CN100595567C - Method for quantitative analyzing metallic element in alloy - Google Patents
Method for quantitative analyzing metallic element in alloy Download PDFInfo
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- CN100595567C CN100595567C CN200610090753A CN200610090753A CN100595567C CN 100595567 C CN100595567 C CN 100595567C CN 200610090753 A CN200610090753 A CN 200610090753A CN 200610090753 A CN200610090753 A CN 200610090753A CN 100595567 C CN100595567 C CN 100595567C
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Abstract
A kind of method of analyzing metal element in alloy, the method includes alloy is dissolved in a event metal salt solution, using atom absorbing spectrometer to analyze density of the metal to be measured in the metal salt solution under absorbing wavelength of metal to be measured, calculated as content of metal to be measured in alloy= 100 %X(density of metal to be measured Xvolume of alloy sample metal salt solution)/quality of metal sample to calculate content of metal element in alloy, thereinto, content of metal element is not lower than 0.5 % of weight, absorbing wavelength of metal ishypo- sensitive absorbing line of metal to be measured. The invention selects hypo- sensitive absorbing line of metal to be measured to analyze by the atom absorbing spectrometer, so alloy sample metal salt solution is diluted for direct analysis, so error induced by dilutedness can be decreased greatly, operation is easy, fast and accuracy is high.
Description
Technical field
The invention relates to the method for metallic element in a kind of quantitative test alloy, especially about a kind of method with metallic element in the Atomic Absorption Spectrometer quantitative test alloy.
Background technology
Usually need in the commercial production to detect that certain content is not less than 0.5 weight % metallic element in the alloy, for example, hydrogen-storage alloy powder is the main negative material of Ni-MH battery, wherein, what of cobalt (Co), manganese (Mn) and nickel metal element contents such as (Ni) are very big to battery performance influence, therefore when the preparation Ni-MH battery, need carry out quantitative test timely and accurately to the content of the cobalt in the hydrogen-storage alloy powder (Co), manganese (Mn) and nickel metallic elements such as (Ni).
But the component of hydrogen-storage alloy powder is a lot, wherein except that containing cobalt (Co), manganese (Mn) and nickel (Ni) etc. to the far-reaching metallic element of battery performance, also contains Al and rare earth element (comprising La, Ce, Pr, Nd etc.).When analyzing hydrogen-storage alloy powder, after with the chemical reagent of high selectivity the above-mentioned component that needs detection being separated one by one earlier usually, again component to be measured is measured with chemical method.Though can obtain the accurate result of component concentration to be measured, the detachment process complex operation causes the analytic sample length that expends time in, and can not satisfy the requirement of rapid and accurate determination in the cell preparation process.
Also there are same problem in cobalt (Co), manganese (Mn) and nickel (Ni) etc. to the far-reaching metallic element of battery performance in the aas determination hydrogen-storage alloy powder and adopt.Existing atomic absorption spectrometry, the general the sensitiveest absorption line of selecting element to be measured earlier changes into metal salt solution with alloy sample then, and this solution dilution for many times is just measured when this concentration of element to be measured reaches the ppm level.Because cobalt (Co), manganese (Mn) and the nickel content of element to be measured in hydrogen-storage alloy powder such as (Ni) differ greatly, need carry out the dilution of different multiples according to different elements to be measured respectively to the metal salt solution of same hydrogen-storage alloy powder sample when therefore measuring, on the sensitiveest absorption line separately, measure then, thereby complex operation.In addition, when the content of metallic element to be measured in hydrogen-storage alloy powder is not less than 0.5 weight %, then the metal salt solution of the hydrogen-storage alloy powder sample multiple that need dilute is excessive (when measuring the Ni constituent content, the hydrogen-storage alloy powder pickling agent need be diluted about 100 times), the error of Ce Lianging can be amplified to the extension rate order of magnitude because of dilution thus.
In sum, the method that content is not less than the metallic element of 0.5 weight % in the existing quantitative test alloy exists complex operation, length consuming time and the big problem of error, therefore, need a kind of easy and simple to handle, quick and precisely content is not less than the method for the metallic element of 0.5 weight % in the quantitative test alloyed powder.
Summary of the invention
The objective of the invention is to overcome that content is not less than the method complex operation of the metallic element of 0.5 weight %, length consuming time and the big shortcoming of error in the prior art quantitative test alloy, provide a kind of easy and simple to handle, quick and precisely content is not less than the method for the metallic element of 0.5 weight % in the quantitative test alloy.
When use Atomic Absorption Spectrometer known in this field is measured metal element content, the precision of measuring under the sensitiveest absorption line of metallic element to be measured is very high, therefore measure alloy at present, when being not less than the metallic elements such as cobalt, manganese and nickel of 0.5 weight %, all select their the sensitiveest absorption lines separately for use such as content in the hydrogen-storage alloy powder.But the present inventor finds, for metallic element composition and the relatively-stationary alloy of content, principal ingredient hydrogen-storage alloy powder as cell negative electrode material, error is very big on the contrary to use the sensitiveest absorption line quantitative test metal element content wherein, because Atomic Absorption Spectrometer is only measured linear range to falling into it under this wavelength, the general content sensitivity that in the metal salt solution of alloy sample, is lower than the metallic element of 0.5 weight % (general assembly (TW) with alloy sample is a benchmark), therefore want to measure content in the different-alloy sample and be not less than the content difference of the metallic element of 0.5 weight %, need carry out the dilution of high multiple to the metal salt solution of this alloy, the error of measurement is enlarged by high power because of dilution for many times.Contain multiple metallic element in the alloy (as hydrogen-storage alloy powder) in addition, reach under the extension rate that to survey at element to be measured, the concentration of other metallic elements is general not in measuring their required ranges of linearity, therefore, measure other metals, need different metals to be diluted complex operation respectively.But generally there are several absorbing wavelength in metallic element, also has the sensitive line that absorbs except that the sensitiveest absorption line many times.The present inventor is through investigating discovery to cobalt, manganese and nickel etc. in the hydrogen-storage alloy powder respectively to every the sensitive line that absorbs of the far-reaching metallic element of battery performance, their threes possess time sensitive line that absorbs separately, can satisfy the alloy sample metal salt solution is not carried out the measurement requirement that dilution for many times is directly measured with Atomic Absorption Spectrometer.
The invention provides the method for metallic element in a kind of quantitative test alloy, this method comprises the metal salt solution of alloy being dissolved into homogeneous, using the concentration of Atomic Absorption Spectrometer quantitative test metal to be measured in this metal salt solution under the absorbing wavelength of metal to be measured, according to content=100% * (to be measured metal concentration * alloy sample metal salt solution the cumulative volume)/metal sample gross mass of metal to be measured in alloy; Calculate the content of metallic element in alloy, wherein, the content of described metallic element to be measured is not less than 0.5 weight %, and the absorbing wavelength of described metallic element to be measured is time sensitive line that absorbs of metallic element to be measured.
According to the present invention, owing to select time sensitive line that absorbs of metallic element to be measured to carry out the Atomic Absorption Spectrometer analysis, therefore need not the alloy sample metal salt solution is carried out dilution for many times, just can directly analyze, thereby content is not less than the method for the metallic element of 0.5 weight % in the quantitative test alloy provided by the invention, can reduce the error of amplifying greatly owing to dilution for many times, easy and simple to handle, quick, the accuracy height.
For example, the used time ratio comparative example of cobalt, manganese and three kinds of metal element contents of nickel 1 is measured the saving at least 45 minutes of above-mentioned three kinds of used times of metal element content in the same sample in the embodiment 1 quantitative test hydrogen-storage alloy powder sample, and the sextupl measurement standard deviation of cobalt in 1 pair of same sample of embodiment only is 0.037; And comparative example 1 reaches 0.126.
Description of drawings
The concentration of Fig. 1 cobalt records the typical curve of absorbance to Atomic Absorption Spectrometer;
The concentration of Fig. 2 manganese records the typical curve of absorbance to Atomic Absorption Spectrometer;
The concentration of Fig. 3 nickel records the typical curve of absorbance to Atomic Absorption Spectrometer.
Embodiment
The invention provides the method for metallic element in a kind of quantitative test alloy, this method comprises the metal salt solution of alloy being dissolved into homogeneous, using the concentration of Atomic Absorption Spectrometer quantitative test metal to be measured in this metal salt solution under the absorbing wavelength of metal to be measured, according to content=100% * (to be measured metal concentration * alloy sample metal salt solution the cumulative volume)/metal sample gross mass of metal to be measured in alloy; Calculate the content of metallic element in alloy, wherein, the content of described metallic element to be measured is not less than 0.5 weight %, and the absorbing wavelength of described metallic element to be measured is time sensitive line that absorbs of metallic element to be measured.
For each metallic element, all have a lot of absorbing wavelength, but prior art only adopts the sensitive line in all absorbing wavelength of metallic element to be measured, utilizes atomic absorption spectrum to carry out the quantitative test of element.Quantitative test of the present invention to as if alloy in metallic element (as influencing the metallic element of battery performance in the hydrogen-storage alloy powder sample), the characteristics of metallic element are that content is not less than 0.5 weight % in this sample, and the general proportions of the various metal element contents of formation alloy is known, so the present inventor finds to use the inferior sensitive line absorption line of above-mentioned metallic element also can satisfy the requirement of metallic element in the above-mentioned alloy being carried out quantitative test.And select several metallic elements time sensitive when absorbing line and analyzing to mixing this metal to be measured that exists in the sample, need not according to the content of different metal element respectively dilution for many times alloy sample metal salt solution just analyze, only need to use the light source of different elements to be measured and regulate corresponding instrument parameter and a alloy sample metal salt solution stoste is directly measured got final product.
Time sensitive line that absorbs of described metal to be measured is time sensitive line that absorbs that does not overlap with the absorbing wavelength of other metals in the alloy.All there is the sensitive line that absorbs many times in every kind of metallic element, if time sensitive line that absorbs that has minority close proximity even coincidence of the metal to be measured of component alloy and other metals, when measuring, can disturb, so time sensitivity that the absorbing wavelength that is not subjected to other metals in the alloy of the preferred metal to be measured of the present invention is disturbed absorbs line.Time sensitive line that absorbs that the absorbing wavelength that is not subjected to other metals in the alloy of described metal to be measured is disturbed refers in the sensitive absorbing wavelength that does not have other metals in line ± 0.1 nanometer range that absorbs of this time.Described the sensitive line that absorbs also need possess the suitable characteristics of contained tenor to be measured in good linearity, sensitivity and the alloy except that noiseless.
The principle of Atomic Absorption Spectrometer is that the solution that will contain metallic element to be measured is sprayed into mist by the atomization system, enters flame with carrier gas, and be dissociated into ground state atom in flame.All absorbing wavelength light that give off element to be measured when hollow cathode lamp weaken because of being absorbed by the ground state atom of element to be measured in the flame during by flame.Therefore, the present invention can adopt this area method commonly used alloy sample to be dissolved into the metal salt solution of homogeneous.The described method that alloy sample is dissolved into the metal salt solution of homogeneous comprises that with behind the described alloy sample of aqua regia dissolution concentrated gained is dissolved with the chloroazotic acid of alloy sample to separating out crystal, adds the crystal that hydrochloric acid and deionized water dissolving are separated out, constant volume.Wherein, the consumption of preferred chloroazotic acid can sample dissolution and excessive slightly.Concentrate and to realize by this area method commonly used that preferred slowly heating can be removed the excessive chloroazotic acid of the overwhelming majority.Be heated to the chloroazotic acid that is dissolved with sample and separate out till the crystal, this moment, excessive chloroazotic acid evaporated, and solution is closely dried, and the metallic element soluble-salt that forms in the sample still keeps stable.In addition, when adding hydrochloric acid and deionized water dissolving are separated out crystal, can quicken the dissolving of soluble-salt in the sample by heating.Method of the present invention is applicable to measures the metallic element that various content in the alloy are not less than 0.5 weight %, in the negative electrode active material hydrogen-storage alloy such as alkaline battery, the necessity that the big metallic element of battery performance influence is measured is bigger, therefore, the metallic element to be measured in the described hydrogen-storage alloy is cobalt, manganese and/or nickel.
Described Atomic Absorption Spectrometer generally includes by light source, atomization system, beam splitting system, detection system to be formed.The most frequently used light source of Atomic Absorption Spectrometer is a hollow cathode lamp, generally is made up of a hollow cylindrical negative electrode and an anode, and negative electrode is made by element simple metal to be measured or its alloy.When two interpolars added certain voltage, then the metallic atom to be measured that sputters out because of cathode surface was excited, and just launches characteristic light.Described atomization system can become atomic vapour with element transformation to be measured, is divided into flame atomization system and no NITRATE BY FLAME ATOMIC system.The flame atomization system comprises sprayer, spray chamber, burner and flame and gas supply part branch.Flame is the energy that the evaporation of sample droplet, dry also process thermal dissociation or reducing action is produced a large amount of ground state atoms, and flame commonly used is air-acetylene flame.Gas supply part divides the height and the angle of combustion head of ratio, the burner of air supply and acetylene to play a crucial role in sample atomization mechanism.It is 7: 1 to 8: 1 that the gas of atomization of the present invention system is supplied with the throughput ratio that is preferably air and acetylene, and the height of combustion head is different because of different metallic elements to be measured with angle.Described beam splitting system comprises parts such as dispersion element, concave mirror, slit.The width of regulating slit can separate the mensuration spectral line of element to be measured with contiguous spectral line, the preferred 0.3-0.5 nanometer of the present invention can guarantee that in this scope time sensitive line that absorbs separates with the near-by interference spectral line.Described detection system is by photomultiplier, amplifier, logarithmic converter, indicator and regulate automatically, calibrate automatically etc. partly formed, and is the device that light signal is transformed into electric signal and measures.
Under the situation that experiment condition is fixed, there is quantitative relationship in the concentration of element ground state atom to be measured in tested wavelength (the sensitiveest absorption line of metallic element to be measured or the inferior sensitive line that absorbs) intensity variations and the flame, promptly observe Lambert-Beer's law, thereby there is quantitative relationship with the concentration of element to be measured in the sample, that is:
A＝KC
In the formula, A represents the absorbance of element to be measured; The coefficient that K representative is relevant with experiment condition is when experiment condition is a constant fixedly the time.
Can adopt this area method of utilizing the atomic spectrograph quantitative test such as calibration curve method and standard addition method commonly used.Wherein the method for drafting of typical curve comprises the working specification by Atomic Absorption Spectrometer, open instrument switch, install element hollow cathode lamp to be measured, after treating instrument stabilizer, adjust instrument parameter, measure the series standard solution absorbency of this element, the concentration with series standard solution is horizontal ordinate then, is ordinate drawing curve with the absorbance of correspondence.Measure the absorbance of alloy sample metal salt solution then, from typical curve, can obtain the concentration of metallic element to be measured the alloy sample metal salt solution.
Described alloy is a hydrogen-storage alloy, and the metallic element to be measured in the described hydrogen-storage alloy is a cobalt, and the slit width of the beam splitting system of preferred described Atomic Absorption Spectrometer is the 0.3-0.5 nanometer, and inferior sensitive absorption line is 252.1 nanometers; The throughput ratio that the gas of atomization system is supplied with to air and acetylene is 7: 1 to 8: 1, and the combustion head height of burner is the 4.5-5.5 millimeter, and the combustion head angle is 42-48 °.More preferably the slit width of the beam splitting system of described Atomic Absorption Spectrometer is 0.4 nanometer, and inferior sensitive absorption line is 252.1 nanometers; The throughput ratio that the gas of atomization system is supplied with to air and acetylene is 7: 1, and the combustion head height of burner is 5 millimeters, and the combustion head angle is 45 °.
Described alloy is a hydrogen-storage alloy, and the metallic element to be measured in the described hydrogen-storage alloy is a manganese, and the slit width of the beam splitting system of preferred described Atomic Absorption Spectrometer is the 0.3-0.5 nanometer, and inferior sensitive absorption line is 403.2 nanometers; The throughput ratio that the gas of atomization system is supplied with to air and acetylene is 7: 1 to 8: 1, and the combustion head height of burner is the 9.5-10.5 millimeter, and the combustion head angle is 0-3 °.More preferably the slit width of the beam splitting system of described Atomic Absorption Spectrometer is 0.4 nanometer, and inferior sensitive absorption line is 403.2 nanometers; The throughput ratio that the gas of atomization system is supplied with to air and acetylene is 7: 1, and the combustion head height of burner is 10 millimeters, and the combustion head angle is 0 °.
Described alloy is a hydrogen-storage alloy, and the metallic element to be measured in the described hydrogen-storage alloy is a nickel, and the slit width of the beam splitting system of preferred described Atomic Absorption Spectrometer is the 0.3-0.5 nanometer, and inferior sensitive absorption line is 323.3 nanometers; The throughput ratio that the gas of atomization system is supplied with to air and acetylene is 7: 1 to 8: 1, and the combustion head height of burner is the 4.5-5.5 millimeter, and the combustion head angle is 0-3 °.More preferably the slit width of the beam splitting system of described Atomic Absorption Spectrometer is 0.4 nanometer, and inferior sensitive absorption line is 323.3 nanometers; The throughput ratio that the gas of atomization system is supplied with to air and acetylene is 7: 1, and the combustion head height of burner is 5 millimeters, and the combustion head angle is 0 °.
Unless stated otherwise, used medicine is commercially available analytical reagent in the specific embodiment of the invention.The present invention is described further below in conjunction with embodiment.
Present embodiment illustrates that content in the quantitative test alloy provided by the invention is not less than the method for the metallic element of 0.5 weight %.
(1) preparation of metallic element to be measured (Co, Mn or Ni) standard stock solution
Accurately take by weighing simple metal (Co, Mn or Ni, purity is 99.99%) 1.0000 grams and place beaker, add an amount of chloroazotic acid (nitric acid: hydrochloric acid=1: 3) about 5 milliliters, slowly be heated to after metal dissolves fully, continue heating and be concentrated into about 1 milliliter, stop heating, cooling.The hydrochloric acid that adds 10 milliliter of 6 mol then, the dissolving crystal of separating out is transferred to the solution of gained in 1000 milliliters of volumetric flasks, with this beaker of deionized water rinsing three times, shifts solution under the flushing in same volumetric flask, and the deionized water constant volume shakes up.
(2) preparation of metal standard solution to be measured
(a) preparation of Co standard solution
Co standard stock solution with (1) prepares with the deionized water dilution, is mixed with the series standard solution of 50 mcg/ml, 100 mcg/ml, 150 mcg/ml, 200 mcg/ml respectively.
(b) preparation of Mn standard solution
Mn standard stock solution with (1) prepares with the deionized water dilution, is mixed with the series standard solution of 10 mcg/ml, 20 mcg/ml, 30 mcg/ml, 40 mcg/ml respectively.
(c) preparation of Ni standard solution
Ni standard stock solution with (1) prepares with the deionized water dilution, is mixed with the series standard solution of 100 mcg/ml, 200 mcg/ml, 300 mcg/ml, 400 mcg/ml respectively.
(3) metal salt solution of preparation alloy sample
Accurately take by weighing 0.1000 gram hydrogen-storage alloy powder sample as in the triangular flask, (nitric acid: hydrochloric acid=1: 3), slowly heating is dissolved sample fully, continues to stop when heating makes gained mixed solution closely dried (having crystal to separate out) heating, cooling to add 15 milliliters of chloroazotic acid.Add the hydrochloric acid that reaches 1 milliliter of 6 mol in 30 ml deionized water, heating makes the soluble-salt dissolving slightly, after the cooling, in the volumetric flask with 250 milliliters of gained solution immigrations, uses the deionized water constant volume, shakes up.
(4) drafting of typical curve
Press the working specification of Atomic Absorption Spectrometer, open instrument switch, install element hollow cathode lamp to be measured, after treating instrument stabilizer, adjust instrument parameter according to table 1, measure the series standard solution absorbency of this element, the concentration with series standard solution is horizontal ordinate then, is ordinate drawing curve with the absorbance of correspondence.The typical curve of gained element to be measured is seen Fig. 1 to Fig. 3.As can be seen from Figure 1, the linear range of quantitative test cobalt of the present invention is 50-200ppm, and the scope up to standard of cobalt element is 100-150ppm in the actual hydrogen-storage alloy powder; As can be seen from Figure 2, the linear range of quantitative test manganese of the present invention is 10-40ppm, and the scope up to standard of manganese element is 22-28ppm in the actual hydrogen-storage alloy powder; As can be seen from Figure 3, the linear range of quantitative test nickel of the present invention is 100-400ppm, and the scope up to standard of nickel element is 220-280ppm in the actual hydrogen-storage alloy powder.
The instrument parameter of table 1 embodiment 1 atomic absorption spectrum
(5) mensuration of metal element content to be measured in the sample
By the absorbance of metallic element to be measured in the method quantitative test sample solution of (4) bioassay standard solution absorbance, on the working curve of respective metal element, find out corresponding concentration value then according to its corresponding absorbance.Calculate the percentage by weight of metallic element in hydrogen-storage alloy powder by following formula then.
Wherein, C represents to record concentration of metal (mcg/ml); V represents sample solution cumulative volume (milliliter); M represents sample quality (gram).
(6) recovery test
Get according to step (1) to (5) and determine the wherein hydrogen-storage alloy powder sample of the quality of Co, Mn and Ni, in its metal salt solution, add Co, Mn and the Ni standard solution of known volume, measure the quality of Co, Mn and Ni behind the mark-on again by above-mentioned steps, be calculated as follows the recovery:
Table 2 recovery of standard addition experimental result
As can be seen from Table 2, when measuring hydrogen-storage alloy powder according to the inventive method, the recovery of measuring Co is between 99.26%-100.57%, and the recovery of measuring Mn is between 98.78%-101.23%, and the recovery of measuring Ni is between 99.83%-100.40%.Therefore content is not less than the method accuracy height of the metallic element of 0.5 weight % in the quantitative test alloy provided by the invention, and is noiseless.
(7) replica test
Cobalt, manganese and three kinds of metallic elements of nickel in the same hydrogen-storage alloy powder sample are carried out replication respectively six times, and test result is as shown in table 3.
Table 3
By table 3 as seen, when measuring hydrogen-storage alloy powder according to the inventive method, the standard deviation of measuring Co is 0.037, and maximum difference is 0.10, and the standard deviation of measuring Mn is 0.031, and maximum difference is 0.09, and the standard deviation of Ni is 0.049, and maximum difference is 0.14.Therefore, content is not less than the method good reproducibility accuracy height of the metallic element of 0.5 weight % in the quantitative test alloy provided by the invention.
Present embodiment illustrates that content in the quantitative test alloy provided by the invention is not less than the method for the metallic element of 0.5 weight %.
According to cobalt manganese nickel in step (1)-(5) quantitative test hydrogen-storage alloy powder of embodiment 1, different is with the steady oxide thing preparing standard solution that contains 1.0000 grams metal to be measured, adjusts the parameter of Atomic Absorption Spectrometer according to table 4.The average recovery of three kinds of metals that record according to the method for embodiment 1 step (6) is respectively 98.85%-101.72%, 98.65-101.76%, 99.1-100.89%; The standard deviation of three kinds of metals that record according to the method for embodiment 1 step (7) is respectively 0.040,0.045,0.055; Illustrate that content in the quantitative test alloy provided by the invention is not less than wide, the good reproducibility, easy, quick of method accuracy height, the range of linearity of the metallic element of 0.5 weight %.
The instrument parameter of table 4 embodiment 2 atomic absorption spectrums
Comparative example 1
Content is not less than the method for the metallic element of 0.5 weight % in this comparative example explanation prior art quantitative test alloy.
(1) preparation of metallic element to be measured (Co, Mn or Ni) standard stock solution
Accurately take by weighing simple metal (Co, Mn or Ni, purity is 99.99%) 1.0000 grams and place beaker, add an amount of chloroazotic acid (nitric acid: hydrochloric acid=1: 3) about 5 milliliters, slowly be heated to after metal dissolves fully, continue heating and be concentrated into about 1 milliliter, stop heating, cooling.The hydrochloric acid that adds 10 milliliter of 6 mol then, the dissolving crystal of separating out is transferred to the solution of gained in 1000 milliliters of volumetric flasks, with this beaker of deionized water rinsing three times, shifts solution under the flushing in same volumetric flask, and the deionized water constant volume shakes up.
(2) preparation of metal standard solution to be measured
(a) preparation of Co standard solution
Co standard stock solution with (1) prepares with the deionized water dilution, is mixed with the series standard solution of 1 mcg/ml, 2 mcg/ml, 3 mcg/ml, 4 mcg/ml respectively.
(b) preparation of Mn standard solution
Mn standard stock solution with (1) prepares with the deionized water dilution, is mixed with the series standard solution of 1 mcg/ml, 2 mcg/ml, 3 mcg/ml, 4 mcg/ml respectively.
(c) preparation of Ni standard solution
Ni standard stock solution with (1) prepares with the deionized water dilution, is mixed with the series standard solution of 1 mcg/ml, 2 mcg/ml, 3 mcg/ml, 4 mcg/ml respectively.
(3) metal salt solution of preparation alloy sample
Accurately take by weighing 0.1000 gram hydrogen-storage alloy powder sample as in the triangular flask, (nitric acid: hydrochloric acid=1: 3), slowly heating is dissolved sample fully, continues to stop when heating makes gained mixed solution closely dried (having crystal to separate out) heating, cooling to add 15 milliliters of chloroazotic acid.Add the hydrochloric acid that reaches 1 milliliter of 6 mol in 30 ml deionized water, heating makes the soluble-salt dissolving slightly, after the cooling, in the volumetric flask with 250 milliliters of gained solution immigrations, uses the deionized water constant volume, shakes up.
(4) dilution of sample solution
The dilution of Co sample solution: accurately pipette 10 milliliters of alloy sample metal salt solutions that (3) obtain in 500 milliliters of volumetric flasks with transfer pipet, and be diluted to scale, shake up.Extension rate is 50 times.
The dilution of Mn sample solution: accurately pipette 10 milliliters of alloy sample metal salt solutions that above-mentioned (3) obtain in 100 milliliters of volumetric flasks with transfer pipet, and be diluted to scale, shake up.Extension rate is 10 times.
The dilution of Ni sample solution: 10 times of dilutions earlier, accurately pipette 10 milliliters of alloy sample metal salt solutions that above-mentioned (3) obtain in 100 milliliters of volumetric flasks with transfer pipet, and be diluted to scale, shake up.Dilute 10 times again, accurately pipette with transfer pipet and above-mentionedly diluted 10 times 10 milliliters of sample solutions in 100 milliliters of volumetric flasks, and be diluted to scale, shake up.Final extension rate reaches 100 times.
(5) drafting of typical curve
Press the working specification of Atomic Absorption Spectrometer, open instrument switch, install element hollow cathode lamp to be measured, after treating instrument stabilizer, adjust instrument parameter according to table 5, measure the series standard solution absorbency of this element, the concentration with series standard solution is horizontal ordinate then, is ordinate drawing curve with the absorbance of correspondence.Just as shown in table 5, because all selecting for use under their the sensitiveest separately absorption lines of metal to be measured measured, therefore the linear range of prior art quantitative test cobalt is 1-4ppm, and the actual scope up to standard of making cobalt element in the hydrogen-storage alloy powder metal salt solution of joining by (4) is 100-150ppm, needs 50 times of dilutions just can reach the range of linearity that satisfies existing method measurement requirement; The linear range of prior art quantitative test manganese is 0-4ppm, and the scope up to standard of manganese element is 22-28ppm in the actual hydrogen-storage alloy powder metal salt solution, needs 10 times of dilutions just can reach the range of linearity that satisfies existing method measurement requirement; The linear range of prior art quantitative test nickel is 1-4ppm, and the scope up to standard of nickel element is 220-280ppm in the actual hydrogen-storage alloy powder; Need 100 times of dilutions just can reach the range of linearity that satisfies existing method measurement requirement.
The instrument parameter of table 5 comparative example 1 atomic absorption spectrum
(6) mensuration of metal element content to be measured in the sample
By the absorbance of metallic element to be measured in the method quantitative test sample solution of (4) bioassay standard solution absorbance, on the working curve of respective metal element, find out corresponding concentration value then according to its corresponding absorbance.Calculate the percentage by weight of metallic element in hydrogen-storage alloy powder by following formula then.
Wherein, C represents to record concentration of metal (mcg/ml); V represents sample solution cumulative volume (milliliter); M represents sample quality (gram).
(7) recovery test
Get according to step (1) to (5) and determine the wherein hydrogen-storage alloy powder sample of the quality of Co, Mn and Ni, in its metal salt solution, add Co, Mn and the Ni standard solution of known volume, measure the quality of Co, Mn and Ni behind the mark-on again by above-mentioned steps, be calculated as follows the recovery:
The recovery of standard addition experimental result is as shown in table 6.
Table 6
As can be seen from Table 6, when measuring hydrogen-storage alloy powder according to art methods, the recovery of measuring Co is between 94.43-101.94%, and the recovery of measuring Mn is between 95.05-102.76%, and the recovery of measuring Ni is between 96.89-102.4%.Therefore content is not less than the method accuracy of metallic element of 0.5 weight % not as good as the present invention in the prior art quantitative test alloy.
(8) replica test
Measure by three kinds of metallic elements of cobalt manganese nickel in the same hydrogen-storage alloy powder sample being carried out six times respectively, the standard deviation of measuring Co content is 0.126, and the standard deviation of Mn content is 0.102, and the standard deviation of Ni is 0.125.Therefore, in the prior art quantitative test alloy content to be not less than the method repeatability of metallic element of 0.5 weight % good not as method of the present invention.And prior art on average dilutes sample and needs the average times that consume 15 minutes more, measures the content of three kinds of metallic elements in the sample identical with embodiment 1, how consuming time at least four ten five minutes.If needed to measure a plurality of batches hydrogen-storage alloy powder sample in one day, then times that consume more more.
Claims (6)
1, the method of metallic element in a kind of quantitative test alloy, this method comprises the metal salt solution of alloy being dissolved into homogeneous, using the concentration of Atomic Absorption Spectrometer quantitative test metal to be measured in this metal salt solution under the absorbing wavelength of metal to be measured, according to content=100% * (to be measured metal concentration * alloy sample metal salt solution the cumulative volume)/metal sample gross mass of metal to be measured in alloy, calculate the content of metallic element in alloy, it is characterized in that, the content of described metallic element to be measured is not less than 0.5 weight %, the absorbing wavelength of described metallic element to be measured is time sensitive line that absorbs of metallic element to be measured, wherein, described alloy is a hydrogen-storage alloy, and the metallic element to be measured in the described hydrogen-storage alloy is cobalt and/or nickel; Time sensitive line that absorbs of described metal to be measured is time sensitive line that absorbs that does not overlap with the absorbing wavelength of other metals in the alloy.
2, method according to claim 1, wherein, the described method that alloy sample is dissolved into the metal salt solution of homogeneous comprises with behind the described alloy sample of aqua regia dissolution, concentrated gained is dissolved with the chloroazotic acid of alloy sample to separating out crystal, add the crystal that hydrochloric acid and deionized water dissolving are separated out, constant volume.
3, method according to claim 1, wherein, described alloy is a hydrogen-storage alloy, and the metallic element to be measured in the described hydrogen-storage alloy is a cobalt, the slit width of the beam splitting system of described Atomic Absorption Spectrometer is the 0.3-0.5 nanometer, and inferior sensitive absorption line is 252.1 nanometers; The throughput ratio that the gas of atomization system is supplied with to air and acetylene is 7: 1 to 8: 1, and the combustion head height of burner is the 4.5-5.5 millimeter, and the combustion head angle is 42-48 °.
4, method according to claim 3, wherein, the slit width of the beam splitting system of described Atomic Absorption Spectrometer is 0.4 nanometer, inferior sensitive absorption line is 252.1 nanometers; The throughput ratio that the gas of atomization system is supplied with to air and acetylene is 7: 1, and the combustion head height of burner is 5 millimeters, and the combustion head angle is 45 °.
5, method according to claim 1, wherein, described alloy is a hydrogen-storage alloy, and the metallic element to be measured in the described hydrogen-storage alloy is a nickel, the slit width of the beam splitting system of described Atomic Absorption Spectrometer is the 0.3-0.5 nanometer, and inferior sensitive absorption line is 323.3 nanometers; The throughput ratio that the gas of atomization system is supplied with to air and acetylene is 7: 1 to 8: 1, and the combustion head height of burner is the 4.5-5.5 millimeter, and the combustion head angle is 0 °.
6, method according to claim 5, wherein, the slit width of the beam splitting system of described Atomic Absorption Spectrometer is 0.4 nanometer, inferior sensitive absorption line is 323.3 nanometers; The throughput ratio that the gas of atomization system is supplied with to air and acetylene is 7: 1, and the combustion head height of burner is 5 millimeters, and the combustion head angle is 0 °.
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| CN102445426B (en) * | 2011-09-28 | 2014-04-16 | 中国一拖集团有限公司 | Method for determining cobalt content in hard alloy product |
| CN104849225A (en) * | 2015-05-06 | 2015-08-19 | 天津渤化石化有限公司 | Method for measuring trace-metal content in dimethylmethane |
| CN105300908A (en) * | 2015-11-10 | 2016-02-03 | 合肥通用机械研究院 | Method for determining trace element lead in centrifugal casting furnace tube and matrix modifier applied thereto |
| CN109596602A (en) * | 2018-12-24 | 2019-04-09 | 南通金源智能技术有限公司 | Cobalt alloy powder component detection method |
| CN114486778B (en) * | 2022-01-18 | 2023-10-03 | 中国科学院西北生态环境资源研究院 | Detection device and method for heavy metal ions |
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