CN108872195A - The method that ICP-OES method measures lead, tin, bi content in aluminium alloy - Google Patents

The method that ICP-OES method measures lead, tin, bi content in aluminium alloy Download PDF

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CN108872195A
CN108872195A CN201810545711.5A CN201810545711A CN108872195A CN 108872195 A CN108872195 A CN 108872195A CN 201810545711 A CN201810545711 A CN 201810545711A CN 108872195 A CN108872195 A CN 108872195A
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雷亚宁
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Cac Metal Material Physical And Chemical Testing Technology Co Ltd
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Abstract

The invention discloses the methods of lead, tin, bi content in ICP-OES method measurement aluminium alloy, and using the content of lead, tin, bismuth in inductively coupled plasma emission spectrography measurement aluminium alloy LD7-4, the present invention uses water and hydrochloric acid volume ratio for 1 on sample:1 dilute hydrochloric acid, then by after dilution hydrochloric acid and the ratio between nitric acid be 10:Nitric acid sample dissolution is added in 1 ratio；And by successively considering that minimum analysis line spectrum, signal is interfered to go out optimized analysis spectral line compared with strong, the lower choice of spectrum of background；Use mass fraction for 99.99% or more rafifinal bottoming additional element after draw working curve, and the instrument main working parameters that may influence test result are adjusted.The present invention has also done the interference correction of Main elements contained by sample, has carried out detection limit, accuracy and precision test.The result shows that testing result of the present invention is accurate, reliable, lead, tin, the measurement of bi content, analysis work suitable for daily aluminium alloy.

Description

The method that ICP-OES method measures lead, tin, bi content in aluminium alloy
Technical field
The invention belongs to Determination of Impurity Elements method and technology fields in aluminium alloy, and in particular to ICP-OES method measures aluminium and closes The method of lead, tin, bismuth in gold.
Background technique
Lead, tin, bismuth belong to five-harmful elements family member, lead in aluminium alloy LD7-4, tin, bismuth category impurity element and be brought into, So wanting its content of strict control when smelting, sometimes for the performance for improving steel, a small amount of lead, tin, bismuth can be purposefully added.Cause This must have the content that a kind of effective detection means accurately detects slicker solder bismuth.
In analytical chemistry, in measurement aluminium alloy there are many ways to lead, tin, bi content：There are atomic absorption method, ICP hair Penetrate spectroscopic methodology, direct-reading method etc..And ICP emission spectrometry, direct-reading method only have content in the inspection of 0.010% or more lead, tin, bismuth at present Survey has been reported that, without the detection method of content lead, tin, bismuth below 0.010%；Atomic absorption method has sampling Graphite Furnace Atomic Absorption Method, flame atomic absorption method etc., graphite oven atomic absorption, flame atomic absorption method also have report to the detection of Trace Lead and Tin bismuth Road, but atomic absorption method detecting step is cumbersome, need one by one element detected, be unsatisfactory for modernizing the progress of short test period It is required that.
Summary of the invention
The object of the present invention is to provide the methods of lead, tin, bi content in ICP-OES method measurement aluminium alloy, solve existing Lead, tin, bi content can not be measured existing for ICP emission spectrometry 0.01% content below the problem of.
The technical scheme adopted by the invention is that the method that ICP-OES method measures lead, tin, bi content in aluminium alloy, specifically Steps are as follows：
Step 1, according to method as defined in GB/T602, prepare lead standard solution, the tin standard solution, bismuth of isoconcentration respectively The manganese standard solution of standard solution and isoconcentration, nickel standard solution, iron standard solution, copper standard solution, magnesium standard solution, zirconium mark Quasi- solution；
Step 2 weighs the rafifinal that n parts of mass fractions are 99.99% or more as matrix original pattern, and wherein n is not less than 5； Hydrochloric acid solution, nitric acid solution are sequentially added into n parts of described matrix original patterns first, is prepared into solution A respectively1, solution A2、…… Solution An, then to the solution A1, solution A2... solution AnMiddle manganese standard solution, the nickel standard solution, iron that isoconcentration is added Standard solution, copper standard solution, magnesium standard solution, zirconium standard solution, respectively obtain solution B1, solution B2... solution Bn, so Backward solution B1, solution B2... solution BnMiddle isoconcentration lead standard solution, the tin standard solution, bismuth standard that suitable gradient is added Solution obtains calibration curve solution C1, calibration curve solution C2... ... calibration curve solution Cn；
Step 3, using inductive coupling plasma emission spectrograph to calibration curve solution C1, solution C2... ... solution Cn It is detected, obtains the intensity of emission spectra of each calibration curve solution, inductive coupling plasma emission spectrograph is respectively with each Lead in calibration curve solution, tin, bismuth concentration be abscissa, with the transmitting of lead, tin and bismuth in each calibration curve solution of measurement Spectral intensity is that ordinate draws out working curve automatically, wherein the analysis spectral line for measuring the lead of selection is 220.353nm, tin Analysis spectral line be 189.927nm, the analysis spectral line of bismuth is 190.171nm；
Hydrochloric acid solution D is first added into aluminium alloy LD7-4 sample in step 4, to after the reaction was completed, then by hydrochloric acid solution D's The ratio between volume and nitric acid solution volume are 10:1~15:1 is added nitric acid solution, prepares the solution to be measured of aluminium alloy LD7-4 sample；
Step 5 detects the solution to be measured that step 4 obtains with the same determination condition of step 3, measures test solution The intensity of emission spectra of middle lead, tin and bismuth obtains lead in test solution, tin and bismuth according to the working curve diagram of calibration curve solution Concentration.
The features of the present invention also characterized in that：
The concrete operation step of step 2 is as follows：
Step 2.1 weighs the rafifinal that n parts of mass fractions are 99.99% or more, is respectively placed in n container；
Step 2.2 by water and hydrochloric acid volume ratio is 1:1~2:1 dilutes excellent pure grade hydrochloric acid solution, and it is molten to obtain n parts of hydrochloric acid Liquid D, wherein top grade pure hydrochloric acid density is 1.19g/ml；
Step 2.3, by the ratio between the quality of rafifinal and hydrochloric acid solution D volume be 1:100~1:300 is equal into each container The hydrochloric acid solution D of equivalent is added, is reacted to hydrochloric acid solution D with rafifinal completion, obtains n parts of solution Es；
The ratio between step 2.4, volume and nitric acid solution volume for pressing hydrochloric acid solution D again are 10:1~30:1 to every part of solution E In the nitric acid solution of equivalent is added, be cooled to room temperature after heating, obtain solution A1, solution A2... solution An, wherein nitric acid Solution uses density for the excellent pure grade nitric acid solution of 1.42/ml；
Step 2.5, to solution A1, solution A2... solution AnIn be separately added into manganese standard solution, the nickel standard of isoconcentration Solution, iron standard solution, copper standard solution, magnesium standard solution, zirconium standard solution, concentration are 1000 μ g/ml, and the amount of addition is controllable System is in a certain range：50 μ L of μ L~200 of manganese standard solution, nickel standard solution 1.0mL~1.4mL, iron standard solution 0.9mL ~1.2mL, copper standard solution 2.1mL~2.7mL, magnesium standard solution 1.3mL~1.7mL, the 10 μ L of μ L~50 of zirconium standard solution, obtain To solution B1, solution B2... solution Bn, wherein n is not less than 5；
Step 2.6, again to solution B1, solution B2... solution BnIn by suitable gradient be added isoconcentration lead standard it is molten Liquid, tin standard solution, bismuth standard solution, concentration 0.01mg/ml, solution B1The lead standard solution of middle addition, tin standard solution, The volume of bismuth standard solution is identical, solution B2The volume phase of the lead standard solution of middle addition, tin standard solution, bismuth standard solution Solution B together ... ...nThe lead standard solution of middle addition, tin standard solution, the volume of bismuth standard solution are identical.It is marked after constant volume Directrix curve solution C1, calibration curve solution C2... calibration curve solution Cn, wherein n is not less than 5.
The heating condition of step 2.4 is：Sample is heated to using 80-120 DEG C to be completely dissolved, then is incited somebody to action using 150-200 DEG C It is clean that solution heating drives away nitrogen oxides.
The concrete operation step of step 4 is as follows：
Step 4.1 weighs aluminium alloy LD7-4 sample, is placed in container；
Step 4.2 by water and hydrochloric acid volume ratio is 1:1~2:1 dilutes excellent pure grade hydrochloric acid solution, obtains hydrochloric acid solution D；
The ratio between step 4.3, the hydrochloric acid solution D volume obtained by the quality of aluminium alloy LD7-4 and through step 2.3 are 1:100 ~1:300 hydrochloric acid solution D is added into container, reacts to hydrochloric acid solution D with the completion of aluminium alloy LD7-4 sample, obtains solution F；
Step 4.4 is 10 by the ratio between the volume of hydrochloric acid solution D and nitric acid solution volume:1~30:1 is added into solution F Nitric acid solution, after be cooled to room temperature, solution to be measured is obtained after constant volume, the volume of constant volume is identical as step 2.6, wherein nitric acid solution Use density for the excellent pure grade nitric acid solution of 1.42/ml.
The condition of the heating of step 4.4 is：Sample is heated to using 80-120 DEG C to be completely dissolved, then uses 150-200 DEG C Solution is heated, drives away nitrogen oxides clean.
The running parameter of inductive coupling plasma emission spectrograph is in step 3：Atomization gas flow 0.8L/min, observation Distance is 15mm, high frequency power 1300W, secondary air amount 0.2L/min, plasma flow 15L/min, sample flow Measure 1.50mL/min.
The beneficial effects of the invention are as follows：
(1) in ICP-OES method of the present invention measurement aluminium alloy lead, tin, bi content method, be using mass fraction 99.99% rafifinal bottoming, the working curve effect drawn after additional element are good；
(2) method that ICP-OES method of the present invention measures lead, tin, bi content in aluminium alloy, eliminates matrix element and main amount The interference of element；
(3) in ICP-OES method of the present invention measurement aluminium alloy lead, tin, bi content method, realize with inductive coupling etc. from Daughter emission spectrometry is to lead, tin, bi content in LD7-4 material in 0.01% measurement below；
(4) method that ICP-OES method of the present invention measures lead, tin, bi content in aluminium alloy, sample pretreatment process is simple, Easy to operate quickly accuracy rate is high, is suitble to batch detection.
Specific embodiment
The present invention is described in detail With reference to embodiment.
ICP-OES method, that is, inductively coupled plasma emission spectrography.
The method that ICP-OES method measures lead, tin, bi content in aluminium alloy, specifically implements according to the following steps：
Step 1, according to method as defined in GB/T602, prepare lead standard solution, the tin standard solution, bismuth of isoconcentration respectively The manganese standard solution of standard solution and isoconcentration, nickel standard solution, iron standard solution, copper standard solution, magnesium standard solution, zirconium mark Quasi- solution；
Step 2 weighs the rafifinal that n parts of mass fractions are 99.99% or more as matrix original pattern, and wherein n is not less than 5； Hydrochloric acid solution, nitric acid solution are sequentially added into n parts of described matrix original patterns first, is prepared into solution A respectively1, solution A2、…… Solution An, then to the solution A1, solution A2... solution AnMiddle manganese standard solution, the nickel standard solution, iron that isoconcentration is added Standard solution, copper standard solution, magnesium standard solution, zirconium standard solution, respectively obtain solution B1, solution B2... solution Bn, so Backward solution B1, solution B2... solution BnMiddle isoconcentration lead standard solution, the tin standard solution, bismuth standard that suitable gradient is added Solution obtains calibration curve solution C1, calibration curve solution C2... ... calibration curve solution Cn；
Step 2.1 weighs the rafifinal that n parts of mass fractions are 99.99% or more, is respectively placed in n container；
Step 2.2 by water and hydrochloric acid volume ratio is 1:1~2:1 dilutes excellent pure grade hydrochloric acid solution, and it is molten to obtain n parts of hydrochloric acid Liquid D, wherein top grade pure hydrochloric acid density is 1.19g/ml；
Step 2.3, by the ratio between the quality of rafifinal and hydrochloric acid solution D volume be 1:100~1:300 is equal into each container The hydrochloric acid solution D of equivalent is added, is reacted to hydrochloric acid solution D with rafifinal completion, obtains n parts of solution Es；
The ratio between step 2.4, volume and nitric acid solution volume for pressing hydrochloric acid solution D again are 10:1~30:1 to every part of solution E In the nitric acid solution of equivalent is added, be cooled to room temperature after heating, obtain solution A1, solution A2... solution An, wherein nitric acid Solution uses density for the excellent pure grade nitric acid solution of 1.42/ml；The heating condition of step 2.4 is：It is heated to using 80-120 DEG C Sample is completely dissolved, then drives away nitrogen oxides completely solution heating using 150-200 DEG C；
Step 2.5, to solution A1, solution A2... solution AnIn be separately added into manganese standard solution, the nickel standard of isoconcentration Solution, iron standard solution, copper standard solution, magnesium standard solution, zirconium standard solution, concentration are 1000 μ g/ml, and the amount of addition is controllable System is in a certain range：50 μ L of μ L~200 of manganese standard solution, nickel standard solution 1.0mL~1.4mL, iron standard solution 0.9mL ~1.2mL, copper standard solution 2.1mL~2.7mL, magnesium standard solution 1.3mL~1.7mL, the 10 μ L of μ L~50 of zirconium standard solution, obtain To solution B1, solution B2... solution Bn, wherein n is not less than 5；
Step 2.6, again to solution B1, solution B2... solution BnIn by suitable gradient be added isoconcentration lead standard it is molten Liquid, tin standard solution, bismuth standard solution, concentration 0.01mg/ml, solution B1The lead standard solution of middle addition, tin standard solution, The volume of bismuth standard solution is identical, solution B2The volume phase of the lead standard solution of middle addition, tin standard solution, bismuth standard solution Solution B together ... ...nThe lead standard solution of middle addition, tin standard solution, the volume of bismuth standard solution are identical.It is marked after constant volume Directrix curve solution C1, calibration curve solution C2... calibration curve solution Cn, wherein n is not less than 5.
Step 3, using inductive coupling plasma emission spectrograph to calibration curve solution C1, solution C2... ... solution Cn It is detected, obtains the intensity of emission spectra of each calibration curve solution, inductive coupling plasma emission spectrograph is respectively with each Lead in calibration curve solution, tin, bismuth concentration be abscissa, with the transmitting of lead, tin and bismuth in each calibration curve solution of measurement Spectral intensity is that ordinate draws out working curve automatically；In general, the selection principle of spectral line when measuring Minor element：It must It must consider to interfere minimum analysis spectral line, then consider further that signal compared with strong, the lower spectral line of background, the equipment that this method uses is soft Lead that part provides, tin, bismuth respectively have a plurality of spectral line available, according to the selection principle of spectral line, the final analysis spectral line for determining lead For 220.353nm, the analysis spectral line of tin is 189.927nm, and the analysis spectral line of bismuth is 190.171nm；
The running parameter of inductive coupling plasma emission spectrograph is in step 3：Atomization gas flow 0.8L/min, observation Distance is 15mm, high frequency power 1300W, secondary air amount 0.2L/min, plasma flow 15L/min, sample flow Measure 1.50mL/min.
Hydrochloric acid solution D is first added into aluminium alloy LD7-4 sample in step 4, to after the reaction was completed, then by hydrochloric acid solution D's The ratio between volume and nitric acid solution volume are 10:1~15:1 is added nitric acid solution, prepares the solution to be measured of aluminium alloy LD7-4 sample；
The concrete operation step of step 4 is as follows：
Step 4.1 weighs aluminium alloy LD7-4 sample, is placed in container；
Step 4.2 by water and hydrochloric acid volume ratio is 1:1~2:1 dilutes excellent pure grade hydrochloric acid solution, obtains hydrochloric acid solution D；
The ratio between step 4.3, the hydrochloric acid solution D volume obtained by the quality of aluminium alloy LD7-4 and through step 2.3 are 1:100 ~1:300 hydrochloric acid solution D is added into container, reacts to hydrochloric acid solution D with the completion of aluminium alloy LD7-4 sample, obtains solution F；
Step 4.4 is 10 by the ratio between the volume of hydrochloric acid solution D and nitric acid solution volume:1~30:1 is added into solution F Nitric acid solution, after be cooled to room temperature, solution to be measured is obtained after constant volume, the volume of constant volume is identical as step 2.6, wherein nitric acid solution Use density for the excellent pure grade nitric acid solution of 1.42/ml.
The condition of the heating of step 4.4 is：It is first heated to 80-120 DEG C using hot plate and is heated to sample being completely dissolved, It is again heated to 150-200 DEG C to heat solution, drives away nitrogen oxides clean.
Step 5 detects the solution to be measured that step 4 obtains with the same determination condition of step 3, measures test solution The intensity of emission spectra of middle lead, tin and bismuth obtains lead in test solution, tin and bismuth according to the working curve diagram of calibration curve solution Concentration.
Embodiment 1
The method that ICP-OES method measures lead, tin, bi content in aluminium alloy, specifically implements according to the following steps：
Step 1, according to method as defined in GB/T602, prepare lead standard solution, the tin standard solution, bismuth of isoconcentration respectively The manganese standard solution of standard solution and isoconcentration, nickel standard solution, iron standard solution, copper standard solution, magnesium standard solution, zirconium mark Quasi- solution；
Step 1.1, according to method as defined in GB/T602, prepare lead standard solution that solution concentration is 0.1mg/ml, molten The bismuth standard solution that the tin standard solution and solution concentration that liquid concentration is 0.1mg/ml are 0.1mg/ml, draws 10.00ml respectively Three kinds of standard solution, and move into 100ml volumetric flask respectively, it is diluted to scale, is shaken up；
Step 1.2 according to method as defined in GB/T602, prepare respectively solution concentration be the copper of 1000 μ g/ml, iron, manganese, Magnesium, nickel, zirconium single element standard solution；
Step 2 weighs the rafifinal that 6 parts of mass fractions are 99.99% or more as matrix original pattern；First to 6 parts of matrixes Hydrochloric acid solution, nitric acid solution are sequentially added in original pattern, are prepared into solution A respectively1, solution A2... solution A6, then to solution A1、 Solution A2... solution A6Middle manganese standard solution, nickel standard solution, iron standard solution, the copper standard solution, magnesium that isoconcentration is added Standard solution, zirconium standard solution, respectively obtain solution B1, solution B2... solution B6, then to solution B1, solution B2... it is molten Liquid B6Middle isoconcentration lead standard solution, tin standard solution, the bismuth standard solution that suitable gradient is added, obtains calibration curve solution C1, Calibration curve solution C2... ... calibration curve solution C6；
Step 2.1 weighs the rafifinal that six parts of mass fractions of rafifinal are 99.99% or more, and every part of 0.1g is accurate to 0.0001g is respectively placed in 6 100ml conical flasks；
Step 2.2 by water and hydrochloric acid solution volume ratio is 1:1 ratio dilutes excellent pure grade hydrochloric acid solution, obtains hydrochloric acid Solution D；
Step 2.3, by the ratio between the quality of rafifinal and hydrochloric acid solution D volume be 1:100 additions etc. into each container The hydrochloric acid solution D of amount reacts with rafifinal completion to hydrochloric acid solution D, obtains 6 parts of solution Es；
The ratio between step 2.4, volume and nitric acid solution volume for pressing hydrochloric acid solution D again are 10:1 adds into every part of solution E Enter the nitric acid solution of equivalent, is cooled to room temperature after heating, obtains solution A1, solution A2... solution A6, wherein nitric acid solution is adopted The excellent pure grade nitric acid solution for being 1.42/ml with density；
It is 80 DEG C by hot plate temperature setting, is heated to rafifinal and is completely dissolved, solution heating is made into nitrogen at 200 DEG C Oxide is driven away completely, is cooled to room temperature, obtains solution A1, solution A2, solution A3, solution A4, solution A5, solution A6；
Step 2.5, into every part of solution A, addition 50 μ L of manganese standard solution, nickel standard solution 1.0mL, iron standard are molten respectively Liquid 0.9mL, copper standard solution 2.1mL, magnesium standard solution 1.3mL, 10 μ L of zirconium standard solution；Obtain solution B1, solution B2, solution B3, solution B4, solution B5, solution B6；
Step 2.6, again to solution B1, solution B2, solution B3, solution B4, solution B5, solution B6In lead, tin, bismuth is added Standard solution, and solution B1The lead of middle addition, tin, bismuth volume are identical, solution B2The lead of middle addition, tin, bismuth volume are identical, solution B3The lead of middle addition, tin, bismuth volume are identical, solution B4The lead of middle addition, tin, bismuth volume are identical, solution B5The lead of middle addition, tin, Bismuth volume is identical, solution B6The lead of middle addition, tin, bismuth volume are identical, solution B1, solution B2, solution B3, solution B4, solution B5, it is molten Liquid B6Middle lead, tin, bismuth standard solution addition volume be successively 0ml, 1ml, 2ml, 5ml, 10ml, 20ml, move into 100ml capacity In bottle, scale is diluted to water, is shaken up, calibration curve solution C is obtained1, calibration curve solution C2, calibration curve solution C3, standard Curve solution C4, calibration curve solution C5, calibration curve solution C6。
Step 3 eliminates background interference：The calibration curve solution that step 2 is obtained is emitted using inductively coupled plasma body Spectrometer is detected, and the intensity emission spectra line chart of each element is obtained.Two background dots are respectively moved to analytical line two sides most The position of low-level line, background correction interference, store method.
The calibration curve solution that step 2 obtains is detected using inductive coupling plasma emission spectrograph, is obtained Calibration curve solution C1, calibration curve solution C2, calibration curve solution C3, calibration curve solution C4, calibration curve solution C5, standard Curve solution C6Lead, tin, bismuth intensity of emission spectra, respectively with lead in each calibration curve solution, tin, bismuth standard solution Concentration is abscissa, automatic to draw using the intensity of emission spectra of lead, tin and bismuth in each calibration curve solution of measurement as ordinate Working curve out.The present embodiment uses 6 point-rendering standard curves, and more than 6 point-rendering standard curves can also be used and treat Survey solution in lead, tin, bismuth content be measured, precision is higher.
The running parameter of inductive coupling plasma emission spectrograph is：Atomization gas flow 0.8L/min, observed range are 15mm, high frequency power 1300W, secondary air amount 0.2L/min, plasma flow 15L/min, sample flow 1.50mL/min, number of repetition 3 times.
Lead that the device software of use provides, tin, bismuth respectively have a plurality of spectral line available, according to the selection principle of spectral line, First consider to interfere minimum analysis spectral line, then considers further that signal compared with strong, the lower spectral line of background.Final choice, the analysis of lead Spectral line is 220.353nm, and the analysis spectral line of tin is 189.927nm, and the analysis spectral line of bismuth is 190.171nm.
This serial lead, tin, bismuth calibration curve solution in the mass concentration of each element be equivalent to each element quality in sample Score.This series standard curve solution is subjected to spectroscopic assay on inductive coupling plasma emission spectrograph, with element Intensity of emission spectra is the longitudinal axis, lead, tin, bismuth mass fraction be that horizontal axis makees linear regression.Related coefficient is calculated, related coefficient is equal Greater than 0.999, measurement result is shown in Table 1.
The mass fraction of lead, tin, bismuth in 1 standard solution of table
Hydrochloric acid solution D is first added into aluminium alloy LD7-4 sample in step 4, to after the reaction was completed, then by hydrochloric acid solution D's The ratio between volume and nitric acid solution volume are 10:1 is added nitric acid solution, prepares the solution to be measured of aluminium alloy LD7-4 sample；
Step 4.1 weighs aluminium alloy LD7-4 sample, is placed in conical flask；
Step 4.2 by water and hydrochloric acid volume ratio is 1:1 dilutes excellent pure grade hydrochloric acid solution, obtains hydrochloric acid solution D；
The ratio between step 4.3, the hydrochloric acid solution D volume obtained by the quality of aluminium alloy LD7-4 and through step 2.3 are 1:100 Hydrochloric acid solution D is added into container, is reacted to hydrochloric acid solution D with the completion of aluminium alloy LD7-4 sample, obtains solution F；
Step 4.4 is 10 by the ratio between the volume of hydrochloric acid solution D and nitric acid solution volume:1 that nitric acid is added into solution F is molten Liquid, after be cooled to room temperature, solution to be measured is obtained after constant volume, the volume of constant volume is identical as step 2.6, and wherein nitric acid solution is using close Degree is the excellent pure grade nitric acid solution of 1.42/ml.
The condition of the heating of step 4.5 is：It is heated to sample using 80 DEG C to be completely dissolved, then will be molten using 150-200 DEG C Liquid heating drives away nitrogen oxides clean.
Solution to be measured is measured by step 5 with the same determination condition of step 3, is checked in from working curve to be tested The concentration of lead, tin and bismuth in liquid.Also software being analyzed by instrument, element to be measured is calculated according to the intensity of element to be measured automatically Mass concentration, and show, the two effect is identical.
Embodiment 2
The method that ICP-OES method measures lead, tin, bi content in aluminium alloy, specifically implements according to the following steps：
Step 1, according to method as defined in GB/T602, prepare lead standard solution, the tin standard solution, bismuth of isoconcentration respectively The manganese standard solution of standard solution and isoconcentration, nickel standard solution, iron standard solution, copper standard solution, magnesium standard solution, zirconium mark Quasi- solution；
Step 1.1, according to method as defined in GB/T602, prepare lead standard solution that solution concentration is 0.1mg/ml, molten The bismuth standard solution that the tin standard solution and solution concentration that liquid concentration is 0.1mg/ml are 0.1mg/ml, draws 10.00ml respectively Three kinds of standard solution, and move into 100ml volumetric flask respectively, it is diluted to scale, is shaken up；
Step 1.2 respectively according to method as defined in GB/T602, prepare copper, iron, manganese that solution concentration is 1000 μ g/ml, Magnesium, nickel, zirconium single element standard solution；
Step 2 weighs the rafifinal that 6 parts of mass fractions are 99.99% or more as matrix original pattern；First to 6 parts of matrixes Hydrochloric acid solution, nitric acid solution are sequentially added in original pattern, are prepared into solution A respectively1, solution A2... solution A6, then to solution A1、 Solution A2... solution A6Middle manganese standard solution, nickel standard solution, iron standard solution, the copper standard solution, magnesium that isoconcentration is added Standard solution, zirconium standard solution, respectively obtain solution B1, solution B2... solution B6, then to solution B1, solution B2... it is molten Liquid B6Middle isoconcentration lead standard solution, tin standard solution, the bismuth standard solution that suitable gradient is added, obtains calibration curve solution C1, Calibration curve solution C2... ... calibration curve solution C6；
Step 2.1 weighs the rafifinal that six parts of mass fractions of rafifinal are 99.99% or more, and every part of 0.1g is accurate to 0.0001g is respectively placed in 6 100ml conical flasks；
Step 2.2 by water and hydrochloric acid solution volume ratio is 1.4:1 ratio dilutes excellent pure grade hydrochloric acid solution, obtains salt Acid solution D；
Step 2.3, by the ratio between the quality of rafifinal and hydrochloric acid solution D volume be 1:150 additions etc. into each container The hydrochloric acid solution D of amount reacts with rafifinal completion to hydrochloric acid solution D, obtains 6 parts of solution Es；
The ratio between step 2.4, volume and nitric acid solution volume for pressing hydrochloric acid solution D again are 15:1 adds into every part of solution E Enter the nitric acid solution of equivalent, is cooled to room temperature after heating, obtains solution A1, solution A2... solution A6, wherein nitric acid solution is adopted The excellent pure grade nitric acid solution for being 1.42/ml with density；
Rafifinal is heated to using 100 DEG C to be completely dissolved, and drives away nitrogen oxides completely solution heating at 170 DEG C, It is cooled to room temperature, obtains solution A1, solution A2, solution A3, solution A4, solution A5, solution A6；
Step 2.5, into every part of solution A, addition 100 μ L of manganese standard solution, nickel standard solution 1.2mL, iron standard are molten respectively Liquid 1.0mL, copper standard solution 2.3mL, magnesium standard solution 1.4mL, 20 μ L of zirconium standard solution；Obtain solution B1, solution B2, solution B3, solution B4, solution B5, solution B6；
Step 2.6, again to solution B1, solution B2, solution B3, solution B4, solution B5, solution B6In lead, tin, bismuth is added Standard solution, and solution B1The lead of middle addition, tin, bismuth volume are identical, solution B2The lead of middle addition, tin, bismuth volume are identical, solution B3The lead of middle addition, tin, bismuth volume are identical, solution B4The lead of middle addition, tin, bismuth volume are identical, solution B5The lead of middle addition, tin, Bismuth volume is identical, solution B6The lead of middle addition, tin, bismuth volume are identical, solution B1, solution B2, solution B3, solution B4, solution B5, it is molten Liquid B6Middle lead, tin, bismuth standard solution addition volume be successively 0ml, 1ml, 2ml, 5ml, 10ml, 20ml, move into 100ml capacity In bottle, scale is diluted to water, is shaken up, calibration curve solution C is obtained1, calibration curve solution C2, calibration curve solution C3, standard Curve solution C4, calibration curve solution C5, calibration curve solution C6。
Step 3 eliminates background interference：The calibration curve solution that step 2 is obtained is emitted using inductively coupled plasma body Spectrometer is detected, and the intensity emission spectra line chart of each element is obtained.Two background dots are respectively moved to analytical line two sides most The position of low-level line, background correction interference, store method.
The calibration curve solution that step 2 obtains is detected using inductive coupling plasma emission spectrograph, is obtained Calibration curve solution C1, calibration curve solution C2, calibration curve solution C3, calibration curve solution C4, calibration curve solution C5, standard Curve solution C6Lead, tin, bismuth intensity of emission spectra, respectively with lead in each calibration curve solution, tin, bismuth standard solution Concentration is abscissa, automatic to draw using the intensity of emission spectra of lead, tin and bismuth in each calibration curve solution of measurement as ordinate Working curve out.The present embodiment uses 6 point-rendering standard curves, and more than 6 point-rendering standard curves can also be used and treat Survey solution in lead, tin, bismuth content be measured, precision is higher.
The running parameter of inductive coupling plasma emission spectrograph is：Atomization gas flow 0.8L/min, observed range are 15mm, high frequency power 1300W, secondary air amount 0.2L/min, plasma flow 15L/min, sample flow 1.50mL/min, number of repetition 4 times.
Lead that the device software of use provides, tin, bismuth respectively have a plurality of spectral line available, according to the selection principle of spectral line, First consider to interfere minimum analysis spectral line, then considers further that signal compared with strong, the lower spectral line of background.Final choice, the analysis of lead Spectral line is 220.353nm, and the analysis spectral line of tin is 189.927nm, and the analysis spectral line of bismuth is 190.171nm.
This serial lead, tin, bismuth calibration curve solution in the mass concentration of each element be equivalent to each element quality in sample Score.This series standard curve solution is subjected to spectroscopic assay on inductive coupling plasma emission spectrograph, with element Intensity of emission spectra is the longitudinal axis, lead, tin, bismuth mass fraction be that horizontal axis makees linear regression.Related coefficient is calculated, related coefficient is equal Greater than 0.999, measurement result is shown in Table 2.
The mass fraction of lead, tin, bismuth in 2 standard solution of table
Hydrochloric acid solution D is first added into aluminium alloy LD7-4 sample in step 4, to after the reaction was completed, then by hydrochloric acid solution D's The ratio between volume and nitric acid solution volume are 12：1:Nitric acid solution is added, prepares the solution to be measured of aluminium alloy LD7-4 sample；
Step 4.1 weighs aluminium alloy LD7-4 sample, is placed in container；
Step 4.2 by water and hydrochloric acid volume ratio is 1.4：1:Excellent pure grade hydrochloric acid solution is diluted, hydrochloric acid solution D is obtained；
The ratio between step 4.3, the hydrochloric acid solution D volume obtained by the quality of aluminium alloy LD7-4 and through step 2.3 are 1:150 Hydrochloric acid solution D is added into container, is reacted to hydrochloric acid solution D with the completion of aluminium alloy LD7-4 sample, obtains solution F；
Step 4.4 is 15 by the ratio between the volume of hydrochloric acid solution D and nitric acid solution volume:1 that nitric acid is added into solution F is molten Liquid, after be cooled to room temperature, solution to be measured is obtained after constant volume, the volume of constant volume is identical as step 2.6, and wherein nitric acid solution is using close Degree is the excellent pure grade nitric acid solution of 1.42/ml.
The condition of the heating of step 4.4 is：It is heated to sample using 90 DEG C to be completely dissolved, then will be molten using 150-200 DEG C Liquid heating drives away nitrogen oxides clean.
Solution to be measured is measured with the same determination condition of step 3, from checked in working curve lead in test solution, The concentration of tin and bismuth.Also it is dense the quality that software calculates element to be measured according to the intensity of element to be measured automatically can be analyzed by instrument Degree, and show, the two effect is identical.
Embodiment 3
The method that ICP-OES method measures lead, tin, bi content in aluminium alloy, specifically implements according to the following steps：
Step 1, according to method as defined in GB/T602, prepare lead standard solution, the tin standard solution, bismuth of isoconcentration respectively The manganese standard solution of standard solution and isoconcentration, nickel standard solution, iron standard solution, copper standard solution, magnesium standard solution, zirconium mark Quasi- solution；
Step 1.1, according to method as defined in GB/T602, prepare lead standard solution that solution concentration is 0.1mg/ml, molten The bismuth standard solution that the tin standard solution and solution concentration that liquid concentration is 0.1mg/ml are 0.1mg/ml, draws 10.00ml respectively Three kinds of standard solution, and move into 100ml volumetric flask respectively, it is diluted to scale, is shaken up；
Step 1.2 respectively according to method as defined in GB/T602, prepare copper, iron, manganese that solution concentration is 1000 μ g/ml, Magnesium, nickel, zirconium single element standard solution；
Step 2 weighs the rafifinal that 6 parts of mass fractions are 99.99% or more as matrix original pattern；First to 6 parts of matrixes Hydrochloric acid solution, nitric acid solution are sequentially added in original pattern, are prepared into solution A respectively1, solution A2... solution A6, then to solution A1、 Solution A2... solution A6Middle manganese standard solution, nickel standard solution, iron standard solution, the copper standard solution, magnesium that isoconcentration is added Standard solution, zirconium standard solution, respectively obtain solution B1, solution B2... solution B6, then to solution B1, solution B2... it is molten Liquid B6Middle isoconcentration lead standard solution, tin standard solution, the bismuth standard solution that suitable gradient is added, obtains calibration curve solution C1, Calibration curve solution C2... ... calibration curve solution C6；
Step 2.1 weighs the rafifinal that six parts of mass fractions of rafifinal are 99.99% or more, and every part of 0.1g is accurate to 0.0001g is respectively placed in 6 100ml conical flasks；
Step 2.2 by water and hydrochloric acid solution volume ratio is 1.7:1 ratio dilutes excellent pure grade hydrochloric acid solution, obtains salt Acid solution D；
Step 2.3, by the ratio between the quality of rafifinal and hydrochloric acid solution D volume be 1:200 additions etc. into each container The hydrochloric acid solution D of amount reacts with rafifinal completion to hydrochloric acid solution D, obtains 6 parts of solution Es；
The ratio between step 2.4, volume and nitric acid solution volume for pressing hydrochloric acid solution D again are 20:1 adds into every part of solution E Enter the nitric acid solution of equivalent, is cooled to room temperature after heating, obtains solution A1, solution A2... solution A6, wherein nitric acid solution is adopted The excellent pure grade nitric acid solution for being 1.42/ml with density；
Rafifinal is heated to using 110 DEG C to be completely dissolved, and drives away nitrogen oxides completely solution heating at 190 DEG C, It is cooled to room temperature, obtains solution A1, solution A2, solution A3, solution A4, solution A5, solution A6；
Step 2.5, into every part of solution A, addition 150 μ L of manganese standard solution, nickel standard solution 1.3mL, iron standard are molten respectively Liquid 1.1mL, copper standard solution 2.5mL, magnesium standard solution 1.6mL, 40 μ L of zirconium standard solution；Obtain solution B1, solution B2, solution B3, solution B4, solution B5, solution B6；
Step 2.6, again to solution B1, solution B2, solution B3, solution B4, solution B5, solution B6In lead, tin, bismuth is added Standard solution, and solution B1The lead of middle addition, tin, bismuth volume are identical, solution B2The lead of middle addition, tin, bismuth volume are identical, solution B3The lead of middle addition, tin, bismuth volume are identical, solution B4The lead of middle addition, tin, bismuth volume are identical, solution B5The lead of middle addition, tin, Bismuth volume is identical, solution B6The lead of middle addition, tin, bismuth volume are identical, solution B1, solution B2, solution B3, solution B4, solution B5, it is molten Liquid B6Middle lead, tin, bismuth standard solution addition volume be successively 0ml, 1ml, 2ml, 5ml, 10ml, 20ml, move into 100ml capacity In bottle, scale is diluted to water, is shaken up, calibration curve solution C is obtained1, calibration curve solution C2, calibration curve solution C3, standard Curve solution C4, calibration curve solution C5, calibration curve solution C6。
Step 3 eliminates background interference：The calibration curve solution that step 2 is obtained is emitted using inductively coupled plasma body Spectrometer is detected, and the intensity emission spectra line chart of each element is obtained.Two background dots are respectively moved to analytical line two sides most The position of low-level line, background correction interference, store method.
The calibration curve solution that step 2 obtains is detected using inductive coupling plasma emission spectrograph, is obtained Calibration curve solution C1, calibration curve solution C2, calibration curve solution C3, calibration curve solution C4, calibration curve solution C5, standard Curve solution C6Lead, tin, bismuth intensity of emission spectra, respectively with lead in each calibration curve solution, tin, bismuth standard solution Concentration is abscissa, automatic to draw using the intensity of emission spectra of lead, tin and bismuth in each calibration curve solution of measurement as ordinate Working curve out.The present embodiment uses 6 point-rendering standard curves, and more than 6 point-rendering standard curves can also be used and treat Survey solution in lead, tin, bismuth content be measured, precision is higher.
The running parameter of inductive coupling plasma emission spectrograph is：Atomization gas flow 0.8L/min, observed range are 15mm, high frequency power 1300W, secondary air amount 0.2L/min, plasma flow 15L/min, sample flow 1.50mL/min, number of repetition 5 times.
Lead that the device software of use provides, tin, bismuth respectively have a plurality of spectral line available, according to the selection principle of spectral line, First consider to interfere minimum analysis spectral line, then considers further that signal compared with strong, the lower spectral line of background.Final choice, the analysis of lead Spectral line is 220.353nm, and the analysis spectral line of tin is 189.927nm, and the analysis spectral line of bismuth is 190.171nm.
This serial lead, tin, bismuth calibration curve solution in the mass concentration of each element be equivalent to each element quality in sample Score.This series standard curve solution is subjected to spectroscopic assay on inductive coupling plasma emission spectrograph, with element Intensity of emission spectra is the longitudinal axis, lead, tin, bismuth mass fraction be that horizontal axis makees linear regression.Related coefficient is calculated, related coefficient is equal Greater than 0.999, measurement result is shown in Table 3.
The mass fraction of lead, tin, bismuth in 3 standard solution of table
Hydrochloric acid solution D is first added into aluminium alloy LD7-4 sample in step 4, to after the reaction was completed, then by hydrochloric acid solution D's The ratio between volume and nitric acid solution volume are 14:1 is added nitric acid solution, prepares the solution to be measured of aluminium alloy LD7-4 sample；
Step 4.1 weighs aluminium alloy LD7-4 sample, is placed in container；
Step 4.2 by water and hydrochloric acid volume ratio is 1.8:1 dilutes excellent pure grade hydrochloric acid solution, obtains hydrochloric acid solution D；
The ratio between step 4.3, the hydrochloric acid solution D volume obtained by the quality of aluminium alloy LD7-4 and through step 2.3 are 1:200 Hydrochloric acid solution D is added into container, is reacted to hydrochloric acid solution D with the completion of aluminium alloy LD7-4 sample, obtains solution F；
Step 4.4 is 20 by the ratio between the volume of hydrochloric acid solution D and nitric acid solution volume:1 that nitric acid is added into solution F is molten Liquid, after be cooled to room temperature, solution to be measured is obtained after constant volume, the volume of constant volume is identical as step 2.6, and wherein nitric acid solution is using close Degree is the excellent pure grade nitric acid solution of 1.42/ml.
The condition of the heating of step 4.5 is：It is heated to sample using 110 DEG C to be completely dissolved, then will be molten using 150-200 DEG C Liquid heating drives away nitrogen oxides clean.
Solution to be measured is measured with the same determination condition of step 3, from checked in working curve lead in test solution, The concentration of tin and bismuth.Also it is dense the quality that software calculates element to be measured according to the intensity of element to be measured automatically can be analyzed by instrument Degree, and show, the two effect is identical.
Embodiment 4
The method that ICP-OES method measures lead, tin, bi content in aluminium alloy, specifically implements according to the following steps：
Step 1, according to method as defined in GB/T602, prepare lead standard solution, the tin standard solution, bismuth of isoconcentration respectively The manganese standard solution of standard solution and isoconcentration, nickel standard solution, iron standard solution, copper standard solution, magnesium standard solution, zirconium mark Quasi- solution；
Step 1.1, according to method as defined in GB/T602, prepare lead standard solution that solution concentration is 0.1mg/ml, molten The bismuth standard solution that the tin standard solution and solution concentration that liquid concentration is 0.1mg/ml are 0.1mg/ml, draws 10.00ml respectively Three kinds of standard solution, and move into 100ml volumetric flask respectively, it is diluted to scale, is shaken up；
Step 1.2 respectively according to method as defined in GB/T602, prepare copper, iron, manganese that solution concentration is 1000 μ g/ml, Magnesium, nickel, zirconium single element standard solution；
Step 2 weighs the rafifinal that 6 parts of mass fractions are 99.99% or more as matrix original pattern；First to 6 parts of matrixes Hydrochloric acid solution, nitric acid solution are sequentially added in original pattern, are prepared into solution A respectively1, solution A2... solution A6, then to solution A1、 Solution A2... solution A6Middle manganese standard solution, nickel standard solution, iron standard solution, the copper standard solution, magnesium that isoconcentration is added Standard solution, zirconium standard solution, respectively obtain solution B1, solution B2... solution B6, then to solution B1, solution B2... it is molten Liquid B6Middle isoconcentration lead standard solution, tin standard solution, the bismuth standard solution that suitable gradient is added, obtains calibration curve solution C1, Calibration curve solution C2... ... calibration curve solution C6；
Step 2.1 weighs the rafifinal that six parts of mass fractions of rafifinal are 99.99% or more, and every part of 0.1g is accurate to 0.0001g is respectively placed in 6 100ml conical flasks；
Step 2.2 by water and hydrochloric acid solution volume ratio is 2:1 ratio dilutes excellent pure grade hydrochloric acid solution, obtains hydrochloric acid Solution D；
Step 2.3, by the ratio between the quality of rafifinal and hydrochloric acid solution D volume be 1:300 additions etc. into each container The hydrochloric acid solution D of amount reacts with rafifinal completion to hydrochloric acid solution D, obtains n parts of solution Es；
The ratio between step 2.4, volume and nitric acid solution volume for pressing hydrochloric acid solution D again are 30:1 adds into every part of solution E Enter the nitric acid solution of equivalent, is cooled to room temperature after heating, obtains solution A1, solution A2... solution A6, wherein nitric acid solution is adopted The excellent pure grade nitric acid solution for being 1.42/ml with density；
Rafifinal is heated to using 120 DEG C to be completely dissolved, and drives away nitrogen oxides completely solution heating at 200 DEG C, It is cooled to room temperature, obtains solution A1, solution A2, solution A3, solution A4, solution A5, solution A6；
Step 2.5, into every part of solution A, addition 200 μ L of manganese standard solution, nickel standard solution 1.4mL, iron standard are molten respectively Liquid 1.2mL, copper standard solution 2.7mL, magnesium standard solution 1.7mL, 50 μ L of zirconium standard solution；Obtain solution B1, solution B2, solution B3, solution B4, solution B5, solution B6；
Step 2.6, again to solution B1, solution B2, solution B3, solution B4, solution B5, solution B6In lead, tin, bismuth is added Standard solution, and solution B1The lead of middle addition, tin, bismuth volume are identical, solution B2The lead of middle addition, tin, bismuth volume are identical, solution B3The lead of middle addition, tin, bismuth volume are identical, solution B4The lead of middle addition, tin, bismuth volume are identical, solution B5The lead of middle addition, tin, Bismuth volume is identical, solution B6The lead of middle addition, tin, bismuth volume are identical, solution B1, solution B2, solution B3, solution B4, solution B5, it is molten Liquid B6Middle lead, tin, bismuth standard solution addition volume be successively 0ml, 1ml, 2ml, 5ml, 10ml, 20ml, move into 100ml capacity In bottle, scale is diluted to water, is shaken up, calibration curve solution C is obtained1, calibration curve solution C2, calibration curve solution C3, standard Curve solution C4, calibration curve solution C5, calibration curve solution C6。
Step 3 eliminates background interference：The calibration curve solution that step 2 is obtained is emitted using inductively coupled plasma body Spectrometer is detected, and the intensity emission spectra line chart of each element is obtained.Two background dots are respectively moved to analytical line two sides most The position of low-level line, background correction interference, store method.
The calibration curve solution that step 2 obtains is detected using inductive coupling plasma emission spectrograph, is obtained Calibration curve solution C1, calibration curve solution C2, calibration curve solution C3, calibration curve solution C4, calibration curve solution C5, standard Curve solution C6Lead, tin, bismuth intensity of emission spectra, respectively with lead in each calibration curve solution, tin, bismuth standard solution Concentration is abscissa, automatic to draw using the intensity of emission spectra of lead, tin and bismuth in each calibration curve solution of measurement as ordinate Working curve out.The present embodiment uses 6 point-rendering standard curves, and more than 6 point-rendering standard curves can also be used and treat Survey solution in lead, tin, bismuth content be measured, precision is higher.
The running parameter of inductive coupling plasma emission spectrograph is：Atomization gas flow 0.8L/min, observed range are 15mm, high frequency power 1300W, secondary air amount 0.2L/min, plasma flow 15L/min, sample flow 1.50mL/min, number of repetition 6 times.
Lead that the device software of use provides, tin, bismuth respectively have a plurality of spectral line available, according to the selection principle of spectral line, First consider to interfere minimum analysis spectral line, then considers further that signal compared with strong, the lower spectral line of background.Final choice, the analysis of lead Spectral line is 220.353nm, and the analysis spectral line of tin is 189.927nm, and the analysis spectral line of bismuth is 190.171nm.This serial lead, tin, The mass concentration of each element is equivalent to each element mass fraction in sample in the calibration curve solution of bismuth.By this series standard curve Solution carries out spectroscopic assay on inductive coupling plasma emission spectrograph, using the intensity of emission spectra of element as the longitudinal axis, lead, Tin, bismuth mass fraction be horizontal axis make linear regression.Related coefficient is calculated, related coefficient is all larger than 0.999, and measurement result is shown in Table 4。
The mass fraction of lead, tin, bismuth in 4 standard solution of table
Hydrochloric acid solution D is first added into aluminium alloy LD7-4 sample in step 4, to after the reaction was completed, then by hydrochloric acid solution D's The ratio between volume and nitric acid solution volume are 15:1 is added nitric acid solution, prepares the solution to be measured of aluminium alloy LD7-4 sample；
Step 4.1 weighs aluminium alloy LD7-4 sample, is placed in container；
Step 4.2 by water and hydrochloric acid volume ratio is 2:1 dilutes excellent pure grade hydrochloric acid solution, obtains hydrochloric acid solution D；
The ratio between step 4.3, the hydrochloric acid solution D volume obtained by the quality of aluminium alloy LD7-4 and through step 2.3 are 1:300 Hydrochloric acid solution D is added into container, is reacted to hydrochloric acid solution D with the completion of aluminium alloy LD7-4 sample, obtains solution F；
Step 4.4 is 30 by the ratio between the volume of hydrochloric acid solution D and nitric acid solution volume:1 that nitric acid is added into solution F is molten Liquid, after be cooled to room temperature, solution to be measured is obtained after constant volume, the volume of constant volume is identical as step 2.6, and wherein nitric acid solution is using close Degree is the excellent pure grade nitric acid solution of 1.42/ml.
The condition of the heating of step 4.4 is：It is heated to sample using 120 DEG C to be completely dissolved, then will be molten using 150-200 DEG C Liquid heating drives away nitrogen oxides clean.
Solution to be measured is measured with the same determination condition of step 3, from checked in working curve lead in test solution, The concentration of tin and bismuth.Also it is dense the quality that software calculates element to be measured according to the intensity of element to be measured automatically can be analyzed by instrument Degree, and show, the two effect is identical.
Experiment condition heuristic process：
1, the selection of sample weighting amount
The characteristics of being analyzed according to ICP-OES method, salt amount increases in test solution, and the viscosity of test solution is increased by, and will lead to lifting capacity Reduction, while consider weighing error and the actual conditions such as dilution error and measurement scale range, sample weighting amount selection 0.1000g is accurate to 0.0001g.
2, the selection of dissolving acid
In order to guarantee the Accurate Determining of element to be measured, the dissolution of sample must assure that component to be measured is totally converted solution In, according to the chemical property of lead, three tin, bismuth elements：Lead can be reacted with concentrated hydrochloric acid, but because the lead chloride for generating indissoluble is covered on Surface causes reaction to terminate soon.It is reacted with dilute sulfuric acid, because generating the sulfuric acid lead coating of indissoluble, reaction terminating.With heat The concentrated sulfuric acid can react；It can be reacted with dilute, concentrated nitric acid；Tin and concentrated hydrochloric acid just have considerable reaction speed, high concentration under heating Nitric acid decomposition samples, tin by concentrated nitric acid rapid oxidation be β-stannic acid not soluble in water, be another variant of stannic acid, it is insoluble In acid, be also insoluble in alkali, so as to cause rate of recovery decline, element sulphur to the measurement of tin there are spectra1 interfer-, and solution viscosity Higher system causes nebulization efficiency to decline；Bismuth is dissolved in chloroazotic acid and concentrated nitric acid, does not dissolve in non-oxidizing acid, the i.e. concentrated sulfuric acid and dense salt Acid is also only just slightly reacted in heat together.
By test of many times, discovery is used by water and hydrochloric acid volume ratio as 1：1 dilutes excellent pure grade salt, obtains hydrochloric acid solution D takes hydrochloric acid solution D10ml, and takes 1ml excellent pure grade nitric acid sample dissolution, and the optimal atomizing effect of lead, tin, bismuth can be obtained.
Interference correction：
(1) disturbed condition of matrix element and Main elements is analyzed：
Lead, tin, bismuth belong to microelement in material LD7-4, and content is generally 0.005% hereinafter, the present invention considers Matrix element, Main elements interference are drawn the solution of standard curve using the method preparation that alloying element is added, improve analysis Accuracy.
In the present invention, using Matrix phase configuration standard solution mass fraction is used to the interference of matrix and reagent Background dot is manually set in analytical line two sides position appropriate for 99.99% rafifinal bottoming, carries out background correction, thus Avoid the interference of matrix and reagent.
In experiments it is found that the magnesium, copper, manganese, zirconium in LD7-4 material can cause overgauge to lead, make the strength signal of lead Enhancing, iron, nickel cause minus deviation to lead, weaken the strength signal of lead；Magnesium, copper, manganese, zirconium, iron, nickel cause overgauge to bismuth, Making the strength signal of bismuth enhances；Magnesium, iron, manganese, zirconium cause minus deviation to tin, weaken the strength signal of tin, copper, nickel cause tin Overgauge enhances the strength signal of tin.So in the present invention, alloy adding alloying element close in sample to be tested Content, eliminate the interference of alloying element.
The presence of interference element will make analytical element generate deviation, need to carry out interference correction.It is possible according to selected spectral line A possibility that interfering and its existing in the base, copper, iron, manganese, magnesium, nickel, the zirconium single element that preparation solution concentration is 1000 μ g/ml Each portion of standard solution carries out interference correction test.Experiments have shown that the coexistence elements of experiment are measured without influence.
(2) preparation of calibration curve solution
The different preparation methods of three kinds of drafting working curve solution are selected to be compared：
Method one：Since the matrix of LD7 and LD7-4 are almost the same, therefore select the bottoming of LD7 standard specimen；
Six parts of LD7 standard specimen 0.1000g is weighed, is first 1 by water and hydrochloric acid volume ratio：1 dilutes excellent pure grade salt, obtains hydrochloric acid Solution D, hydrochloric acid use the top grade pure hydrochloric acid of ρ=1.19g/ml；10ml hydrochloric acid solution D is added to every part of LD7 standard specimen again, to violent After reaction, 1ml nitric acid solution is added, nitric acid is all made of the excellent pure grade of ρ=1.42/ml, obtains 6 parts of substrate solutions；Then to In six parts of substrate solutions be added lead, tin, bismuth standard solution, lead, tin, bismuth standard solution volume are identical, by 0ml, 1ml, 2ml, Lead, tin, bismuth standard solution is added in six kinds of volumes of 5ml, 10ml, 20ml, then moves into 100ml volumetric flask, is diluted to scale with water, It mixes.
Method two：The rafifinal bottoming for being 99.99% or more with mass fraction；
Six parts of rafifinal 0.1000g are weighed, is first 1 by water and hydrochloric acid volume ratio：1 dilutes excellent pure grade salt, obtains hydrochloric acid Solution D, hydrochloric acid use the top grade pure hydrochloric acid of ρ=1.19g/ml；10ml hydrochloric acid solution D is added to every rafifinal again, to acutely anti- Ying Hou adds 1ml nitric acid solution, and nitric acid is all made of the excellent pure grade of ρ=1.42/ml, obtains six parts of substrate solutions；Then to every Lead, tin, bismuth standard solution, the lead being added in every part of substrate solution, tin, bismuth standard solution volume are separately added into part substrate solution It is identical, it is molten that the lead of addition 0ml, 1ml, 2ml, 5ml, 10ml, 20ml, tin, bismuth standard in basad solution are distinguished by six kinds of volumes Liquid, then move into 100ml volumetric flask, scale is diluted to water, is mixed.
Method three：Alloying element bottoming is added with the rafifinal that mass fraction is 99.99% or more；
Six parts of rafifinal are weighed, is first 1 by water and hydrochloric acid volume ratio：1 dilutes excellent pure grade salt, obtains hydrochloric acid solution D, salt Acid uses the top grade pure hydrochloric acid of ρ=1.19g/ml；10ml hydrochloric acid solution D is added into every part of rafifinal again, after vigorous reaction, 1ml nitric acid solution is added, nitric acid is all made of the excellent pure grade of ρ=1.42/ml, obtains 6 parts of substrate solutions；First respectively to every part of base Manganese standard solution 1ml, nickel standard solution 1ml, iron Standard Stock solutions 1ml, copper Standard Stock solutions are added in the solution of bottom Then 2.2ml, magnesium standard solution 1.5ml, zirconium standard solution 1ml are separately added into lead, tin, bismuth standard into six parts of substrate solutions Solution, lead, tin, bismuth standard solution volume are identical, successively by six kinds of volumes 0ml, 1ml, 2ml, 5ml, 10ml, 20ml respectively to base Lead, tin, bismuth standard solution are added in the solution of bottom, then moves into 100ml volumetric flask, scale is diluted to water, mixes.
This serial lead, tin, bismuth calibration curve solution in the mass concentration of each element be equivalent to each element quality in sample Score.The method for drawing working curve solution using three kinds of different preparations, is carried out on instrument with this series standard curve solution Spectroscopic assay, measure element hair intensity of emission spectra, using it as Y-axis, lead, tin, bismuth mass fraction be X-axis make linear regression. And the standard curve drawn using three kinds of methods is measured the mass fraction of lead in same sample, tin, bismuth, measures standard song Lead in line solution, tin, bismuth element mass fraction be shown in Table 5.
5 three kinds of methods of table measure the mass fraction of lead in same sample, tin, bismuth
As can be seen from the above table：
The linear coefficient that calibration curve solution that three kinds of methods prepare draws standard curve is all very considerable, but with different The standard curve that method bottoming is depicted as but makes a world of difference to the measurement result of sample.This is because when drawing standard curve, There are the inconsistent caused of constituent content for solution used in standard curve and sample.
Standard sample LD7 bottoming used in method one is depicted as standard curve, although LD7 and LD7-4 each element content It is almost the same, but LD7 does not provide the standard content of lead, tin, bismuth, can be seen by the content of measurement sample lead, tin, bismuth Out, for the content of lead and tin higher than the content of lead and tin in sample, leading to final measurement result is negative value in standard specimen LD7.
It is 99.99% or more rafifinal bottoming that method two, which uses mass fraction, is not had in solution used in standard curve There is the interference of other components, and contain other components in solution to be measured, there is interference, and then affect measurement result.
The rafifinal additional element bottoming that method three is 99.99% or more using mass fraction, the group with sample to be tested Point content is consistent, and measurement result is closest to true value.
Finally, it selects Matrix phase to prepare substrate solution, i.e., is added using the rafifinal that mass fraction is 99.99% or more Alloying element bottoming.
(3) accuracy test：
The aluminium alloy LD7-4 standard sample of actual concentrations known to 10 parts is weighed, every part of 0.1000g is separately added into thereto A certain amount of lead, tin, bismuth do recovery test, the rafifinal bottoming for the use of mass fraction being 99.99%, draw after additional element The method of standard curve processed is detected, testing result such as table 6.
The measurement result of certain standard sample after certain element to be measured is added in table 6
(4) precision test
10 parts of aluminium alloy LD7-4 standard samples are weighed, the rafifinal bottoming for the use of mass fraction being 99.99%, adduction gold The working curve drawn after element is detected, and lead, tin, bi content are measured, and calculating average value, standard deviation, relative standard are inclined Difference the results are shown in Table 7.
The repetitive test measurement result of 7 standard sample of table
(5) method detection limit
Using the standard curve established, 8 measurements are carried out to blank solution, using 3 times of standard deviation as this method Detection limit is shown in Table 8.
The measurement result of 8 blank test of table
The present invention, which is realized, exists to lead, tin, bi content in LD7-4 material with inductively coupled plasma emission spectrography 0.01% measurement below, and the rate of recovery of lead, tin, bismuth is between 96%~105%；Detection is limited to Pb：0.00042mg, Bi：0.00039mg, Sn：0.00042mg, RSD are followed successively by：Pb：0.0104%, Bi：0.0080%, Sn：0.0103%.
Sample pretreatment process of the present invention is simple, and easy to operate quickly accuracy rate is high, is suitble to batch detection, solves inspection The technical issues of surveying present in work to microelement Accurate Determining.

Claims (6)

  1. The method that 1.ICP-OES method measures lead, tin, bi content in aluminium alloy, which is characterized in that specifically implement according to the following steps：
    Step 1, according to method as defined in GB/T602, prepare the lead standard solution, tin standard solution, bismuth standard of isoconcentration respectively The manganese standard solution of solution and isoconcentration, nickel standard solution, iron standard solution, copper standard solution, magnesium standard solution, zirconium standard are molten Liquid；
    Step 2 weighs the rafifinal that n parts of mass fractions are 99.99% or more as matrix original pattern, and wherein n is not less than 5；First Hydrochloric acid solution, nitric acid solution are sequentially added into n parts of described matrix original patterns, is prepared into solution A respectively1, solution A2... solution An, then to the solution A1, solution A2... solution AnEvery portion in that the manganese standard solution of isoconcentration, nickel standard is added is molten Liquid, iron standard solution, copper standard solution, magnesium standard solution, zirconium standard solution, respectively obtain solution B1, solution B2... solution Bn, then to solution B1, solution B2... solution BnIt is every portion in be added suitable gradient isoconcentration lead standard solution, tin mark Quasi- solution, bismuth standard solution, obtain calibration curve solution C1, calibration curve solution C2... ... calibration curve solution Cn；
    Step 3, using inductive coupling plasma emission spectrograph to calibration curve solution C1, solution C2... ... solution CnIt carries out Detection, obtains the intensity of emission spectra of each calibration curve solution, inductive coupling plasma emission spectrograph is respectively with each standard Lead in curve solution, tin, bismuth concentration be abscissa, with the emission spectrum of lead, tin and bismuth in each calibration curve solution of measurement Intensity is that ordinate draws out working curve automatically, wherein the analysis spectral line for measuring the lead of selection is 220.353nm, point of tin Analysis spectral line is 189.927nm, and the analysis spectral line of bismuth is 190.171nm；
    Hydrochloric acid solution D is first added into aluminium alloy LD7-4 sample in step 4, to after the reaction was completed, then presses the volume of hydrochloric acid solution D It is 10 with the ratio between nitric acid solution volume:1~15:1 is added nitric acid solution, prepares the solution to be measured of aluminium alloy LD7-4 sample；
    Step 5 detects the solution to be measured that step 4 obtains with the same determination condition of step 3, measures in test solution The intensity of emission spectra of lead, tin and bismuth obtains lead in test solution, tin and bismuth according to the working curve diagram of calibration curve solution Concentration.
  2. 2. according to the method for lead, tin, bi content in ICP-OES method measurement aluminium alloy as stated in claim 1, feature exists In the concrete operation step of step 2 is as follows：
    Step 2.1 weighs the rafifinal that n parts of mass fractions are 99.99% or more, is respectively placed in n container；
    Step 2.2 by water and hydrochloric acid volume ratio is 1:1~2:1 dilutes excellent pure grade hydrochloric acid solution, obtains n parts of hydrochloric acid solution D, Wherein top grade pure hydrochloric acid density is 1.19g/ml；
    Step 2.3, by the ratio between the quality of rafifinal and hydrochloric acid solution D volume be 1:100~1:300 are added into each container The hydrochloric acid solution D of equivalent reacts with rafifinal completion to hydrochloric acid solution D, obtains n parts of solution Es；
    The ratio between step 2.4, volume and nitric acid solution volume for pressing hydrochloric acid solution D again are 10:1~30:1 is equal into every part of solution E The nitric acid solution of equivalent is added, is cooled to room temperature after heating, obtains solution A1, solution A2... solution An, wherein nitric acid solution Use density for the excellent pure grade nitric acid solution of 1.42/ml；
    Step 2.5, to solution A1, solution A2... solution AnIn be separately added into the manganese standard solution of isoconcentration, nickel standard solution, Iron standard solution, copper standard solution, magnesium standard solution, zirconium standard solution, concentration are 1000 μ g/ml, and the amount of addition is can be controlled in In certain range：50 μ L of μ L~200 of manganese standard solution, nickel standard solution 1.0mL~1.4mL, iron standard solution 0.9mL~ 1.2mL, copper standard solution 2.1mL~2.7mL, magnesium standard solution 1.3mL~1.7mL, the 10 μ L of μ L~50 of zirconium standard solution, obtain Solution B1, solution B2... solution Bn, wherein n is not less than 5；
    Step 2.6, again to solution B1, solution B2... solution BnIn by suitable gradient be added isoconcentration lead standard solution, Tin standard solution, bismuth standard solution, concentration 0.01mg/ml, solution B1Lead standard solution, the tin standard solution, bismuth of middle addition The volume of standard solution is identical, solution B2The volume phase of the lead standard solution of middle addition, tin standard solution, bismuth standard solution Solution B together ... ...nThe lead standard solution of middle addition, tin standard solution, the volume of bismuth standard solution are identical.It is marked after constant volume Directrix curve solution C1, calibration curve solution C2... calibration curve solution Cn, wherein n is not less than 5.
  3. 3. according to the method for lead, tin, bi content in ICP-OES method measurement aluminium alloy described in claim requirement 2, feature exists In the heating condition of the step 2.4 is：It is heated to sample using 80-120 DEG C to be completely dissolved, then will be molten using 150-200 DEG C It is clean that liquid heating drives away nitrogen oxides.
  4. 4. according to the method for lead, tin, bi content in ICP-OES method measurement aluminium alloy as stated in claim 1, feature exists In the concrete operation step of the step 4 is as follows：
    Step 4.1 weighs aluminium alloy LD7-4 sample, is placed in container；
    Step 4.2 by water and hydrochloric acid volume ratio is 1:1~2:1 dilutes excellent pure grade hydrochloric acid solution, obtains hydrochloric acid solution D；
    The ratio between step 4.3, the hydrochloric acid solution D volume obtained by the quality of aluminium alloy LD7-4 and through step 2.3 are 1:100~1: 300 hydrochloric acid solution D is added into container, reacts to hydrochloric acid solution D with the completion of aluminium alloy LD7-4 sample, obtains solution F；
    Step 4.4 is 10 by the ratio between the volume of hydrochloric acid solution D and nitric acid solution volume:1~30:1 is added nitric acid into solution F Solution, after be cooled to room temperature, solution to be measured is obtained after constant volume, the volume of constant volume is identical as step 2.6, wherein nitric acid solution use Density is the excellent pure grade nitric acid solution of 1.42/ml.
  5. 5. according to the method for lead, tin, bi content in ICP-OES method measurement aluminium alloy described in claim requirement 4, feature exists In the condition of the heating of the step 4.4 is：Sample is heated to using 80-120 DEG C to be completely dissolved, then is incited somebody to action using 150-200 DEG C Solution heating drives away nitrogen oxides clean.
  6. 6. according to the method for lead, tin, bi content in ICP-OES method measurement aluminium alloy as stated in claim 1, feature exists In the running parameter of inductive coupling plasma emission spectrograph is in the step 3：Atomization gas flow 0.8L/min, observation Distance is 15mm, high frequency power 1300W, secondary air amount 0.2L/min, plasma flow 15L/min, sample flow Measure 1.50mL/min.
CN201810545711.5A 2018-05-25 2018-05-25 The method that ICP-OES method measures lead, tin, bi content in aluminium alloy Pending CN108872195A (en)

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