CN116008257A - Method for detecting impurity elements in gallium metal - Google Patents
Method for detecting impurity elements in gallium metal Download PDFInfo
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- CN116008257A CN116008257A CN202211743436.0A CN202211743436A CN116008257A CN 116008257 A CN116008257 A CN 116008257A CN 202211743436 A CN202211743436 A CN 202211743436A CN 116008257 A CN116008257 A CN 116008257A
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Abstract
The invention discloses a method for detecting impurity elements in gallium metal. The method is based on the strong oxidizing property of mixed acid and the coordination effect of negative ions, and the transition metal impurities which are difficult to dissolve are converted into soluble complex ions, and then the soluble complex ions are converted into metal cations by an oxidant; furthermore, when the standard solution is prepared, high-purity gallium with the purity of more than 6N grade is selected for preparation, so that the fluctuation of a detection result is effectively avoided, and the rapid and accurate detection of impurity elements in a gallium metal sample is realized. The whole process of the method does not need to use large-scale instruments such as microwave digestion, ICP-MS and the like, has high test sensitivity, and meets the trace analysis of impurity elements in the gallium metal production process, thereby realizing the rapid on-line detection of samples in the gallium metal production process.
Description
Technical Field
The invention relates to a detection method of impurity elements, in particular to a detection method of impurity elements in metallic gallium, and belongs to the technical field of analysis and detection.
Background
Gallium (gallum) is a grayish blue or silvery white metal, elemental symbol Ga, atomic weight 69.723. Gallium has a very low melting point, only 29.76 ℃ and can be melted in the palm center, but has a very high boiling point reaching 2403 ℃. Pure liquid gallium has a remarkable supercooling tendency, and is easy to oxidize in air to form an oxide film.
The metal gallium is generally recycled and extracted from bauxite or zinc blende and gallium-containing materials, and is mainly recycled and extracted from zinc smelting waste residues, aluminum smelting waste residues and gallium-containing materials.
The industrial production uses industrial grade gallium as raw material, and further purifies by electrolytic method, vacuum distillation method, fractional crystallization method and zone melting method to obtain high purity gallium. The electrolytic process uses 99.99% industrial grade gallium as raw material, and the purity of the high purity gallium is more than or equal to 99.999% through electrolytic refining and other processes. The high purity gallium with the purity of more than or equal to 99.999 percent is used as a raw material, and is further purified by pulling single crystals or other purification processes, so that the purity of the high purity gallium is more than or equal to 99.99999 percent.
Gallium is mainly used for manufacturing semiconductor doping elements of semiconductor gallium nitride, gallium arsenide, gallium phosphide and germanium; pure gallium and low-melting alloy can be used as heat exchange medium for nuclear reaction; the wide temperature range of liquid gallium and its very low vapor pressure make it useful for high temperature thermometers and high temperature manometers; the catalyst is used as a catalyst for the di-esterification in the organic reaction.
The impurity elements such as copper, lead, nickel, zinc and tin in the gallium belong to one of impurity elements which are relatively difficult to remove in the gallium production process, and the quality of the gallium is determined by the content of the impurity elements in the gallium. So the detection of impurity elements in gallium metal is of great importance.
Determination of impurity elements by industry Standard YS/T473-2005 Industrial gallium chemical analysis method inductively coupled plasma Mass Spectrometry determines that impurity element copper is dissolved by microwave digestion and then determined by ICP-MS. In this method, microwave digestion to be used belongs to a relatively expensive device, a general laboratory is not necessarily configured, and an inductively coupled plasma mass spectrometer (ICP-MS) belongs to a large-scale precision device, and is relatively expensive, and the general laboratory is not necessarily configured. Moreover, the method has long analysis time, is not suitable for timely detection on a gallium metal production site and guides production.
Therefore, the establishment of a method suitable for rapidly detecting impurity elements in gallium is of great importance, and has great guiding significance for gallium-containing material process recovery and gallium bilateral trade.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for detecting impurity elements in metal gallium, which is based on the strong oxidizing property of mixed acid and the coordination action of negative ions, and is used for converting transition metal impurities which are difficult to dissolve into soluble complex ions, and then converting the soluble complex ions into metal cations through an oxidant; furthermore, when the standard solution is prepared, high-purity gallium with the purity of more than 6N grade is selected for preparation, so that the fluctuation of a detection result is effectively avoided, and the rapid and accurate detection of impurity elements in a gallium metal sample is realized. Based on the rapid and thorough dissolution of the gallium metal sample in the detection method provided by the invention, large-scale instruments such as microwave digestion, ICP-MS and the like are not needed, so that the rapid on-line detection of the sample in the gallium metal production process is realized.
In order to achieve the technical purpose, the invention provides a method for detecting impurity elements in metallic gallium, which comprises the following steps:
1) Dissolving gallium metal in mixed acid, adding an oxidant for oxidation reaction when the volume of the solution is reduced by 70-90%, and then fixing the volume to obtain a liquid to be measured;
2) Dissolving high-purity gallium in mixed acid, adding an oxidant for oxidation reaction when the volume of the solution is reduced by 70-90%, then fixing the volume, adding a copper standard substance to obtain a standard solution, measuring the impurity element content of the standard solution and the solution to be measured by an inductively coupled plasma emission spectrometer, and fitting by a standard curve method to obtain the high-purity gallium-based mixed acid;
the mixed acid is any two of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid; the oxidant is any one of nitric acid, sulfuric acid and hydrogen peroxide.
The detection method provided by the invention is based on the strong oxidizing property of mixed acid and the coordination effect of negative ions, so that transition metal impurities which are difficult to dissolve are converted into soluble complex ions, and then the soluble complex ions are converted into metal cations through an oxidant; furthermore, when the standard solution is prepared, high-purity gallium with the purity of more than 6N grade is selected for preparation, so that the fluctuation of a detection result is effectively avoided, and the rapid and accurate detection of impurity elements in a gallium metal sample is realized.
As a preferable scheme, the mixed acid is concentrated hydrochloric acid and concentrated nitric acid according to the mass ratio of 1:0.3 to 3. Further, the mixed acid is concentrated hydrochloric acid and concentrated nitric acid according to the mass ratio of 1: 3.
The proportion of the mixed acid is strictly required to be carried out according to the requirements, if the concentration of the concentrated hydrochloric acid is too high, the oxidability of the mixed acid is too low, and soluble complex ions cannot be formed with impurity elements; if the proportion of the concentrated nitric acid is too high, the complex anions in the mixed acid are insufficient, the surface energy of the impurity element is difficult to reduce, and complete oxidation and complexation cannot be realized.
As a preferred embodiment, the concentration of the oxidizing agent is 30 to 75wt%.
As a preferred embodiment, the metallic gallium is composed of a gallium element and an impurity element.
As a preferred embodiment, the impurities include: cu, pb, zn, al, ca, fe, sn and Ni, the total amount of the impurities being 10 -3 ％～10 -1 ％。
As a preferable scheme, the volume ratio of the mixed acid to the oxidant is 1.5-2.5:1. The addition of the mixed acid and the oxidant is strictly carried out according to the proportion, and if the proportion of the mixed acid is too high, the concentration of the oxidant is too low, and all soluble complex ions are difficult to be converted into metal cations; if the amount of the oxidizing agent added is too large, peroxidation occurs, and a poorly soluble metal oxide is produced.
As a preferred embodiment, the oxidizing agent is nitric acid.
As a preferred embodiment, the dissolution conditions are: the stirring speed is 5-15 rpm, the temperature is 40-70 ℃ and the time is 15-30 min.
As a preferred embodiment, the oxidation reaction conditions are: the stirring speed is 5-15 rpm, the temperature is 60-90 ℃ and the time is 5-10 min.
As a preferable scheme, the high-purity gallium is metallic gallium with the purity more than or equal to 6N grade. The standard solution must be based on the above requirements, and if the purity of the base is too low, the test results will have too high fluctuation and overall low test results.
As a preferred scheme, the method for detecting the impurity element in the gallium metal further comprises an optimization process, wherein the optimization process is as follows: and (3) testing the content of impurity elements in the gallium through trace analysis, and carrying out contrast correction on the result obtained in the step (2).
As a preferred embodiment, the trace analysis is inductively coupled plasma mass spectrometry and/or glow discharge mass spectrometry.
Compared with the prior art, the invention has the beneficial technical effects that:
1) The detection method provided by the invention is based on the strong oxidizing property of mixed acid and the coordination effect of negative ions, so that transition metal impurities which are difficult to dissolve are converted into soluble complex ions, and then the soluble complex ions are converted into metal cations through an oxidant; furthermore, when the standard solution is prepared, high-purity gallium with the purity of more than 6N grade is selected for preparation, so that the fluctuation of a detection result is effectively avoided, and the rapid and accurate detection of impurity elements in a gallium metal sample is realized.
2) According to the technical scheme provided by the invention, based on the synergistic effect between the mixed acid and the oxidant, the insoluble impurity element is oxidized into the soluble metal cation through two steps of acidity, so that the rapid and thorough dissolution of the metal gallium sample is realized. The whole process has high test sensitivity without the help of large-scale instruments such as microwave digestion, ICP-MS and the like, and meets the analysis of impurity element content in the gallium metal production process, thereby realizing the rapid on-line detection of samples in the gallium metal production process.
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the claims.
The method for accurately measuring the impurity copper element in the A batch sample is carried out by referring to an inductively coupled plasma mass spectrometry (YS/T473-2015) of measuring the impurity element in an industrial gallium chemical analysis method, and comprises the following steps:
weighing a lot of 0.1002 g gallium samples, placing the samples in a polytetrafluoroethylene digestion tank, simultaneously blanking the samples, adding 1.7mL of UP-level nitric acid and 0.3mL of UP-level hydrochloric acid, digesting in a microwave digestion instrument, cooling the dissolved samples to room temperature, transferring the cooled samples to a 100mL volumetric flask, adding a rhodium standard solution (the final concentration is 5.0 ng/mL), diluting to a scale with deionized water, and shaking uniformly.
And under the optimal condition of the selected optimal inductively coupled plasma mass spectrometer, the content of impurity element copper is measured to be 4.2 mug/g by adopting a standard curve method and internal standard correction.
The batch of gallium samples was sent to a third party laboratory for GD-MS detection with a detection result of 4.1. Mu.g/g. The copper content in the batch of gallium metal was determined to be 4.2 mug/g as a reliable result by a two-round test.
Example 1
20 ml of UP grade hydrochloric acid and 60 ml of UP grade nitric acid are added into a clean beaker to prepare mixed acid.
Batch a, 1.0015 g gallium metal sample, was weighed into a 100ml polytetrafluoroethylene beaker while blank was performed. Adding 10 ml of mixed acid, stirring, dissolving at low temperature until the volume of the solution is about 2ml, adding 5 ml of nitric acid, stirring, heating to dissolve completely, cooling to constant volume of 50 ml, and mixing uniformly.
Weighing 4 parts of a 7N high-purity gallium sample in a 100ml polytetrafluoroethylene beaker, adding 10 ml of mixed acid, stirring, dissolving at low temperature until the volume of the solution is about 2ml, adding 5 ml of nitric acid, stirring, heating to dissolve completely, cooling to constant volume of 50 ml, and uniformly mixing; and adding copper standard solutions 0, 2.5, 5.0 and 25.0 mug respectively, and uniformly mixing, wherein the copper standard solutions respectively contain copper: 0. 0.05, 0.10, 0.50. Mu.g/mL.
And sequentially measuring the intensities of copper element spectral lines 324.7nm and 327.4nm on an inductively coupled plasma emission spectrometer, drawing a working curve according to a least square method with the corresponding concentrations, and measuring the intensity of a sample to obtain the concentration of impurity elements in the gallium metal sample of 4.3 mug/g.
This result was consistent with ICP-MS and GD-MS results.
Comparative example 1
20 ml of UP grade hydrochloric acid and 60 ml of UP grade nitric acid are added into a clean beaker to prepare mixed acid.
Batch a, 1.0010 g gallium metal sample, was weighed into a 100ml polytetrafluoroethylene beaker while blank was performed. 10 ml of mixed acid is added, stirred and dissolved at low temperature until the volume of the solution is about 2ml, cooled to constant volume of 50 ml and evenly mixed.
Weighing 4 parts of a 7N Gao Chunjia 0.100.100 g gallium metal sample in a 100ml polytetrafluoroethylene beaker, adding 10 ml of mixed acid, stirring, dissolving at a low temperature until the volume of the solution is about 2ml, adding 5 ml of nitric acid, stirring, heating to dissolve completely, cooling to constant volume of 50 ml, and uniformly mixing; and adding copper standard solutions 0, 2.5, 5.0 and 25.0 mug respectively, and uniformly mixing, wherein the copper standard solutions respectively contain copper: 0. 0.05, 0.10, 0.50. Mu.g/mL.
And sequentially measuring the intensities of copper element spectral lines 324.7nm and 327.4nm on an inductively coupled plasma emission spectrometer, drawing a working curve according to a least square method with the corresponding concentrations, and measuring the intensity of a sample to obtain the concentration of impurity elements in the gallium metal sample of 0.1 mug/g.
Comparative example 2
20 ml of UP grade hydrochloric acid and 60 ml of UP grade nitric acid are added into a clean beaker to prepare mixed acid.
Batch a, 1.0015 g gallium metal sample, was weighed into a 100ml polytetrafluoroethylene beaker while blank was performed. Adding 10 ml of mixed acid, stirring, dissolving at low temperature until the volume of the solution is about 2ml, adding 5 ml of nitric acid, stirring, heating to dissolve completely, cooling to constant volume of 50 ml, and mixing uniformly.
Copper standard solutions 0, 2.5, 5.0 and 25.0 mug are respectively added into 4 50 ml volumetric flasks, 2.5 ml UP nitric acid is added, and the standard solutions are uniformly mixed, wherein the copper content of the standard solutions is as follows: 0. 0.05, 0.10, 0.50. Mu.g/mL.
And sequentially measuring the intensities of copper element spectral lines 324.7nm and 327.4nm on an inductively coupled plasma emission spectrometer, drawing a working curve with the corresponding concentration according to a least square method, and measuring the intensity of a sample to obtain the concentration of impurity elements in the gallium metal sample of 3.2 mug/g.
Comparative example 1 differs from example 1 in that no further addition of the oxidizing agent resulted in a few solids at the bottom of the cup that were not completely dissolved. The results obtained in comparative example 1 are very different from those of ICP-MS and GD-MS. The reason is that the metal gallium has higher activity than copper, and in the process of mixed acid dissolution, the mixed acid firstly reacts with gallium to generate soluble complex ions, and then further reacts with an oxidant to generate gallium ions. Therefore, when gallium is not completely dissolved or soluble complex gallium ions cannot be converted into gallium ions, copper impurities cannot be completely dissolved.
From this example, it can be seen that the copper impurity in metallic gallium is measured and the sample must be sufficiently dissolved. In order to ensure that the gallium metal sample is fully dissolved, the method is ensured from two aspects, on one hand, the synergistic effect of mixed acid and oxidant is utilized, firstly, mixed calculation is adopted to dissolve the gallium metal, and secondly, concentrated nitric acid is used to dissolve and oxidize impurities possibly remained; on the other hand, the gallium is not active by low-temperature dissolution, and can be thoroughly dissolved by low-temperature long-time dissolution. Thus, the thoroughness of dissolution of gallium metal and impurities is ensured, and the reliability of the result is ensured.
Comparative example 2 is most different from example 1 in that the standard solution prepared using high purity gallium was not added. The results differ considerably from the ICP-MS and GD-MS results. The reason is that the process adopts a pure standard curve method, and the influence of matrix gallium on copper determination is not considered. Generally, in the presence of a substrate, the strength of the element to be measured is inhibited to a certain extent, and if correction is not performed at first, the test result is smaller and is not consistent with the actual value.
Claims (8)
1. A method for detecting an impurity element in gallium metal, comprising:
1) Dissolving gallium metal in mixed acid, adding an oxidant for oxidation reaction when the volume of the solution is reduced by 70-90%, and then fixing the volume to obtain a liquid to be measured;
2) Dissolving high-purity gallium in mixed acid, adding an oxidant for oxidation reaction when the volume of the solution is reduced by 70-90%, then fixing the volume, adding a copper standard substance to obtain a standard solution, measuring the impurity element content of the standard solution and the solution to be measured by an inductively coupled plasma emission spectrometer, and fitting by a standard curve method to obtain the high-purity gallium-based mixed acid;
the mixed acid is any two of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid; the oxidant is any one of nitric acid, sulfuric acid and hydrogen peroxide.
2. The method for detecting an impurity element in gallium according to claim 1, wherein: the mixed acid is mixed acid of concentrated hydrochloric acid and concentrated nitric acid according to the mass ratio of 1:0.3-3; the concentration of the oxidant is 30-75wt%.
3. The method for detecting an impurity element in gallium according to claim 1, wherein: the metal gallium consists of gallium element and impurity element; the impurities include: cu, pb, zn, al, ca, fe, sn and Ni, the total amount of the impurities being 10 -3 ％～10 -1 ％。
4. The method for detecting an impurity element in gallium according to claim 1, wherein: the volume ratio of the mixed acid to the oxidant is 1.5-2.5:1; the oxidant is nitric acid.
5. The method for detecting an impurity element in gallium according to claim 1, wherein: the dissolution conditions are as follows: stirring speed is 5-15 rpm, temperature is 40-70 ℃ and time is 15-30 min; the conditions of the oxidation reaction are as follows: the stirring speed is 5-15 rpm, the temperature is 60-90 ℃ and the time is 5-10 min.
6. The method for detecting an impurity element in gallium according to claim 1, wherein: the high-purity gallium is metal gallium with the purity more than or equal to 6N level.
7. The method for detecting an impurity element in gallium according to any one of claims 1 to 6, wherein: the method also comprises an optimization process, wherein the optimization process is as follows: and (3) testing the content of impurity elements in the gallium through trace analysis, and carrying out contrast correction on the result obtained in the step (2).
8. The method for detecting an impurity element in gallium according to claim 7, wherein: the trace analysis is inductively coupled plasma mass spectrometry and/or glow discharge mass spectrometry.
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