CN117388240A - Method for testing low-concentration impurity zirconium in high-purity hafnium oxide - Google Patents
Method for testing low-concentration impurity zirconium in high-purity hafnium oxide Download PDFInfo
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- CN117388240A CN117388240A CN202311421323.3A CN202311421323A CN117388240A CN 117388240 A CN117388240 A CN 117388240A CN 202311421323 A CN202311421323 A CN 202311421323A CN 117388240 A CN117388240 A CN 117388240A
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 49
- 238000012360 testing method Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910000449 hafnium oxide Inorganic materials 0.000 title claims abstract description 29
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000012535 impurity Substances 0.000 title claims abstract description 28
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 36
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 29
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- 230000004044 response Effects 0.000 claims abstract description 11
- 238000010790 dilution Methods 0.000 claims abstract description 7
- 239000012895 dilution Substances 0.000 claims abstract description 7
- 238000009616 inductively coupled plasma Methods 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 238000012544 monitoring process Methods 0.000 claims abstract description 4
- 239000012086 standard solution Substances 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000011084 recovery Methods 0.000 description 12
- 239000000523 sample Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 4
- 238000012795 verification Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 229910001029 Hf alloy Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- INIGCWGJTZDVRY-UHFFFAOYSA-N hafnium zirconium Chemical compound [Zr].[Hf] INIGCWGJTZDVRY-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Plasma & Fusion (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to the field of element determination methods, in particular to a method for testing low-concentration impurity zirconium in high-purity hafnium oxide, which comprises the following steps of 1, weighing a hafnium matrix with a set amount, and dissolving the hafnium matrix with a set volume through a preset step to obtain a hafnium matrix solution with a preset content; step 2, according to a plurality of preset standard curve points in the range of 0ppm to 500ppm, the dilution ratio of the inductively coupled plasma spectrometer is 1:100, the test range of the standard curve points is extended, and the instrument is used for testing; and 3, fitting data of the intensity and the concentration of the instrument response, and monitoring zirconium impurity. The invention can accurately test the low-concentration impurity zirconium in the high-purity hafnium oxide.
Description
Technical Field
The invention relates to the field of element measurement methods, in particular to a method for testing low-concentration impurity zirconium in high-purity hafnium oxide.
Background
Hafnium oxide is white crystal powder, and is used as a raw material for producing metal hafnium and hafnium alloy, and has wide application prospect due to the advantages of good corrosion resistance, conductivity and the like, but the market has extremely high purity requirements on the hafnium oxide, and the hafnium oxide is: the purity is more than or equal to 99.99 percent. The purity of the product is directly influenced by the zirconium content of the hafnium oxide product in the production process, the control limit of the zirconium content in the hafnium oxide is below 3%, and the detection precision of impurity zirconium in the method is 1000ppm by a matrix matching method.
However, this method has the problems that: for the high-purity hafnium oxide with the purity more than or equal to 99.99 percent, the impurity zirconium content is less than 100ppm and cannot be monitored.
Disclosure of Invention
The invention aims to provide a method for testing low-concentration impurity zirconium in high-purity hafnium oxide, so as to solve the problem that the existing method cannot measure the content of impurity zirconium in high-purity hafnium oxide.
The method for testing the low-concentration impurity zirconium in the high-purity hafnium oxide comprises the following steps:
step 1, weighing a preset amount of hafnium matrix, and dissolving the hafnium matrix to a preset volume through a preset step to obtain a hafnium matrix solution with a preset content;
further comprises:
step 2, according to a plurality of preset standard curve points in the range of 0ppm to 500ppm, the dilution ratio of the inductively coupled plasma spectrometer is 1:100, the test range of the standard curve points is extended, and the instrument is used for testing;
and 3, fitting data of the intensity and the concentration of the instrument response, and monitoring zirconium impurity.
Further, in the step 1, the set amount is 100g, the preset step sequentially comprises acid washing, water washing, adding hydrofluoric acid for dissolution and fixing the volume to 1000mL, and the preset content is 100g/L.
Further, in the step 2, six standard curve points are set, and are respectively: 0ppm, 10ppm, 50ppm, 100ppm, 200ppm, 500ppm.
Further, in the step 2, a fixed amount of hafnium base solution and different preset amounts of zirconium standard solution are removed according to each standard curve point, and the volume is fixed to 100mL for dilution.
Further, in the step 2, for a standard curve point of 0 ppm: transferring 10mL of hafnium substrate solution into a 100mL volumetric flask, and fixing the volume to 100 mL;
for 10ppm standard curve point: transferring 10ml of hafnium matrix solution and 0.1 ml of 10000ppm zirconium standard solution into a 100ml volumetric flask, and fixing the volume to 100 ml;
for 50ppm standard curve points: transferring 10ml of hafnium matrix solution and 0.5 ml of 10000ppm zirconium standard solution into a 100ml volumetric flask, and fixing the volume to 100 ml;
for 100ppm standard curve points: transferring 10ml of hafnium matrix solution and 1.0 ml of 10000ppm zirconium standard solution into a 100ml volumetric flask, and fixing the volume to 100 ml;
standard curve point for 200 ppm: transferring 10ml of hafnium matrix solution and 2.0 ml of 10000ppm zirconium standard solution into a 100ml volumetric flask, and fixing the volume to 100 ml;
standard curve point for 500 ppm: 10ml of hafnium base solution and 5.0 ml of 10000ppm zirconium standard solution were removed in a 100ml volumetric flask and the volume was fixed to 100 ml.
In step 3, the diluted solution is injected into an inductively coupled plasma spectrometer, and the wavelength is selected according to the strong wavelength response intensity and the response curve without interference with other elements, so as to perform the test.
The beneficial effect of this scheme is:
because zirconium hafnium is in a symbiotic relationship, a very small amount of journal zirconium existing in the high-purity hafnium oxide is difficult to detect, and can cause faults of subsequent power generation equipment, and the like, the method can accurately test impurity zirconium on the premise that the test duration and the test cost are not increased at a limited point by setting the concentration of six points to test low-concentration impurity zirconium in the high-purity hafnium oxide, and can improve the product quality of the hafnium oxide in the production process, so that the faults or abnormal probability of the subsequent power generation equipment is reduced.
Drawings
FIG. 1 is a flow chart of an embodiment of a method for testing low concentration zirconium impurity in high purity hafnium oxide according to the present invention;
FIG. 2 is a schematic diagram showing a fitting of test results of a test example of a test method for low-concentration impurity zirconium in high-purity hafnium oxide according to the present invention;
FIG. 3 is a graph showing the results of 21 discrete test samples of the test method of the low concentration zirconium impurity in the high purity hafnium oxide according to the present invention;
FIG. 4 is a bar graph of a test method for testing zirconium as a low concentration impurity in high purity hafnium oxide according to the present invention for verification of the same sample addition recovery method;
FIG. 5 is a bar graph of the test method of the invention for testing zirconium as a low concentration impurity in high purity hafnium oxide, showing the test example of the method for recovering the different samples by the standard addition method.
Detailed Description
Further details are provided below with reference to the specific embodiments.
Examples
The method for testing the zirconium with low concentration impurity in the high-purity hafnium oxide is shown in fig. 1, and comprises the following steps:
step 1, weighing a set amount of hafnium matrix, dissolving the hafnium matrix to a fixed volume through a preset step to obtain a hafnium matrix solution with a preset content, wherein the preset amount is 100g, the preset step sequentially comprises acid washing, water washing, adding hydrofluoric acid for dissolution and fixing the volume to 1000mL, and the preset content is 100g/L.
And 2, extending the test range of the standard curve point by using the dilution ratio of the inductively coupled plasma spectrometer to 1:100 according to a plurality of preset standard curve points within the range of 0ppm to 500ppm, and testing by using an instrument. Six standard curve points are arranged, and the standard curve points are respectively: 0ppm, 10ppm, 50ppm, 100ppm, 200ppm and 500ppm, and a fixed amount of hafnium base solution and different preset amounts of zirconium standard solution are removed according to each standard curve point, and the fixed volume is adjusted to 100mL for dilution, specifically:
for the 0ppm standard curve point: transferring 10mL of hafnium substrate solution into a 100mL volumetric flask, and fixing the volume to 100 mL;
for 10ppm standard curve point: transferring 10ml of hafnium matrix solution and 0.1 ml of 10000ppm zirconium standard solution into a 100ml volumetric flask, and fixing the volume to 100 ml;
for 50ppm standard curve points: transferring 10ml of hafnium matrix solution and 0.5 ml of 10000ppm zirconium standard solution into a 100ml volumetric flask, and fixing the volume to 100 ml;
for 100ppm standard curve points: transferring 10ml of hafnium matrix solution and 1.0 ml of 10000ppm zirconium standard solution into a 100ml volumetric flask, and fixing the volume to 100 ml;
standard curve point for 200 ppm: transferring 10ml of hafnium matrix solution and 2.0 ml of 10000ppm zirconium standard solution into a 100ml volumetric flask, and fixing the volume to 100 ml;
standard curve point for 500 ppm: 10ml of hafnium base solution and 5.0 ml of 10000ppm zirconium standard solution were removed in a 100ml volumetric flask and the volume was fixed to 100 ml.
And 3, injecting the diluted solution into an inductively coupled plasma spectrometer, selecting wavelength according to strong wavelength response intensity and no interference between a response curve and other elements, testing, fitting the intensity and the concentration of instrument response with data, and monitoring zirconium impurity.
Test examples
Taking a hafnium substrate with the trade name of 4915 as an example, weighing 100g, washing with acid, washing with water, adding hydrofluoric acid for dissolution, and dissolving in a 1000ml polytetrafluoroethylene volumetric flask to form 100g/L hafnium substrate solution. According to the method steps of the embodiment, the data fitting is carried out on the intensity and the concentration of the obtained instrument response, the result diagram is shown in fig. 2, and as compared with the existing four-point fitting method, the standard curve diagram of the test example covers a larger concentration range than the original coverage range, the fitting rate of six-point linear fitting is 0.9986, and the linear fitting requirement is met.
And (3) verifying the accuracy of the test result of the embodiment method: the check sample was tested for accuracy by performing 21 discrete tests, the control limit of the check sample was defined as 35550-38600ppm, and the check sample results were shown to be within the upper and lower limits of the original control, as shown in fig. 3.
The report limit and the detection precision are determined by carrying out 21 times of discontinuous three days of testing on blank samples. The results of the tests shown in Table 1 were obtained.
TABLE 1 statistical table of results of three discontinuous days of blank samples
The detection limit mdl=s×t (n-1, 0.99), the t value was 3.14 when the number of parallel measurements n=7, and the standard deviation was 2ppm by performing the above-mentioned discontinuous 21 tests, and the detection limit mdl=3.14×2=7 ppm (rounded).
100ppm, 200ppm and 500ppm were added to the same sample (231000 XN 1) by the labeled recovery method, and the sample was sampled and tested, and the data are shown in Table 2 and FIG. 4.
TABLE 2 verification results Table of labeled recovery method for the same sample
As can be seen from Table 2 and FIG. 4, the standard recovery rate of 95% -104% is obtained in the same sample by using the standard recovery method, and the allowable limit of recovery rate is 95% -105% when the content of the detected component is 100mg/L (100 ppm) in the experimental analysis method of the embodiment with reference to GB/T27404-2008 standard for physical and chemical detection of laboratory quality control Specification food.
By using a standard recovery method, three different samples are respectively added with 100ppm, 200ppm and 500ppm, and sample injection test is performed, and the test verification of the sample injection standard curve point setting effect is performed, so that the results shown in table 3 and fig. 5 are obtained.
TABLE 3 verification results Table of labeled recovery method for different samples
As can be seen from Table 3 and FIG. 5, the standard recovery rate is within the range of 100% -103% by using the standard recovery method in different samples, and the allowable limit of recovery rate is 95% -105% when the content of the tested component is 100mg/L (100 ppm) in the experimental analysis method.
By comparing the same sample with different samples in a standard recovery method, the tested standard curve point component can be verified to be in the range of 100ppm, and the method of the embodiment can accurately detect zirconium impurity in high-purity hafnium oxide.
The foregoing is merely exemplary embodiments of the present invention, and specific structures and features that are well known in the art are not described in detail herein. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the structure of the present invention, and these should also be considered as the scope of the present invention, which does not affect the effect of the implementation of the present invention and the utility of the patent. The protection scope of the present application shall be subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (6)
1. The method comprises the following steps of 1, weighing a preset amount of hafnium matrix, and dissolving the hafnium matrix to a preset volume through a preset step to obtain a hafnium matrix solution with a preset content;
characterized by further comprising:
step 2, according to a plurality of preset standard curve points in the range of 0ppm to 500ppm, the dilution ratio of the inductively coupled plasma spectrometer is 1:100, the test range of the standard curve points is extended, and the instrument is used for testing;
and 3, fitting data of the intensity and the concentration of the instrument response, and monitoring zirconium impurity.
2. The method for testing low concentration impurity zirconium in high purity hafnium oxide according to claim 1, wherein: in the step 1, the set amount is 100g, the preset steps sequentially comprise acid washing, water washing, adding hydrofluoric acid for dissolution and fixing the volume to 1000mL, and the preset content is 100g/L.
3. The method for testing low-concentration impurity zirconium in high-purity hafnium oxide according to claim 2, wherein: in the step 2, six standard curve points are set, and are respectively: 0ppm, 10ppm, 50ppm, 100ppm, 200ppm, 500ppm.
4. The method for testing low concentration impurity zirconium in high purity hafnium oxide according to claim 3, wherein: in the step 2, a fixed amount of hafnium base solution and different preset amounts of zirconium standard solution are removed according to each standard curve point, and the volume is fixed to 100mL for dilution.
5. The method for testing low concentration impurity zirconium in high purity hafnium oxide according to claim 4, wherein: in the step 2, for a standard curve point of 0 ppm: transferring 10mL of hafnium substrate solution into a 100mL volumetric flask, and fixing the volume to 100 mL;
for 10ppm standard curve point: transferring 10ml of hafnium matrix solution and 0.1 ml of 10000ppm zirconium standard solution into a 100ml volumetric flask, and fixing the volume to 100 ml;
for 50ppm standard curve points: transferring 10ml of hafnium matrix solution and 0.5 ml of 10000ppm zirconium standard solution into a 100ml volumetric flask, and fixing the volume to 100 ml;
for 100ppm standard curve points: transferring 10ml of hafnium matrix solution and 1.0 ml of 10000ppm zirconium standard solution into a 100ml volumetric flask, and fixing the volume to 100 ml;
standard curve point for 200 ppm: transferring 10ml of hafnium matrix solution and 2.0 ml of 10000ppm zirconium standard solution into a 100ml volumetric flask, and fixing the volume to 100 ml;
standard curve point for 500 ppm: 10ml of hafnium base solution and 5.0 ml of 10000ppm zirconium standard solution were removed in a 100ml volumetric flask and the volume was fixed to 100 ml.
6. The method for testing low concentration impurity zirconium in high purity hafnium oxide according to claim 5, wherein: in the step 3, the diluted solution is injected into an inductively coupled plasma spectrometer, and the wavelength is selected according to the wavelength response intensity and the response curve without interference with other elements, so as to perform the test.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311421323.3A CN117388240A (en) | 2023-10-27 | 2023-10-27 | Method for testing low-concentration impurity zirconium in high-purity hafnium oxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311421323.3A CN117388240A (en) | 2023-10-27 | 2023-10-27 | Method for testing low-concentration impurity zirconium in high-purity hafnium oxide |
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| CN117388240A true CN117388240A (en) | 2024-01-12 |
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| CN202311421323.3A Pending CN117388240A (en) | 2023-10-27 | 2023-10-27 | Method for testing low-concentration impurity zirconium in high-purity hafnium oxide |
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