CN104697985A - Method for measuring beryllium and potassium content in zirconium and zirconium alloy at the same time - Google Patents
Method for measuring beryllium and potassium content in zirconium and zirconium alloy at the same time Download PDFInfo
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Abstract
The invention provides a method for measuring the beryllium and potassium content in zirconium and zirconium alloy at the same time. The method includes the following steps that 1, pure zirconium or zirconium alloy is turned to obtain cuttings-shaped samples, and then the samples are cleaned and dried; 2, coning and quartering are adopted to conduct sampling; 3, the samples are dissolved, a solution is transferred to a volumetric flask to conduct constant volume, and a solution to be measured is obtained; 4, a series of beryllium-potassium correction solutions of different concentration are mixed; 5, the element feature spectral intensity of beryllium and potassium in the beryllium-potassium correction solutions of all concentration is measured one by one through an inductive coupling plasma emission spectrometer, and a correction curve is established; 6, the element feature spectral intensity of the beryllium and potassium in the solution to be measured is measured through the inductive coupling plasma emission spectrometer, and the beryllium content and the potassium content in the pure zirconium samples or the zirconium alloy samples are worked out according to the correction curve. By means of the method, the difficulty that a vertical observation technology is prone to being interfered when measuring elements which are ionized easily can be overcome, and the nuclear industry zirconium and zirconium alloy detection requirement is met.
Description
Technical field
The invention belongs to chemical analysis technology field, be specifically related to the method for beryllium potassium content in a kind of Simultaneously test zirconium and it's alloy.
Background technology
Metal zirconium and alloy thereof are widely used in cladding materials and the core structural material of water-cooled power reactor.The zirconium and it's alloy chemical analysis method of current domestic open report is mainly the GB/T 13747 zirconium and it's alloy chemical analysis method GB of promulgating for 1992, and the inductively coupled plasma emission spectrography that the people such as Li Gangs in 2012 delivers measures 17 kinds of constants and trace element in nuclear grade zirconium alloy.All do not relate to the assay method of beryllium in zirconium and it's alloy, potassium element in these documents, major technique difficulty is as follows:
The inductive coupling plasma emission spectrograph of current main flow is Vertical Observation quarter bend, Vertical Observation technology is very easily interfered in mensuration easily ionizable dvielement (alkaline metal and earth alkali metal), and matrix effect is also particularly evident to Easily ionized elements interferences, cause measurement result poor stability, do not meet quantitative test requirement.Usual use chemical analysis method measures Easily ionizing element, or accident Easily ionizing element.Beryllium element is No. four element in the periodic table of elements, the light and easily ionizable of atomic weight, and potassium element is typical alkaline metal, very easily ionizes, use Vertical Observation technology measure beryllium, potassium content difficulty very big.
Summary of the invention
Technical matters to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides the method for beryllium potassium content in a kind of Simultaneously test zirconium and it's alloy.The method is by adopting 360B zircaloy standard substance as the matrix of calibration solution, and a large amount of choice experiment is carried out to conditions such as characteristic spectrum spectral lines, overcome difficulty that in Vertical Observation technology, Easily ionizing element is easily disturbed and inductive coupling plasma emission spectrograph measures the difficulty that zirconium matrix hypersaline environment detection limit is discontented with footprint component analysis, provide a kind of method that inductive coupling plasma emission spectrograph measures beryllium and potassium content in zirconium and it's alloy, meet nuclear industry zirconium and it's alloy and detect demand.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method of beryllium potassium content in Simultaneously test zirconium and it's alloy, and it is characterized in that, the method comprises the following steps:
Step one, turning is carried out to pure zirconium or zircaloy, obtain bits shape sample, then bits shape sample is cleaned up post-drying for subsequent use;
Step 2, employing coning and quartering carry out division sampling to the bits shape sample after oven dry in step one, obtain treating test sample;
Step 3, to treating described in step 2 that dripping hydrofluorite-nitric acid compound acid solution in test sample dissolves, and then proceeds in volumetric flask by solution, shakes up with after pure water constant volume, obtain liquid to be measured; The volume V of described hydrofluorite-nitric acid compound acid solution meets: 8m≤V≤10m, and wherein m is the quality treating test sample, and the unit of m is the unit of g, V is mL;
Step 4, the 360B zircaloy standard substance several parts of quality being m are placed in multiple beaker, each dropping volume is that the hydrofluorite-nitric acid compound acid solution of V is dissolved, obtain many parts of matrix mother liquors, then multiple volumetric flask is got, each part matrix mother liquor and the beryllium standard solution of metering and the potassium standard solution of metering are moved in each volumetric flask respectively, use pure water constant volume respectively afterwards, after shaking up, obtain the beryllium-potassium calibration solution of a series of variable concentrations;
The characteristic spectrum intensity of step 5, employing inductive coupling plasma emission spectrograph beryllium element in the 313.042nm place beryllium of variable concentrations described in determination step four one by one-potassium calibration solution, measure the characteristic spectrum intensity of potassium element in variable concentrations beryllium-potassium calibration solution one by one in 766.491nm place simultaneously, set up the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation in beryllium-potassium calibration solution thus, and beryllium-potassium calibrates the concentration of potassium and the calibration curve of potassium element characteristic spectrum intensity corresponding relation in solution;
Step 6, adopt inductive coupling plasma emission spectrograph in the beryllium element characteristic spectrum intensity of liquid to be measured described in 313.042nm place determination step three, measure the potassium element characteristic spectrum intensity of liquid to be measured in 766.491nm place simultaneously, then the concentration of beryllium in liquid to be measured is calculated according to the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation in the beryllium set up in step 5-potassium calibration solution, the concentration of potassium in liquid to be measured is calculated according to the concentration of potassium and the calibration curve of potassium element characteristic spectrum intensity corresponding relation in beryllium-potassium calibration solution, finally calculate the mass content of beryllium and the mass content of potassium in pure zirconium or zircaloy sample.
In above-mentioned a kind of Simultaneously test zirconium and it's alloy, the method for beryllium potassium content, is characterized in that, in hydrofluorite-nitric acid compound acid solution described in step 3 and step 4, the mass percentage of HF is 12% ~ 18%, HNO
3mass percentage be 5% ~ 9%.
In above-mentioned a kind of Simultaneously test zirconium and it's alloy, the method for beryllium potassium content, is characterized in that, described in step 3 and step 4, m is all satisfied: 0.5g≤m≤1g, and described in step 3 and step 4, the specification of volumetric flask is 50mL or 100mL.
The method of beryllium potassium content in above-mentioned a kind of Simultaneously test zirconium and it's alloy, it is characterized in that, in the beryllium-potassium calibration solution of a series of variable concentrations described in step 4, the concentration of beryllium is respectively 0mg/L, 0.01mg/L, 0.02mg/L, 0.1mg/L and 0.2mg/L, and in the beryllium-potassium calibration solution of described a series of variable concentrations, the concentration of potassium is respectively 0mg/L, 0.01mg/L, 0.02mg/L, 0.1mg/L and 0.2mg/L.
The method of beryllium potassium content in above-mentioned a kind of Simultaneously test zirconium and it's alloy, it is characterized in that, described in step 5 and step 6, the running parameter of inductive coupling plasma emission spectrograph is: radio-frequency generator power 1.1kW ~ 1.4kW, plasma gas flow rate 12L/min ~ 15L/min, assisted gas flow 0.7L/min ~ 1.1L/min, atomization gas flow 0.7L/min ~ 1.1L/min, peristaltic pump pump speed 15rpm ~ 45rpm, observed altitude 15mm ~ 16mm, integral time 2s ~ 5s.
The method of beryllium potassium content in above-mentioned a kind of Simultaneously test zirconium and it's alloy, it is characterized in that, the linearly dependent coefficient that in beryllium described in step 5-potassium calibration solution, the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation and beryllium-potassium calibrate the concentration of potassium in solution and the calibration curve of potassium element characteristic spectrum intensity corresponding relation is all not less than 0.999.
The present invention compared with prior art has the following advantages:
1, the present invention adopts 360B zircaloy standard substance as the matrix of calibration solution, effectively reduces matrix effect, improves the accuracy of detection method.
2, the present invention adopts by the 360B zircaloy standard substance of NIST certification, beryllium standard solution and potassium standard solution preparation beryllium-potassium calibration solution, and accuracy is high, precision is high, international endorsement degree is high.
3, the present invention adopts beryllium element content in inductively coupled plasma emission spectrography Simultaneously test zirconium and it's alloy and Determination of Potassium, spirit density is high, precision is high, accuracy is high, analytical procedure is simply easy to grasp, and analysis speed is fast, meets nuclear industry zirconium and it's alloy and detects demand.
5, the present invention establishes the method for beryllium potassium content in a kind of Simultaneously test zirconium and it's alloy, makes up the domestic blank that there is no beryllium in zirconium and it's alloy, potassium element assay method, meets nuclear industry zirconium and it's alloy and detects demand.
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is that beryllium-potassium that embodiment of the present invention 1-3 sets up on inductive coupling plasma emission spectrograph calibrates the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation in solution.
Fig. 2 is that beryllium-potassium that embodiment of the present invention 1-3 sets up on inductive coupling plasma emission spectrograph calibrates the concentration of potassium and the calibration curve of potassium element characteristic spectrum intensity corresponding relation in solution.
Embodiment
Embodiment 1
The method that the present embodiment measures beryllium, potassium content in zirconium and it's alloy comprises the following steps:
Step one, turning is carried out to pure zirconium or zircaloy, obtain bits shape sample, then bits shape sample is cleaned up post-drying for subsequent use;
The present embodiment, in specific implementation process, first cleans pure zirconium or zircaloy bits shape more than sample 30s by soaked in absolute ethyl alcohol, then uses pure water rinsing sample more than 10 times, dried by bits shape sample afterwards under the condition being no more than 50 DEG C of temperature; Described absolute ethyl alcohol is for analyzing the above specification of pure level, and pure water meets the one-level water requirement of GB/T 6682 laboratory;
Step 2, employing coning and quartering carry out division sampling to the pure zirconium after oven dry in step one or zircaloy sample, obtain treating test sample;
The present embodiment adopts the rear precise 1g sample of coning and quartering sampling, is accurate to 0.0020g;
Step 3, to dissolve to treating described in step 2 to drip in test sample in 10mL hydrofluorite-nitric acid compound acid solution, then solution being proceeded in 100mL volumetric flask, shaking up with after pure water constant volume, obtaining liquid to be measured; In described hydrofluorite-nitric acid compound acid solution, the mass percentage of HF is 14.4%, HNO
3mass percentage be 6.8%;
The present embodiment is in specific implementation process, first the 1g that step 2 weighs is treated that test sample is placed in 50mL hydrofluoric acid resistant beaker, add 8mL pure water submergence sample, then 10mL hydrofluorite-nitric acid compound acid solution sample dissolution is dropwise slowly added, afterwards solution is all transferred in 100mL hydrofluoric acid resistant volumetric flask, use pure water constant volume, shake up; Described hydrofluorite-nitric acid compound acid solution is formed by commercially available red fuming nitric acid (RFNA), commercially available hydrofluorite and pure water mixed preparing, and described commercially available red fuming nitric acid (RFNA) and commercially available hydrofluorite are the pure above specification of top grade;
Step 4, accurate weighing number part quality are the 360B zircaloy standard substance of 1g, be accurate to 0.0001g, be placed in multiple beaker, drip in 10mL hydrofluorite-nitric acid compound acid solution respectively and dissolve, obtain matrix mother liquor, then get multiple 100mL volumetric flask, each part matrix mother liquor and the beryllium standard solution of metering and the potassium standard solution of metering are moved in each volumetric flask respectively, use pure water constant volume respectively afterwards, after shaking up, obtain the beryllium-potassium calibration solution of a series of variable concentrations;
360B zircaloy standard substance, beryllium standard solution and potassium standard solution that the present embodiment adopts all meet NIST standard-required; The present embodiment is in specific implementation process, prepare beryllium standard solution and potassium standard solution that two kinds can be traceable to NIST, use wherein a kind of beryllium-potassium calibration solution for preparing a series of variable concentrations, use another kind of for preparing beryllium-potassium check standard solution (concentration of beryllium and potassium is 0.2mg/L), it is identical that its compound method and serial beryllium-potassium calibrate solution;
In the beryllium-potassium calibration solution of a series of variable concentrations that the present embodiment is prepared, the concentration of beryllium is respectively 0mg/L, 0.01mg/L, 0.02mg/L, 0.1mg/L and 0.2mg/L, and the concentration of potassium is respectively 0mg/L, 0.01mg/L, 0.02mg/L, 0.1mg/L and 0.2mg/L.In concrete process for preparation, accurate weighing five parts of quality are the 360B zircaloy standard substance of 1g, be accurate to 0.0001g, be placed in five 50mL hydrofluoric acid resistant beakers respectively, respectively add 8mL pure water submergence sample, then 10mL hydrofluorite-nitric acid compound acid solution sample dissolution is dropwise slowly added respectively, successively solution is all transferred to afterwards in five 100mL hydrofluoric acid resistant volumetric flasks, and add the beryllium standard solution of five parts of meterings and the potassium standard solution of metering, finally use pure water constant volume, shake up, obtain the beryllium-potassium calibration solution of a series of variable concentrations; And the beryllium-potassium check standard solution of 0.02mg/L is according to the method configuration beryllium and potassium concn;
Step 5, employing inductive coupling plasma emission spectrograph be beryllium element characteristic spectrum intensity in the 313.042nm place beryllium of variable concentrations described in determination step four one by one-potassium calibration solution; Simultaneously, potassium element characteristic spectrum intensity in variable concentrations beryllium-potassium calibration solution is measured one by one in 766.491nm place, setting running parameter is as follows: radio-frequency generator power 1.35kW, plasma gas flow rate 13L/min, assisted gas flow 0.8L/min, atomization gas flow 0.85L/min, peristaltic pump pump speed 30rpm, integral time 2s; Set up the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation in beryllium-potassium calibration solution thus, and beryllium-potassium calibrates the concentration of potassium and the calibration curve of potassium element characteristic spectrum intensity corresponding relation in solution;
The present embodiment adopts the upper beryllium-potassium set up of ICP-OES to calibrate the calibration curve of the concentration of beryllium in solution and beryllium element characteristic spectrum intensity corresponding relation as shown in Figure 1, linearly dependent coefficient >=0.999 of this calibration curve as shown in Figure 1.The present embodiment adopts the upper beryllium-potassium set up of ICP-OES to calibrate the calibration curve of the concentration of potassium in solution and potassium element characteristic spectrum intensity corresponding relation as shown in Figure 2, linearly dependent coefficient >=0.999 of this calibration curve as shown in Figure 2.
Adopt ICP-OES to be that 313.042nm place measures beryllium element characteristic spectrum at wavelength, measure potassium element characteristic spectrum at 766.491nm place, the beryllium-potassium check standard solution of preparation is measured, to verify the accuracy of calibration curve.Through verifying, beryllium check standard measured in solution result is 0.020mg/L, and potassium check standard measured in solution result is 0.021mg/L, and the calibration curve accurate and effective that the present embodiment obtains can be described thus;
Step 6, employing inductive coupling plasma emission spectrograph are in the beryllium element characteristic spectrum intensity of liquid to be measured described in 313.042nm place determination step three, simultaneously, in the potassium element characteristic spectrum intensity of liquid to be measured described in 766.491nm place determination step three, setting running parameter is as follows: radio-frequency generator power 1.35kW, plasma gas flow rate 13L/min, assisted gas flow 0.8L/min, atomization gas flow 0.85L/min, peristaltic pump pump speed 30rpm, integral time 2s; Then beryllium-the potassium set up according to step 5 is calibrated the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation in solution and is calculated the concentration of beryllium in liquid to be measured, calculate the concentration of potassium in liquid to be measured according to the concentration of potassium and the calibration curve of potassium element characteristic spectrum intensity corresponding relation in beryllium-potassium calibration solution, finally calculate the mass content of beryllium and the mass content of potassium in pure zirconium or zircaloy sample.
The present embodiment according to beryllium and Determination of Potassium in calibrating curve determining liquid to be measured, and does three parallel laboratory tests, and calculating mean value is measurement result, in table 1.
Table 1 embodiment 1 measurement result
Embodiment 2
The method that the present embodiment measures beryllium, potassium content in zirconium and it's alloy comprises the following steps:
Step one, turning is carried out to pure zirconium or zircaloy, obtain bits shape sample, then bits shape sample is cleaned up post-drying for subsequent use;
The present embodiment, in specific implementation process, first cleans pure zirconium or zircaloy bits shape more than sample 30s by soaked in absolute ethyl alcohol, then uses pure water rinsing sample more than 10 times, dried by bits shape sample afterwards under the condition being no more than 50 DEG C of temperature; Described absolute ethyl alcohol is for analyzing the above specification of pure level, and pure water meets the one-level water requirement of GB/T 6682 laboratory;
Step 2, employing coning and quartering carry out division sampling to the pure zirconium after oven dry in step one or zircaloy sample, obtain treating test sample;
The present embodiment adopts the rear precise 0.5g sample of coning and quartering sampling, is accurate to 0.0010g;
Step 3, to treating described in step 2 that dripping 4mL hydrofluorite-nitric acid compound acid solution in test sample dissolves, and then proceeds to solution in 50mL volumetric flask, shakes up with after pure water constant volume, obtain liquid to be measured; In described hydrofluorite-nitric acid compound acid solution, the mass percentage of HF is 18%, HNO
3mass percentage be 9%;
The present embodiment is in specific implementation process, first the 0.5g that step 2 weighs is treated that test sample is placed in 50mL hydrofluoric acid resistant beaker, add 4mL pure water submergence sample, then 4mL hydrofluorite-nitric acid compound acid solution sample dissolution is dropwise slowly added, afterwards solution is all transferred in 50mL hydrofluoric acid resistant volumetric flask, use pure water constant volume, shake up; Described hydrofluorite-nitric acid compound acid solution is formed by commercially available red fuming nitric acid (RFNA), commercially available hydrofluorite and pure water mixed preparing, and described commercially available red fuming nitric acid (RFNA) and commercially available hydrofluorite are the pure above specification of top grade;
Step 4, accurate weighing number part quality are the 360B zircaloy standard substance of 0.5g, be accurate to 0.0001g, be placed in multiple beaker, drip in 4mL hydrofluorite-nitric acid compound acid solution respectively and dissolve, obtain matrix mother liquor, then get multiple 50mL volumetric flask, each part matrix mother liquor and the beryllium standard solution of metering and the potassium standard solution of metering are moved in each volumetric flask respectively, use pure water constant volume respectively afterwards, after shaking up, obtain the beryllium of a series of variable concentrations, potassium calibration solution;
360B zircaloy standard substance, beryllium standard solution and potassium standard solution that the present embodiment adopts all meet NIST standard-required; The present embodiment is in specific implementation process, prepare beryllium standard solution and potassium standard solution that two kinds can be traceable to NIST, use wherein a kind of beryllium-potassium calibration solution for preparing a series of variable concentrations, use another kind of for preparing beryllium-potassium check standard solution (concentration of beryllium and potassium is 0.2mg/L), it is identical that its compound method and serial beryllium-potassium calibrate solution;
In the beryllium-potassium calibration solution of a series of variable concentrations that the present embodiment is prepared, the concentration of beryllium is respectively 0mg/L, 0.01mg/L, 0.02mg/L, 0.1mg/L and 0.2mg/L, and the concentration of potassium is respectively 0mg/L, 0.01mg/L, 0.02mg/L, 0.1mg/L and 0.2mg/L.In concrete process for preparation, accurate weighing five parts of quality are the 360B zircaloy standard substance of 1g, be accurate to 0.0001g, be placed in five 50mL hydrofluoric acid resistant beakers respectively, respectively add 8mL pure water submergence sample, then 10mL hydrofluorite-nitric acid compound acid solution sample dissolution is dropwise slowly added respectively, successively solution is all transferred to afterwards in five 100mL hydrofluoric acid resistant volumetric flasks, and add beryllium, the potassium standard solution of five parts of meterings, finally use pure water constant volume, shake up, obtain the beryllium-potassium calibration solution of a series of variable concentrations; And the beryllium-potassium check standard solution of 0.02mg/L is according to the method preparation beryllium and potassium concn;
Step 5, employing inductive coupling plasma emission spectrograph be beryllium element characteristic spectrum intensity in the 313.042nm place beryllium of variable concentrations described in determination step four one by one-potassium calibration solution; Simultaneously, potassium element characteristic spectrum intensity in variable concentrations beryllium-potassium calibration solution is measured one by one in 766.491nm place, setting running parameter is as follows: radio-frequency generator power 1.35kW, plasma gas flow rate 13L/min, assisted gas flow 0.8L/min, atomization gas flow 0.85L/min, peristaltic pump pump speed 30rpm, integral time 5s; Set up the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation in beryllium-potassium calibration solution thus, and beryllium-potassium calibrates the concentration of potassium and the calibration curve of potassium element characteristic spectrum intensity corresponding relation in solution;
The present embodiment adopts the upper beryllium-potassium set up of ICP-OES to calibrate the calibration curve of the concentration of beryllium in solution and beryllium element characteristic spectrum intensity corresponding relation as shown in Figure 1, linearly dependent coefficient >=0.999 of this calibration curve as shown in Figure 1.The present embodiment adopts the upper beryllium-potassium set up of ICP-OES to calibrate the calibration curve of the concentration of potassium in solution and potassium element characteristic spectrum intensity corresponding relation as shown in Figure 2, linearly dependent coefficient >=0.999 of this calibration curve as shown in Figure 2.
Adopt ICP-OES to be that 313.042nm place measures beryllium element characteristic spectrum at wavelength, measure potassium element characteristic spectrum at 766.491nm place, the 0.02mg/L beryllium-check standard solution of preparation is measured, to verify the accuracy of calibration curve.Through verifying, beryllium check standard measured in solution result is 0.021mg/L, and potassium check standard measured in solution result is 0.019mg/L, thus calibration curve accurate and effective can be described;
Step 6, employing inductive coupling plasma emission spectrograph are in the beryllium element characteristic spectrum intensity of liquid to be measured described in 313.042nm place determination step three; Simultaneously, in the potassium element characteristic spectrum intensity of liquid to be measured described in 766.491nm place determination step three, setting running parameter is as follows: radio-frequency generator power 1.35kW, plasma gas flow rate 13L/min, assisted gas flow 0.8L/min, atomization gas flow 0.85L/min, peristaltic pump pump speed 30rpm, integral time 5s; Then beryllium-the potassium set up according to step 5 is calibrated the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation in solution and is calculated the concentration of beryllium in liquid to be measured, calculate the concentration of potassium in liquid to be measured according to the concentration of potassium and the calibration curve of potassium element characteristic spectrum intensity corresponding relation in beryllium-potassium calibration solution, finally calculate the mass content of beryllium and the mass content of potassium in pure zirconium or zircaloy sample.
The present embodiment according to beryllium and Determination of Potassium in calibrating curve determining liquid to be measured, and does three parallel laboratory tests, and calculating mean value is measurement result, in table 2.
Table 2 embodiment 2 measurement result
Embodiment 3
The method that the present embodiment measures beryllium, potassium content in zirconium and it's alloy comprises the following steps:
Step one, turning is carried out to pure zirconium or zircaloy, obtain bits shape sample, then bits shape sample is cleaned up post-drying for subsequent use;
The present embodiment, in specific implementation process, first cleans pure zirconium or zircaloy bits shape more than sample 30s by soaked in absolute ethyl alcohol, then uses pure water rinsing sample more than 10 times, dried by bits shape sample afterwards under the condition being no more than 50 DEG C of temperature; Described absolute ethyl alcohol is for analyzing the above specification of pure level, and pure water meets the one-level water requirement of GB/T 6682 laboratory;
Step 2, employing coning and quartering carry out division sampling to the pure zirconium after oven dry in step one or zircaloy sample, obtain treating test sample;
The present embodiment adopts the rear precise 1g sample of coning and quartering sampling, is accurate to 0.0020g;
Step 3, to treating described in step 2 that dripping 10mL hydrofluorite-nitric acid compound acid solution in test sample dissolves, and then proceeds to solution in 100mL volumetric flask, shakes up with after pure water constant volume, obtain liquid to be measured; In described hydrofluorite-nitric acid compound acid solution, the mass percentage of HF is 12%, HNO
3mass percentage be 5%;
The present embodiment is in specific implementation process, first the 1g that step 2 weighs is treated that test sample is placed in 50mL hydrofluoric acid resistant beaker, add 8mL pure water submergence sample, then 10mL hydrofluorite-nitric acid compound acid solution sample dissolution is dropwise slowly added, afterwards solution is all transferred in 100mL hydrofluoric acid resistant volumetric flask, use pure water constant volume, shake up; Described hydrofluorite-nitric acid compound acid solution is formed by commercially available red fuming nitric acid (RFNA), commercially available hydrofluorite and pure water mixed preparing, and described commercially available red fuming nitric acid (RFNA) and commercially available hydrofluorite are the pure above specification of top grade;
Step 4, accurate weighing number part quality are the 360B zircaloy standard substance of 1g, be accurate to 0.0001g, be placed in multiple beaker, drip in 10mL hydrofluorite-nitric acid compound acid solution respectively and dissolve, obtain matrix mother liquor, then get multiple 100mL volumetric flask, each part matrix mother liquor and the beryllium standard solution of metering and the potassium standard solution of metering are moved in each volumetric flask respectively, use pure water constant volume respectively afterwards, after shaking up, obtain the beryllium-potassium calibration solution of a series of variable concentrations;
The 360B zircaloy standard substance that the present embodiment adopts and beryllium, potassium standard solution all meet NIST standard-required; The present embodiment is in specific implementation process, prepare beryllium, potassium standard solution that two kinds can be traceable to NIST, use wherein a kind of beryllium, potassium calibration solution for preparing a series of variable concentrations, use another kind of for preparing beryllium-potassium check standard solution (concentration of beryllium and potassium is 0.2mg/L), it is identical that its compound method and serial beryllium-potassium calibrate solution;
In the beryllium-potassium calibration solution of a series of variable concentrations that the present embodiment is prepared, the concentration of beryllium is respectively 0mg/L, 0.01mg/L, 0.02mg/L, 0.1mg/L and 0.2mg/L, and the concentration of potassium is respectively 0mg/L, 0.01mg/L, 0.02mg/L, 0.1mg/L and 0.2mg/L.In concrete process for preparation, accurate weighing five parts of quality are the 360B zircaloy standard substance of 1g, be accurate to 0.0001g, be placed in five 50mL hydrofluoric acid resistant beakers respectively, respectively add 8mL pure water submergence sample, then 10mL hydrofluorite-nitric acid compound acid solution sample dissolution is dropwise slowly added respectively, successively solution is all transferred to afterwards in five 100mL hydrofluoric acid resistant volumetric flasks, and add beryllium, the potassium standard solution of five parts of meterings, finally use pure water constant volume, shake up, obtain the beryllium-potassium calibration solution of a series of variable concentrations; And the beryllium-potassium check standard solution of 0.02mg/L is according to the method preparation beryllium and potassium concn;
Step 5, employing inductive coupling plasma emission spectrograph be beryllium element characteristic spectrum intensity in the 313.042nm place beryllium of variable concentrations described in determination step four one by one-potassium calibration solution; Simultaneously, potassium element characteristic spectrum intensity in variable concentrations beryllium-potassium calibration solution is measured one by one in 766.491nm place, setting running parameter is as follows: setting running parameter is as follows: radio-frequency generator power 1.35kW, plasma gas flow rate 13L/min, assisted gas flow 0.8L/min, atomization gas flow 0.85L/min, peristaltic pump pump speed 30rpm, integral time 3s; Set up the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation in beryllium-potassium calibration solution thus, and beryllium-potassium calibrates the concentration of potassium and the calibration curve of potassium element characteristic spectrum intensity corresponding relation in solution;
The present embodiment adopts the upper beryllium-potassium set up of ICP-OES to calibrate the calibration curve of the concentration of beryllium in solution and beryllium element characteristic spectrum intensity corresponding relation as shown in Figure 1, linearly dependent coefficient >=0.999 of this calibration curve as shown in Figure 1.The present embodiment adopts the upper beryllium-potassium set up of ICP-OES to calibrate the calibration curve of the concentration of potassium in solution and potassium element characteristic spectrum intensity corresponding relation as shown in Figure 2, linearly dependent coefficient >=0.999 of this calibration curve as shown in Figure 2.
Adopt ICP-OES to be that 313.042nm place measures beryllium element characteristic spectrum at wavelength, measure potassium element characteristic spectrum at 766.491nm place, the beryllium-potassium check standard solution of preparation is measured, to verify the accuracy of calibration curve.Through verifying, beryllium check standard measured in solution result is 0.021mg/L, and potassium check standard measured in solution result is 0.020mg/L, thus calibration curve accurate and effective can be described;
Step 6, employing inductive coupling plasma emission spectrograph are in the beryllium element characteristic spectrum intensity of liquid to be measured described in 313.042nm place determination step three; Simultaneously, in the potassium element characteristic spectrum intensity of liquid to be measured described in 766.491nm place determination step three, setting running parameter is as follows: radio-frequency generator power 1.35kW, plasma gas flow rate 13L/min, assisted gas flow 0.8L/min, atomization gas flow 0.85L/min, peristaltic pump pump speed 30rpm, integral time 3s; Then beryllium-the potassium set up according to step 5 is calibrated the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation in solution and is calculated the concentration of beryllium in liquid to be measured, calculate the concentration of potassium in liquid to be measured according to the concentration of potassium and the calibration curve of potassium element characteristic spectrum intensity corresponding relation in beryllium-potassium calibration solution, finally calculate the mass content of beryllium and the mass content of potassium in pure zirconium or zircaloy sample.
The present embodiment according to beryllium, Determination of Potassium in calibrating curve determining liquid to be measured, and does three parallel laboratory tests, and calculating mean value is measurement result, in table 3.
Table 3 embodiment 3 measurement result
Adopt recovery of standard addition experimental verification accuracy of the present invention.Prepare sample solution by step one to three, and add the standard solution of variable concentrations.Recovery testu the results are shown in Table 4.
Table 4 recovery of standard addition result
Known by table 4, the recovery, between 95% ~ 105%, illustrates the equal accurate and effective of measurement result of the present invention embodiment of the present invention 1-3 accurately and reliably thus.
The above is only preferred embodiment of the present invention, not imposes any restrictions the present invention.Every above embodiment is done according to invention technical spirit any simple modification, change and equivalence change, all still belong in the protection domain of technical solution of the present invention.
Claims (6)
1. the method for beryllium potassium content in Simultaneously test zirconium and it's alloy, it is characterized in that, the method comprises the following steps:
Step one, turning is carried out to pure zirconium or zircaloy, obtain bits shape sample, then bits shape sample is cleaned up post-drying for subsequent use;
Step 2, employing coning and quartering carry out division sampling to the bits shape sample after oven dry in step one, obtain treating test sample;
Step 3, to treating described in step 2 that dripping hydrofluorite-nitric acid compound acid solution in test sample dissolves, and then proceeds in volumetric flask by solution, shakes up with after pure water constant volume, obtain liquid to be measured; The volume V of described hydrofluorite-nitric acid compound acid solution meets: 8m≤V≤10m, and wherein m is the quality treating test sample, and the unit of m is the unit of g, V is mL;
Step 4, the 360B zircaloy standard substance several parts of quality being m are placed in multiple beaker, each dropping volume is that the hydrofluorite-nitric acid compound acid solution of V is dissolved, obtain many parts of matrix mother liquors, then multiple volumetric flask is got, each part matrix mother liquor and the beryllium standard solution of metering and the potassium standard solution of metering are moved in each volumetric flask respectively, use pure water constant volume respectively afterwards, after shaking up, obtain the beryllium-potassium calibration solution of a series of variable concentrations;
The characteristic spectrum intensity of step 5, employing inductive coupling plasma emission spectrograph beryllium element in the 313.042nm place beryllium of variable concentrations described in determination step four one by one-potassium calibration solution, measure the characteristic spectrum intensity of potassium element in variable concentrations beryllium-potassium calibration solution one by one in 766.491nm place simultaneously, set up the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation in beryllium-potassium calibration solution thus, and beryllium-potassium calibrates the concentration of potassium and the calibration curve of potassium element characteristic spectrum intensity corresponding relation in solution;
Step 6, adopt inductive coupling plasma emission spectrograph in the beryllium element characteristic spectrum intensity of liquid to be measured described in 313.042nm place determination step three, measure the potassium element characteristic spectrum intensity of liquid to be measured in 766.491nm place simultaneously, then the concentration of beryllium in liquid to be measured is calculated according to the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation in the beryllium set up in step 5-potassium calibration solution, the concentration of potassium in liquid to be measured is calculated according to the concentration of potassium and the calibration curve of potassium element characteristic spectrum intensity corresponding relation in beryllium-potassium calibration solution, finally calculate the mass content of beryllium and the mass content of potassium in pure zirconium or zircaloy sample.
2. the method for beryllium potassium content in a kind of Simultaneously test zirconium and it's alloy according to claim 1, is characterized in that, in hydrofluorite-nitric acid compound acid solution described in step 3 and step 4, the mass percentage of HF is 12% ~ 18%, HNO
3mass percentage be 5% ~ 9%.
3. the method for beryllium potassium content in a kind of Simultaneously test zirconium and it's alloy according to claim 1, it is characterized in that, described in step 3 and step 4, m is all satisfied: 0.5g≤m≤1g, and described in step 3 and step 4, the specification of volumetric flask is 50mL or 100mL.
4. the method for beryllium potassium content in a kind of Simultaneously test zirconium and it's alloy according to claim 1, it is characterized in that, in the beryllium-potassium calibration solution of a series of variable concentrations described in step 4, the concentration of beryllium is respectively 0mg/L, 0.01mg/L, 0.02mg/L, 0.1mg/L and 0.2mg/L, and in the beryllium-potassium calibration solution of described a series of variable concentrations, the concentration of potassium is respectively 0mg/L, 0.01mg/L, 0.02mg/L, 0.1mg/L and 0.2mg/L.
5. the method for beryllium potassium content in a kind of Simultaneously test zirconium and it's alloy according to claim 1, it is characterized in that, described in step 5 and step 6, the running parameter of inductive coupling plasma emission spectrograph is: radio-frequency generator power 1.1kW ~ 1.4kW, plasma gas flow rate 12L/min ~ 15L/min, assisted gas flow 0.7L/min ~ 1.1L/min, atomization gas flow 0.7L/min ~ 1.1L/min, peristaltic pump pump speed 15rpm ~ 45rpm, observed altitude 15mm ~ 16mm, integral time 2s ~ 5s.
6. the method for beryllium potassium content in a kind of Simultaneously test zirconium and it's alloy according to claim 1, it is characterized in that, the linearly dependent coefficient that in beryllium described in step 5-potassium calibration solution, the concentration of beryllium and the calibration curve of beryllium element characteristic spectrum intensity corresponding relation and beryllium-potassium calibrate the concentration of potassium in solution and the calibration curve of potassium element characteristic spectrum intensity corresponding relation is all not less than 0.999.
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| CN104020032A (en) * | 2014-06-17 | 2014-09-03 | 攀钢集团攀枝花钢钒有限公司 | Preparation method of test specimens for unbreakable ferro-vanadium chemical analysis |
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