Summary of the invention
Purpose of the present invention is exactly the deficiency that the above-mentioned prior art of specific aim exists, and a kind of sensitivity and accuracy, raising analysis efficiency that can effectively improve mensuration is provided, saves the plumbous method of trace in the mensuration aluminium ingot of analysis cost, protection environment
Method of the present invention is achieved through the following technical solutions.
The plumbous assay method of trace in a kind of aluminium ingot, it is characterized in that its test process is the sample that will take by weighing, use aqua regia dissolution, adding oxygenant makes the lead ion of sample middle or low price attitude be oxidized to high valence state, with the acidity of sodium hydroxide solution control solution,, make lead ion in the sample solution be converted into the hydride of gaseous state again with the reductive agent reaction, do carrier gas with argon gas and be introduced into the atomic fluorescence spectrometer measuring system, measure.
The plumbous assay method of trace in a kind of aluminium ingot of the present invention is characterized in that its testing procedure comprises:
(1) course of dissolution of sample
Take by weighing sample 0.1000g, place beaker, add little water, add 15ml chloroazotic acid (1+1) and cover surface plate, after treating that vigorous reaction stops, being placed on heating for dissolving on the electric furnace, and steaming near and do, take off, be cooled to room temperature, solution is moved in the 100mL volumetric flask, hydrochloric acid solution constant volume with 2%;
(2) the mensuration process of sample:
The sample that above dissolving is good and contain the mixed solution of NaOH of potassium borohydride, the 11g/L potassium ferricyanide, the 12g/L of 10g/L is done current-carrying with 2% hydrochloric acid and is together introduced reactive system in the atomic fluorescence spectrometer, the PbH that is produced
4Gas is done carrier gas with argon gas and is introduced in the atomic fluorescence spectrometer, and under selected Instrument measuring parameter, according to the relation that fluorescence intensity and plumbous concentration are directly proportional, the trace in the quantitative measurement aluminium ingot product is plumbous.
Method of the present invention must preparation reagent have 1, Pb standard solution (1mg/mL), the time spent is diluted to 10 μ g/L; 2, KBH
4Solution 10g/L; 3, K
3Fe (CN)
6Solution 11g/L; 4, NaOH solution 12g/L; 5, HCL solution 2%; 6, chloroazotic acid (1+1); 7, argon gas (99.99%).
It is atomic fluorescence spectrometer that method of the present invention is measured employed instrument.
The employed sample of method of the present invention should be processed into the chip that thickness is not more than 1mm.
The selected Instrument measuring parameter of method of the present invention is: 200 ℃ of negative high voltage 260V, lamp current 60mA, observed altitude 8em atomization temperatures, carrier gas flux 400mL/min, shield gas flow amount 800mL/min (atomic fluorescence spectrometer of different model is owing to the sensitivity difference, and location parameter is slightly different).
A kind of control of passing through the reaction conditions of sample of method of the present invention takes place the micro-plumbous richness in the aluminium ingot is amassed with hydride, measures with atomic fluorescence spectrometry, has obtained good result.Can determine the plumbous content of trace in the aluminium ingot accurately and rapidly, be applicable to that all aluminium ingot manufacturers in the whole nation carry out the plumbous analysis of trace, to produce the aluminium ingot product of the quality requirements that is up to state standards.
Embodiment
The plumbous assay method of trace in a kind of aluminium ingot, its test process is the sample that will take by weighing, use aqua regia dissolution, adding oxygenant makes the lead ion of sample middle or low price attitude be oxidized to high valence state, with the acidity of sodium hydroxide solution control solution,, make lead ion in the sample solution be converted into the hydride of gaseous state again with the reductive agent reaction, do carrier gas with argon gas and be introduced into the atomic fluorescence spectrometer measuring system, measure.
Its testing procedure comprises: the course of dissolution of (1) sample: take by weighing sample 0.1000g, place beaker, add little water, add 15ml chloroazotic acid (1+1) and cover surface plate, treat that vigorous reaction stops after, be placed on heating for dissolving on the electric furnace, and steam near and do, take off, be cooled to room temperature, solution is moved in the 100mL volumetric flask hydrochloric acid solution constant volume with 2%; (2) the mensuration process of sample: the mixed solution of sample that above dissolving is good and the NaOH of the potassium borohydride that contains 10g/L, the 11g/L potassium ferricyanide, 12g/L, do current-carrying with 2% hydrochloric acid and together introduce reactive system in the atomic fluorescence spectrometer, the PbH that is produced
4Gas is done carrier gas with argon gas and is introduced in the atomic fluorescence spectrometer, and under selected Instrument measuring parameter, according to the relation that fluorescence intensity and plumbous concentration are directly proportional, the trace in the quantitative measurement aluminium ingot product is plumbous.
That the invention will be further described is as follows in conjunction with example:
The condition determination of atomic fluorescence spectrometer is: lamp current 60mA, negative high voltage 260V, observed altitude 8mm, 200 ℃ of atomization temperatures, carrier gas flux 400mL/min, shield gas flow amount 800mL/min.Different instrumental sensitivity differences, condition determination are slightly different.
Embodiment 1
Get the aluminium ingot sample that domestic certain factory produces, be processed into the chip that thickness is not more than 1mm.
Take by weighing 2 parts in 0.1000g sample, content plumbous in the sample is respectively 0.0004%-0.0022%, and sample is placed the 300ml beaker, add little water, add 15mL wang aqueous solution (1+1), cover surface plate, treat that vigorous reaction stops after, be placed on heating for dissolving on the electric furnace, and steam near and do, take off, be cooled to room temperature, solution is moved in the 100mL volumetric flask hydrochloric acid solution constant volume with 2%.
Other takes by weighing 3.6g NaOH in the 500mL beaker that fills little water, after the dissolving, adds the stirring of 3.0g potassium borohydride and makes its dissolving, then, adds the 3.3g potassium ferricyanide again, is diluted to 300mL with deionized water.The addition sequence of reagent can not be put upside down.
Pipette 10.0mL top grade pure hydrochloric acid in the 500mL volumetric flask, be diluted to scale with deionized water, mixing is used as current-carrying.Do blank test in company with sample.
The mixed solution of sample that above dissolving is good and the NaOH (acidity adjustment) of the potassium borohydride (reductive agent) that contains 10g/L, the 11g/L potassium ferricyanide (oxygenant and screening agent), 12g/L, do current-carrying with 2% hydrochloric acid and together introduce reactive system in the atomic fluorescence spectrometer, the PbH that reaction is produced
4Gas is done carrier gas with argon gas and is introduced in the atomic fluorescence spectrometer, under selected Instrument measuring parameter, measures.
Finish when shared 1.5 hours from taking by weighing sample (plumbous content 0.0004%) to measuring, the mean value of measuring fluorescence intensities for 11 times is 976.08, standard deviation 9.3661, coefficient of alteration 0.96%.
Finish when shared 1.5 hours from taking by weighing sample (plumbous content 0.0022%) to measuring, the mean value of measuring fluorescence intensities for 11 times is 332.89, standard deviation 2.6608, coefficient of alteration 0.8%.
Embodiment 2
Get the aluminium ingot sample that domestic certain factory produces, be processed into the chip that thickness is not more than 1mm.
Take by weighing the 0.1000g sample, sample is placed the 300ml beaker, add little water, add 15mL wang aqueous solution (1+1), cover surface plate, after treating that vigorous reaction stops, being placed on heating for dissolving on the electric furnace, and steaming near and do, take off, be cooled to room temperature, solution is moved in the 100mL volumetric flask, hydrochloric acid solution constant volume with 2%.
Preparation contains the serial solution of potassium ferricyanide 8g/L, 10g/L, 11g/L, 12g/L, 14g/L respectively, preparation simultaneously contains NaOH 12g/L, the mixed solution and the sample solution that contain potassium borohydride 10g/L are together introduced atomic fluorescence spectrometer reactive system, the PbH that is produced
4Gas is done carrier gas with argon gas and is introduced in the atomic fluorescence spectrometer mensuration system, under selected Instrument measuring parameter, measures.The results are shown in Table 1
The test of table 1 potassium ferricyanide concentration
K
3Fe(CN)
6 (g/L)
| 8 | 10 | 11 | 12 | 14 |
Fluorescence intensity | 407.16 | 473.94 | 555.07 | 373.51 | 250.17 |
As can be seen from Table 1, the concentration of the potassium ferricyanide is the fluorescence intensity maximum when 11g/L, uses concentration so elect as to measure.
Embodiment 3
Use the sample identical with embodiment 2.
Take by weighing the 0.1000g sample, sample is placed the 300ml beaker, add little water, add 15mL wang aqueous solution (1+1), cover surface plate, after treating that vigorous reaction stops, being placed on heating for dissolving on the electric furnace, and steaming near and do, take off, be cooled to room temperature, solution is moved in the 100mL volumetric flask, hydrochloric acid solution constant volume with 2%.
Preparation contains the serial solution of potassium borohydride 8g/L, 10g/L, 11g/L, 12g/L, 14g/L respectively, preparation simultaneously contains NaOH 12g/L, the mixed solution of potassium ferricyanide 11g/L and sample solution are together introduced the reactive system of atomic fluorescence spectrometer, the PbH that is produced
4Gas is done carrier gas with argon gas and is introduced in the atomic fluorescence spectrometer mensuration system, under selected Instrument measuring parameter, measures.The results are shown in Table 2.
The test of table 2 potassium borohydride concentration
KBH
4(g/L)
| 8 | 10 | 11 | 12 | 14 |
Fluorescence intensity | 417.64 | 455.33 | 457.07 | 464.23 | 480.93 |
Potassium borohydride concentration is between 10g/L~12g/L as can be seen from Table 2, and fluorescence intensity changes little, but when 10g/L the blank value minimum, be mensuration concentration so select it.
Embodiment 4
Use the sample identical with embodiment 2.
Take by weighing the 0.1000g sample, sample is placed the 300ml beaker, add little water, add 15mL wang aqueous solution (1+1), cover surface plate, after treating that vigorous reaction stops, being placed on heating for dissolving on the electric furnace, and steaming near and do, take off, be cooled to room temperature, solution is moved in the 100mL volumetric flask, hydrochloric acid solution constant volume with 2%.
Preparation contains the serial solution of NaOH 8g/L, 10g/L, 11g/L, 12g/L, 14g/L respectively, preparation simultaneously contains potassium borohydride 10g/L, the mixed solution of potassium ferricyanide 11g/L and sample solution are together introduced the reactive system of atomic fluorescence spectrometer, the PbH that is produced
4Gas is done carrier gas with argon gas and is introduced in the atomic fluorescence spectrometer mensuration system, measures under selected Instrument measuring parameter, the results are shown in Table 3
The test of table 3 naoh concentration
NaOH(g/L) | 8 | 10 | 11 | 12 | 13 |
Fluorescence intensity | 364.79 | 453.9 | 460.73 | 492.98 | 490.2 |
The size of the acidity of solution is bigger to result's influence as can be seen from Table 3, and the NaOH that contains 12g/L is favourable to measuring.It is ancient so the present invention adopts the naoh concentration of 12g/L as mensuration concentration.
Embodiment 5
Get the aluminium ingot sample that domestic certain factory produces, be processed into the chip that thickness is not more than 1mm.
Take by weighing two parts in 0.1000g sample and place 2 300ml beakers, the plumbous standard solution that adds different content respectively adds little water, adds 15mL wang aqueous solution (1+1), cover surface plate, after treating that vigorous reaction stops, being placed on heating for dissolving on the electric furnace, and steaming near and do, take off, be cooled to room temperature, solution is moved in the 100mL volumetric flask, hydrochloric acid solution constant volume with 2%.Below measure with embodiment 1.Mark-on reclaims and the results are shown in Table 4.
Table 4 mark-on recovery test
Sequence number | Sample lead content μ g/L | Addition μ g/L | The amount of recording μ g/L | Recovery % |
1# | 7.1 | 1.0 | 8.17 | 107 |
2# | 7.1 | 2.0 | 9.08 | 99 |
By recovery test as can be seen, the recovery of the inventive method is 99%~107%, and accuracy is higher.