55Mn, 56Fe, 60Ni, 93Nb, 95Mo, 184W, were established in the same manner, as shown in fig. 6, 7, 8, 9, 10, 11, and 12, respectively.
In fig. 6, the standard linear equation corresponding to the 52Cr element is f (x) =3222.9667×x+331.8723, and the correlation coefficient R 2 ＝0.9999，BEC＝0.103ppb，LoD＝0.0069ppb。
In fig. 7, the standard linear equation corresponding to the 55Mn element is f (x) =2218.3563×x+293.5954, and the correlation coefficient R 2 ＝1.0000，BEC＝0.132ppb，LoD＝0.0250ppb。
In fig. 8, the standard linear equation corresponding to 56Fe element is f (x) =77.9991×x+301.3364, and the correlation coefficient R 2 ＝0.9998，BEC＝3.863ppb，LoD＝0.3562ppb。
In fig. 9, the standard linear equation corresponding to 60Ni element is f (x) =1189.2782×x+1245.9438, and the correlationCoefficient R 2 ＝0.9999，BEC＝1.048ppb，LoD＝0.2286ppb。
In fig. 10, the standard linear equation corresponding to 93Nb element is f (x) =7919.2984×x+550.9986, and the correlation coefficient R 2 ＝1.0000，BEC＝0.070ppb，LoD＝0.0015ppb。
In fig. 11, the standard linear equation corresponding to the 95Mo element is f (x) =1947.0951×x+23.0807, and the correlation coefficient R 2 ＝0.9999，BEC＝0.012ppb，LoD＝0.0068ppb。
In fig. 12, the standard linear equation corresponding to element 184W is f (x) =6183.2770×x+647.2296, r 2 ＝0.9999，BEC＝0.105ppb，LoD＝0.0050ppb。
As shown in FIGS. 4 to 12, the corresponding standard curves of the impurity elements have very good linear correlation and the linear correlation coefficient R 2 All are above 0.9994, and the sensitivity of the equipment shown in the figure 3 is proved to be completely up to the standard.
Step 6: under the condition of optimizing the equipment performance, placing the tantalum sample to-be-measured solution obtained In the step 2 into an inductively coupled plasma mass spectrometer, selecting to-be-measured impurity elements of 24Mg, 48Ti, 52Cr, 55Mn, 56Fe, 60Ni, 93Nb, 95Mo and 184W, selecting internal standard solution elements of 7Li, 45Sc, 73Ge, 89Y, 103Rh, 115In and 209Bi, selecting KED (Kinetic Energy Discrimination, collision cell technology) In a Measurement mode, and setting the preset scanning times to 30 times.
When testing 24Mg element, selecting a corresponding 24Mg standard curve (shown in fig. 4) from a measurement interface, testing the signal intensity corresponding to the 24Mg element to be tested through an inductively coupled plasma mass spectrometer, and finally calculating the concentration content value of the 24Mg impurity element in the tantalum sample solution to be tested according to the 24Mg standard curve shown in fig. 4.
When the concentration content value of the 48Ti impurity element in the tantalum sample to be measured is required to be measured, a corresponding 48Ti standard curve (shown in fig. 5) is selected from a measurement interface, the signal intensity corresponding to the 48Ti to be measured is tested through an inductively coupled plasma mass spectrometer, and the concentration content value of the 48Ti impurity element in the tantalum sample to be measured is finally calculated according to the 48Ti standard curve shown in fig. 5.
When the concentration content value of the 52Cr impurity element in the tantalum sample to be measured is required to be measured, a corresponding 52Cr standard curve (shown in fig. 6) is selected from a measurement interface, the signal intensity corresponding to the 52Cr to be measured is tested through an inductively coupled plasma mass spectrometer, and the concentration content value of the 52Cr impurity element in the tantalum sample to be measured is finally calculated according to the 52Cr standard curve shown in fig. 6.
According to the same method, the concentration content values of the total 9 impurity elements of 24Mg, 48Ti, 52Cr, 55Mn, 56Fe, 60Ni, 93Nb, 95Mo and 184W in the tantalum sample solution to be detected can be finally calculated respectively, and the test results are shown in table 1.
As can be seen from Table 1, three determinations were made for each of the four tantalum powders, and the accuracy and precision were calculated. The impurity element contents of the four tantalum powders are all within the working curve range set by the method, and the relative standard deviation RSD of the chemical impurity contents of each powder type parallel sample can be very low (RSD is less than 1). This demonstrates that the high purity tantalum trace impurity determination method of the present application has extremely high test accuracy while ensuring determination accuracy.
In order to verify the accuracy of the test results, the experiment was finally followed by a label recovery test. The standard deviation of the parallel sample of each impurity element is used for verifying the precision of the method. The test results and test accuracy of the 12 samples obtained are shown in table 2 below.
Table 2E, F powder type addition recovery verification results
| ICP-MS verification powder | Mg | Ti | Cr | Mn | Fe | Ni | Nb | Mo | W |
| Before adding mark | 6.76 | 0.15 | 1.12 | 1.82 | 2.99 | 2.92 | 0.25 | 0.03 | 0.02 |
| After the addition of the mark (+20 ppm) | 26.38 | 20.22 | 21.85 | 21.69 | 23.52 | 23.66 | 20.89 | 20.34 | 20.06 |
| E type tantalum powder (recovery rate) | 98.1 | 100.35 | 103.65 | 99.35 | 102.65 | 103.7 | 103.2 | 101.6 | 100.2 |
| Before adding mark | 3.12 | 0.39 | 5.35 | 0.58 | 12.1 | 4.65 | 0.22 | 0.16 | 0.21 |
| After the addition of the mark (+20 ppm) | 22.96 | 20.06 | 26.03 | 20.41 | 32.66 | 25.06 | 20.54 | 20.76 | 20.68 |
| F-type tantalum powder | 99.2 | 98.35 | 103.4 | 99.15 | 102.8 | 102.05 | 101.6 | 103 | 102.4 |
As can be seen from Table 2, the E-type tantalum powder and the F-type tantalum powder are subjected to a standard adding and recycling test, the recycling rate is in the range of 98% -104%, and compared with 100% + -20% of the industry standard, the impurity element of the high-purity tantalum measured by the method has high accuracy, and the standard adding and recycling test proves that the method is high in reliability.
In conclusion, the ICP-MS measuring method special for the high-purity tantalum-based chemical impurity element uses a standard curve stock solution sample preparation method, can effectively eliminate the matrix effect influence caused by high-purity tantalum metal base effect, is simple in established standard curve and higher in accuracy, and improves the measuring reliability of the impurity element.
According to the method, the ICP-MS equipment is used for completing the content measurement of 9 chemical impurity elements required to be measured in the high-purity tantalum powder at one time, so that the test duration is greatly shortened, and the test efficiency is effectively improved. The method enhances the controllability of the mass spectrum testing process and improves the stability of the testing result between parallel samples, thereby greatly improving the accuracy of impurity element determination.
It should be noted that, without conflict, features in the embodiments of the present application may be combined with each other.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (10)
1. A method for determining trace impurity elements in high purity tantalum, comprising the steps of:
preparing a tantalum sample solution to be tested;
respectively establishing standard curves of impurity elements to be detected;
placing the tantalum sample solution to be tested in an inductively coupled plasma mass spectrometer, and respectively testing to obtain the signal intensity of the impurity element to be tested;
and respectively calculating the concentration content value of the impurity element to be detected in the tantalum sample solution to be detected according to the signal intensity of the impurity element to be detected and the standard curve of the impurity element to be detected.
2. The method for determining trace impurity elements in high purity tantalum according to claim 1, wherein said preparing a tantalum sample test solution comprises:
weighing a tantalum sample with preset mass, and adding nitric acid with preset capacity;
after the tantalum sample is fully infiltrated, dropwise adding hydrofluoric acid to fully dissolve the tantalum sample, and adopting graphite to digest for a preset time;
and preparing the tantalum sample to-be-measured solution after the tantalum sample is fully dissolved, and fixing the volume in a volumetric flask.
3. The method for measuring trace impurity elements in high purity tantalum according to claim 1, wherein prior to said preparing a tantalum sample test solution, said method further comprises:
and dissolving high-purity tantalum by using nitric acid and hydrofluoric acid, and digesting by using graphite to prepare a stock solution with preset concentration, wherein the purity of the high-purity tantalum is more than 99.8%.
4. The method for measuring trace impurity elements in high purity tantalum according to claim 3, wherein said respectively establishing standard curves of impurity elements to be measured comprises:
adding current impurity elements to be detected with different preset concentrations into the stock solution according to the concentration range of each impurity element to be detected;
respectively testing the corresponding signal intensity of the impurity element to be tested at each preset concentration by the inductively coupled plasma mass spectrometer;
and establishing a standard curve of each impurity element to be detected according to different preset concentrations and the corresponding signal intensity of the current impurity element to be detected under each preset concentration.
5. The method of claim 1, further comprising, after said placing said tantalum sample test solution in an inductively coupled plasma mass spectrometer:
and determining preset detection conditions according to the full-axis scanning surface measurement setting interface, wherein the preset detection conditions comprise preset radio frequency power, preset cooling air flow, preset atomization air flow, preset pump speed, preset sample lifting rate, preset measurement mode and preset scanning times.
6. The method for measuring trace impurity elements in high purity tantalum according to claim 1, wherein an abscissa of a standard curve of the impurity element to be measured represents a concentration content value of the impurity element to be measured, an ordinate of a standard curve of the impurity element to be measured represents a signal intensity of the impurity element to be measured, and the concentration content value of the impurity element to be measured in the tantalum sample measurement solution is calculated according to the signal intensity of the impurity element to be measured and the standard curve of the impurity element to be measured, respectively, comprising:
substituting the signal intensity of the impurity element to be detected into the standard curve of the impurity element to be detected, and respectively calculating to obtain the concentration content value of the impurity element to be detected in the tantalum sample solution to be detected.
7. The method for determining trace impurity elements in high purity tantalum according to claim 1, further comprising:
selecting target detection tantalum powder, and performing a labeling recovery verification test;
and determining the recovery rate of the target detection tantalum powder according to the test result.
8. The method for measuring trace impurity elements in high purity tantalum according to claim 3, wherein said predetermined concentration is 0ppb, 1ppb, 5ppb, 20ppb, 100ppb.
9. The method for determining trace impurity elements in high purity tantalum according to claim 1, further comprising: an internal standard solution was prepared for concentration correction treatment.
10. The method for measuring trace impurity elements in high-purity tantalum according to claim 1, wherein the isotopes selected from the impurity elements to be measured are 24Mg, 48Ti, 52Cr, 55Mn, 56Fe, 60Ni, 93Nb, 95Mo, 184W.
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