CN103424399B - Analytic method for simultaneously determining percentage content of nine impurity elements in titanium sponge - Google Patents
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Abstract
The invention discloses an analytic method for simultaneously determining the percentage content of nine impurity elements in titanium sponge. The nine impurity elements are Sn, As, Sb, Cr, Cu, V, Ni, Zn and Nb, five types of working curve standard solutions containing the nine impurity elements are prepared through a ti-based solution and a related reference solution, under the premise of determining the working parameters of the atomic emission spectrometer of an inductively coupled plasma, scanning is respectively performed on the five types of working curve standard solutions and a to-be-detected solution of titanium sponge, related spectral lines are selected as analysis spectral lines and background correction is performed on the analysis spectral lines, all related coefficients are higher than 0.995, detection limits are all below 0.00040 percent, except several analysis spectral lines of which the relative standard deviation is below 20 percent, the relative standard deviation of other analysis spectral lines are all below 10 percent, the requirements of a common micro trace analysis are met, the method provided by the invention can meet the requirements of analysis to the percentage content of the nine impurity elements in the titanium sponge, recovery tests show that the method is feasible, and a basis for quality grade of titanium sponge is provided.
Description
Technical field
The invention belongs to chemical element determination techniques field, especially the analytical approach of nine kinds of impurity element percentage compositions in Simultaneously test titanium sponge, described nine kinds of impurity elements really refer to for tin Sn, arsenic As, antimony Sb, chromium Cr, copper Cu, vanadium V, nickel, zinc Zn, niobium Nb.
Background technology
Titanium sponge is used widely as the raw material producing titanium or titanium alloy, but such as the content of Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb of impurity element wherein directly has influence on the performance of titanium or titanium alloy, the height of titanium sponge purity also reduces its taste because of the existence of these impurity elements.If the percentage composition of titanium in titanium sponge can be detected, also adding and result of all impurity element percentage compositions in titanium sponge can be estimated, but because of titanium in titanium sponge detection method existing for error can't meet at present titanium sponge purity differentiate demand, for titanium sponge purity detection still by removal titanium sponge in adding of impurity element judge with total amount.Each titanium sponge production producer also just carries out analysis and control according to the major impurity element of Fe in GB/T 4698 pairs of titanium sponges, Si, Mn, Mg, Cl, C, N, H, O at present, impurities analysis comprehensively by directly causing the erroneous judgement of titanium sponge grade or directly having influence on the technique of titanium alloy and goods thereof, processing and properties of product, is not therefore made express-analysis to the percentage composition of the nine kinds of impurity elements of Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb in titanium sponge and is just seemed particularly important.
To the impurities analysis standard in titanium sponge be at present: GB GB/T 4698 and U.S. ASTM standard E1447-09, E1941-10, E1409-08 and E2371-04.GB GB/T 4698.1-4698.25-1996, GB/T 4698.7.14.15-2011 have respectively provided the analytical approach of Cu, Fe, Si, Mn, Mo, B, N, Al, Sn, Cr, V, Zr, Y, Nb, Pd, Ni, Cl, Mg, C, H, O element in titanium sponge, titanium or titanium alloy, and E1447-09, E1941-10, E1409-08 and E2371-04 have respectively provided the analytical approach of H, C, O, Al, B, Cr, Cu, Fe, Mn, Mo, Ni, Si, Sn, V, Y, Zr element in titanium or titanium alloy.
Above-mentioned standard Problems existing is:
1, GB and American Standard all do not specify the analysis of As, Sb, Zn in titanium sponge;
2, the analyst coverage of GB and American Standard can not meet the demand of microscratch amount impurities analysis in titanium sponge, as:
(1), for the mensuration of tin, GB/T 4698.1-96 adopts Potassiumiodate titration measuring tin amount, and test specification is 1 ~ 12%; GB/T 4698.18-96 adopts Flame Atomic Absorption Spectrometry Determination tin amount, and test specification is 1 ~ 5%; These two kinds of assay methods cannot measure for the titanium sponge of Theil indices below 0.10%.
(2), for the mensuration of vanadium, GB/T 4698.12-96 adopts ferrous ammonium sulfate titration vanadium amount, and test specification is 1 ~ 15%, cannot measure for the vanadium of content of vanadium below 0.10%.
(3), for the mensuration of chromium, GB/T 4698.10-96 and GB/T 4698.11-96 adopts ferrous ammonium sulfate titration chromium amount, and test specification is all 0.3-12%, cannot measure for the chromium of chromium content below 0.10%.
(4), for the mensuration of niobium, nickel, aluminium etc., the method testing scope that GB/T 4698 specifies is respectively: Nb 0.20 ~ 3.0%, Ni 0.20 ~ 3.0%, 0.80 ~ 8.0%, all can not meet the analysis demand of low content niobium, nickel, aluminium in titanium sponge.
(5) GB/T 4698.21-96 adopts direct-current arc emission spectrographic determination, wherein also there is Ni, Cr, Sn, the analysis of Cu, but because of its operation steps numerous and diverse and need by the test portion handled well and carbon dust by a certain percentage the even rear pressure brimmer shape carbon electrode of mixer mill carry out spectrographic analysis, standard give method linear analysis narrow range, analyst coverage is Ni 0.02 ~ 0.2% respectively, Cr 0.02 ~ 0.2%, Sn 0.01 ~ 0.15%, Cu0.01 ~ 0.15%, for the Ni being less than 0.02%, Cr and be less than 0.01% Sn, Cu and be greater than 0.2% Ni, Cr and be greater than 0.15% Sn, Cu cannot measure, also the application of GB/T 4698.21-96 is made to be subject to a definite limitation.
The test specification of American Standard ASTM is respectively Al0.001 ~ 8.0%, Cr 0.005 ~ 4.0 %, Cu 0.002 ~ 0.5%, Fe 0.004 ~ 3.0%, Ni 0.001 ~ 1.0%, Si 0.02 ~ 0.4%, Sn 0.02 ~ 3.0%, V0.01 ~ 15.0%, analyst coverage for titanium or titanium alloy fixed, but cannot measure for the Sn being less than 0.02%, in American Standard, not specify the method for testing of As, Sb, V, Zn, Nb.
The analyst coverage of Cr, Cu, Ni element with reference to employing, because not providing specific works parameter and detailed analysis details in American Standard, and can not provide detailed Instrument working parameter, causing using although can meet the demands in American Standard.
3, namely analysis speed needs to measure respectively each element slowly, and step is many, and analytical cycle is long.
Relevant report is yet there are no by the analytical approach of Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb nine kinds of impurity element percentage compositions in same tester Simultaneously test titanium sponge.
Summary of the invention
For solving Sn in titanium sponge, As, Sb, Cr, Cu, V, Ni, Zn, Nb nine kinds of impurity elements Rapid Simultaneous Determination problem under same tester, the invention provides the analytical approach of nine kinds of impurity element percentage compositions in a kind of Simultaneously test titanium sponge, this analytical approach is prepared by titanium based sols, each standard reserving solution preparation of nine kinds of impurity elements, each titer preparation of nine kinds of impurity elements, the mixing mark liquid preparation of nine kinds of impurity elements, and then prepare five kinds of corresponding working curve titers, under the running parameter condition determining inductively coupled plasma atomic emission spectrometer, five kinds of working curve titers and titanium sponge liquid to be measured are scanned respectively, selected analysis spectral line also carries out background correction to it, nine of five kinds of working curve titers kinds of impurity element spectral line of emission intensity are established corresponding working curve with its concentration value and obtains each side's method linear equation, by measuring the spectral line of emission intensity of titanium sponge liquid to be measured, inductively coupled plasma atomic emission spectrometer can calculate the percentage composition of nine kinds of impurity elements in titanium sponge automatically, perfect GB and ASTM standard, for the quality grade dividing titanium sponge provides reference frame.
For achieving the above object, the present invention adopts following technical scheme:
An analytical approach for nine kinds of impurity element percentage compositions in Simultaneously test titanium sponge, described nine kinds of impurity elements really refer to for Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb, the reagent used in this analytical approach and test articles for use mainly contain hydrofluorite, nitric acid, distilled water, hydrochloric acid, sulfuric acid, high purity titanium, purity Metal Tin, arsenic trioxide, high purity antimony, High Pure Chromium, high purity copper, high purity vanadium metal, high purity nickel, high purity zinc, High-purity Niobium, King beaker, plastics volumetric flask, beaker, electric furnace, volumetric flask, the tester used is inductively coupled plasma atomic emission spectrometer, and this analytical approach is prepared by titanium based sols, each standard reserving solution preparation of described nine kinds of impurity elements, each titer preparation of described nine kinds of impurity elements, be respectively the mixing mark liquid preparation of 1 μ g/mL containing described nine kinds of impurity elements, determine the blank working curve titer preparation of 0.00 μ g/mL, prepared by the working curve titer a being respectively 0.01 ~ 0.08 μ g/mL containing described nine kinds of impurity elements, prepared by the working curve titer b being respectively 1.00 ~ 3.00 μ g/mL containing described nine kinds of impurity elements, prepared by the working curve titer c being respectively 4.00 ~ 8.00 μ g/mL containing described nine kinds of impurity elements, the molten d preparation of working curve standard of 10.00 ~ 20.00 μ g/mL is containing Sn and Cu, under the running parameter prerequisite determining inductively coupled plasma atomic emission spectrometer, above-mentioned five kinds of working curve titers and titanium sponge liquid to be measured are scanned respectively, select each analysis spectral line of described nine kinds of impurity elements and background correction is carried out to it, the spectral line of emission intensity of above-mentioned five kinds of working curve titers and its concentration value are set up working curve and obtains method linear equation, measure the titanium sponge prepared liquid to be measured, inductively coupled plasma atomic emission spectrometer can calculate the percentage composition of nine kinds of impurity elements described in titanium sponge automatically, above-mentioned each correlated process is described below:
prepared by titanium based sols
Take 1.0000g purity be the high purity titanium of 99.99% and be placed in the King beaker of 250mL, the hydrochloric acid that 15.00mL mass concentration is 36.0 ~ 38.0% is added again with after a small amount of distilled water flushing King beaker, dropwise being added in King beaker by the hydrofluorite of 5.00 ~ 10.00mL mass concentration >=40.0% makes high purity titanium be dissolved, instill in King beaker again after high purity titanium dissolves 1.00 ~ 4.00mL mass concentration be 65.0 ~ 68.0% nitric acid make it clarify and be cooled to room temperature to move in the plastics volumetric flask of 100mL again, clean King beaker at least three times with distilled water and pour in plastics volumetric flask and be settled to the titanium based sols that 100mL prepares titaniferous 10mg/mL,
each standard reserving solution preparation of described nine kinds of impurity elements
Take the high-purity Sn of 1.0000g and be placed in 250mL beaker and add the hydrochloric acid that 100.00mL mass concentration is 36.0 ~ 38.0%, beaker is placed in and electric furnace carries out heating and boil Sn is dissolved, dissolve the complete beaker that takes off be cooled to room temperature and move in 1000mL volumetric flask, be settled to 1000mL with distilled water cleaning beaker at least three times pouring in volumetric flask and prepare Sn standard reserving solution containing Sn1mg/mL;
Take 1.3203g arsenic trioxide and be placed in 250mL beaker and add the hydrochloric acid that 50.00mL mass concentration is 36.0 ~ 38.0%, beaker is placed in and electric furnace carries out heating and boil arsenic trioxide is dissolved, dissolve the complete beaker that takes off be cooled to room temperature and move in 1000mL volumetric flask, be settled to 1000mL with distilled water cleaning beaker at least three times pouring in volumetric flask and prepare As standard reserving solution containing As1mg/mL;
Take the high-purity Sb of 1.0000g and be placed in 250mL beaker and add 15.00mL mass concentration be 36.0 ~ 38.0% hydrochloric acid and 5.00mL mass concentration be the nitric acid of 65.0 ~ 68.0%, beaker is placed in and electric furnace carries out heating and boil Sb is dissolved, dissolve complete taking off after beaker is cooled to room temperature and add the hydrochloric acid that 35.00mL mass concentration is 36.0 ~ 38.0% again, move into afterwards in 1000mL volumetric flask, pour in volumetric flask and be settled to 1000mL with distilled water cleaning beaker at least three times and prepare Sb standard reserving solution containing Sb1mg/mL;
Take the high-purity Cr of 1.000g and be placed in 250mL beaker and add the hydrochloric acid that 50.00mL mass concentration is 36.0 ~ 38.0%, beaker is placed in and electric furnace carries out heating and boil Cr is dissolved, dissolve the complete beaker that takes off be cooled to room temperature and move in 1000mL volumetric flask, be settled to 1000mL with distilled water cleaning beaker at least three times pouring in volumetric flask and prepare Cr standard reserving solution containing Cr1mg/mL;
Take the high-purity Cu of 1.0000g and be placed in 250mL beaker and add 50.00mL distilled water and 50.00mL mass concentration is the nitric acid of 65.0 ~ 68.0%, beaker is placed in and electric furnace carries out heating and boil Cu is dissolved, dissolve the complete beaker that takes off be cooled to room temperature and move in 1000mL volumetric flask, be settled to 1000mL with distilled water cleaning beaker at least three times pouring in volumetric flask and prepare Cu standard reserving solution containing Cu1mg/mL;
In like manner, 1000mL can also be prepared respectively with reference to said process: the V standard reserving solution containing V1mg/mL, the Ni standard reserving solution containing Ni1mg/mL and the Zn standard reserving solution containing Zn1mg/mL;
Take 1.0000g high-purity N b and be placed in 250mL King beaker and dropwise add the hydrofluorite of 5.00mL mass concentration >=40.0%, dropwise add the nitric acid that 2.00mL mass concentration is 65.0 ~ 68.0% again, dissolve complete until Nb and move into when being cooled to room temperature in 1000mL volumetric flask, clean King beaker at least three times with distilled water and pour in volumetric flask and be settled to 1000mL, move in plastic bottle the Nb standard reserving solution prepared containing Nb1mg/mL afterwards;
each titer preparation of described nine kinds of impurity elements
Sn standard reserving solution described in 10.00mL be placed in 100mL volumetric flask and add the hydrochloric acid that 10.00mL mass concentration is 36.0 ~ 38.0%, in volumetric flask, then adding distilled water be settled to the Sn titer that 100mL prepares stanniferous 100 μ g/mL;
In like manner, each 100mL can also be prepared with reference to said process: the As titer containing As100 μ g/mL, the Sb titer containing Sb100 μ g/mL, the Cr titer containing Cr100 μ g/mL, the Cu titer containing Cu100 μ g/mL, the V titer containing V100 μ g/mL, the Ni titer containing Ni100 μ g/mL, the Zn titer containing Zn100 μ g/mL and the Nb titer containing Nb100 μ g/mL;
the mixing mark liquid preparation of 1 μ g/mL is respectively containing described nine kinds of impurity elements
Described Sn standard reserving solution, described As standard reserving solution, described Sb standard reserving solution, described Cr standard reserving solution, described Cu standard reserving solution, described V standard reserving solution, described Ni standard reserving solution, described Zn standard reserving solution and described Nb standard reserving solution are respectively pipetted 1.00mL together to be joined in the plastics volumetric flask of 100mL, add the hydrochloric acid that 10.00mL mass concentration is 36.0 ~ 38.0% again, be settled to 100mL with distilled water and prepare the mixing mark liquid A being respectively 10 μ g/mL containing described nine kinds of impurity elements;
Mixing mark liquid A described in 10.00mL is placed in 100mL plastics volumetric flask and adds the hydrochloric acid that 10mL mass concentration is 36.0 ~ 38.0%, in plastics volumetric flask, then adds distilled water be settled to 100mL and prepare the mixing mark liquid being respectively 1 μ g/mL containing described nine kinds of impurity elements;
the blank working curve titer preparation of 0.00 μ g/mL
By 4.00 ~ 8.00mL mass concentration 95.0% ~ 98.0% sulfuric acid join and add distilled water and be about in the 100mL plastics volumetric flask of 30mL, to be cooledly to room temperature, be settled to 100mL with distilled water prepare the blank working curve titer of 0.00 μ g/mL;
prepared by the working curve titer a being respectively 0.01 ~ 0.08 μ g/mL containing described nine kinds of impurity elements
The mixing mark liquid of 1.00 ~ 8.00mL and the titanium based sols of 10.00 mL are together joined in 100mL plastics volumetric flask, add again 4.00 ~ 8.00mL mass concentration 95.0 ~ 98.0% sulfuric acid, after being cooled to room temperature, being settled to 100mL with distilled water and preparing the working curve titer a being respectively 0.01 ~ 0.08 μ g/mL containing described nine kinds of impurity elements;
prepared by the working curve titer b being respectively 1.00 ~ 3.00 μ g/mL containing described nine kinds of impurity elements
Get described Sn titer, described As titer, described Sb titer, described Cr titer, described Cu titer, described V titer, described Ni titer, described Zn titer, each 1.00 ~ 3.00mL of described Nb titer and 10.00 mL titanium based sols together join in 100mL plastics volumetric flask, add the sulfuric acid that 4.00 ~ 8.00mL mass concentration is 95.0 ~ 98.0% again, to be cooledly to room temperature, be settled to 100mL with distilled water prepare the working curve titer b being respectively 1.00 ~ 3.00 μ g/mL containing described nine kinds of impurity elements;
prepared by the working curve titer c being respectively 4.00 ~ 8.00 μ g/mL containing described nine kinds of impurity elements
Get described Sn titer, described As titer, described Sb titer, described Cr titer, described Cu titer, described V titer, described Ni titer, described Zn titer, each 4.00 ~ 8.00mL of described Nb titer and 10.00 mL titanium based sols together join in 100mL plastics volumetric flask, add the sulfuric acid that 4.00 ~ 8.00mL mass concentration is 95.0 ~ 98.0% again, to be cooledly to room temperature, be settled to 100mL with distilled water prepare the working curve titer c being respectively 4.00 ~ 8.00 μ g/mL containing described nine kinds of impurity elements;
the molten d preparation of working curve standard of 10.00 ~ 20.00 μ g/mL is containing Sn and Cu
The titanium based sols getting described Sn standard reserving solution and each 1.00 ~ 2.00mL of described Cu standard reserving solution and 10.00 mL together joins in 100mL plastics volumetric flask, add the sulfuric acid that 4.00 ~ 8.00mL mass concentration is 95.0 ~ 98.0% again, to be cooledly to room temperature, be settled to 100mL with distilled water prepare the working curve titer d being 10.00 ~ 20.00 μ g/mL containing Sn and Cu;
the preparation of titanium sponge liquid to be measured
Take the titanium sponge of 0.0900 ~ 0.3000g and be placed in the dual-purpose bottle of 100mL, with distilled water flushing bottle wall, add the sulfuric acid that 4.00 ~ 8.00mL mass concentration is 95.0 ~ 98.0%, after titanium sponge heating for dissolving, drip 1 ~ 5 mass concentration be again the nitric acid of 65.0 ~ 68.0% and with distilled water flushing bottle wall, take off dual-purpose bottle time tranquil until limpid by the above-mentioned solution heated in dual-purpose bottle, liquid level and after being cooled to room temperature, be settled to 100mL and prepare titanium sponge liquid to be measured;
the running parameter of inductively coupled plasma atomic emission spectrometer is determined and analysis spectral line is determined
The running parameter determination scope of inductively coupled plasma atomic emission spectrometer is as follows:
Inductive coupling plasma emission spectrograph optimum working parameter scope: power: 1.00 ~ 1.35KW; Plasma flow amount: 14 ~ 16L/min; Assisted gas flow: 0.15 ~ 0.40L/min; Atomization gas flow: 0.60 ~ 0.85L/min; Sample wash flow: 1.3 ~ 1.6 mL/min; Light stability time delay: 15 ~ 23s; Sample promotes time: 15 ~ 21s; The sample wash time: 5 ~ 20s; Duplicate measurements number of times: 1 ~ 3 time;
Time from element spectral line table, select many spectral lines of Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb element in advance, scan respectively described blank working curve titer, described working curve titer a, described working curve titer b, described working curve titer c, described working curve titer d and titanium sponge liquid to be measured respectively with selected spectral line, the interference result that scanning produces is summarized as follows:
Sn189.927 nm analysis spectral line is subject to the interference of Os189.950 nm, Ti189.975 nm and W189.987 nm;
Sn242.170 nm analysis spectral line is subject to the interference of Ti242.130 nm;
As197.197 nm analysis spectral line is subject to the interference of Ti197.200 nm and W197.313 nm;
As193.696 nm analysis spectral line is subject to the interference of Cr193.696 nm, V193.684 nm, Fe193.668 nm and Fe193.619 nm;
As188.979 nm analysis spectral line is subject to the interference of As188.984 nm;
Sb217.582 nm analysis spectral line is subject to the interference of Zr217.582 nm, Re217.621 nm and Ni217.515 nm;
Sb231.146 nm analysis spectral line is subject to the interference of V231.146 nm, Nb231.146 nm, Nb231.168 nm, Ni231.223 nm, Ag231.241 nm and Ni231.096 nm;
Cr283.563 nm analysis spectral line is subject to the interference of U283.557 nm and Ti283.660 nm;
Cr 267.716 nm analysis spectral line is subject to the interference of Mn267.785 nm;
Cu327.393 nm analysis spectral line is subject to the interference of Co327.393 nm, Ce327.393 nm, Ti327.405 nm, Ti327.440 nm, Nb327.479 nm Th327.507 nm, Ti327.529 nm and Sm327.348 nm;
Cu224.700 nm analysis spectral line is subject to the interference of Mo224.711 nm and Sn224.606 nm;
V292.464 nm analysis spectral line is subject to the interference of Zr292.464 nm, Fe292.399 and U292.350 nm;
V310.230 nm analysis spectral line is subject to the interference of Fe310.214 nm, Fe310.236 nm, Gd310.255 nm, Ti310.298 nm, Cr310.347 nm and Ti310.153 nm;
V292.402 analysis spectral line is subject to the interference of Si292.401 nm, Rh292.402 nm, W292.354 nm, V292.464 nm and Ti292.292 nm;
Ni231.604 nm analysis spectral line is subject to the interference of Ta231.604 nm and Ti231.598 nm;
Ni231.003 nm analysis spectral line is subject to the interference of Nb232.024 nm, Ni231.976 nm and Zr232.080 nm;
Zn206.200nm analysis spectral line is subject to the interference of V206.200 nm, Os206.169 nm and V206.156 nm;
Zn213.857nm analysis spectral line is subject to the interference of Hf213.857 nm, Ti213.836 nm, Ti213.925 nm and Ti213.787 nm;
Zn202.548nm analysis spectral line is subject to the interference of Cu202.548 nm, Nb202.531 nm and Os202.512 nm;
Nb309.418nm analysis spectral line is subject to the interference of V309.419 nm, Sn309.469 nm, Cr309.549 nm and V309.310 nm;
Nb269.706nm analysis spectral line is subject to the interference of Ta269.830 nm and Mn269.596 nm;
Can differentiate out in conjunction with spectrogram situation, annoyance level, Interference Peaks, the test comparison situation of signal-to-background ratio situation and each working curve titer containing described nine kinds of impurity elements, the analysis spectral line that final selected following spectral line is nine kinds of impurity elements described in titanium sponge:
Sn-242.170nm and Sn-189.927nm;
As-193.696nm and As-188.979nm;
Sb—217.582nm；
Cr—283.563nm；
Cu-327.393nm and Cu-224.700nm;
V-292.464nm and V-292.402nm;
Ni-231.604nm and Ni-232.003nm;
Zn-206.200nm, Zn-213.857nm and Zn-202.548nm;
Nb-309.418nm and Nb-269.706nm;
analyze the interference correction measured
The Physical Interference existed in measuring described nine kinds of impurities analysis adopts Matrix phase to eliminate, and adopts peg method to eliminate to its spectra1 interfer-, and the background correction point adopted above-mentioned selected each analysis spectral line is as follows:
Sn242.170nm background correction point is: BGC
1for-0.075nm, BGC
2for+0.039nm;
Sn189.927nm background correction point is: BGC
1for-0.033nm, BGC
2for+0.069nm;
As193.696nm background correction point is: BGC
1for-0.048nm, BGC
2for+0.063nm;
As188.979nm background correction point is: BGC
1for-0.043nm, BGC
2for+0.069nm;
Sb217.582nm background correction point is: BGC
1for-0.089nm, BGC
2for+0.020nm;
Cr283.563nm background correction point is: BGC
1for-0.063nm, BGC
2for+0.043nm;
Cu327.393nm background correction point is: BGC
1for-0.070nm, BGC
2for+0.070nm;
Cu 224.700nm background correction point is: BGC
1for-0.065nm, BGC
2for+0.071nm;
V292.464nm background correction point is: BGC
1for-0.030nm, BGC
2for+0.091nm;
V 292.402nm background correction point is: BGC
1for-0.064nm, BGC
2for+0.103nm;
Ni231.604nm background correction point is: BGC
1for-0.056nm, BGC
2for+0.039nm;
Ni 232.003nm background correction point is: BGC
1for-0.078nm, BGC
2for+0.048nm;
Zn206.200nm background correction point is: BGC
1for-0.079nm, BGC
2for+0.043nm;
Zn213.857nm background correction point is: BGC
1for-0.039nm, BGC
2for+0.045nm;
Zn202.548nm background correction point is: BGC
1for-0.067nm, BGC
2for+0.023nm;
Nb309.418nm background correction point is: BGC
1for-0.095nm, BGC
2for+0.071nm;
Nb269.706nm background correction point is: BGC
1for-0.050nm, BGC
2for+0.029nm;
method linear equation, detection limit and relative standard deviation
Establish corresponding working curve according to the spectral line of emission intensity level of described blank working curve titer, described working curve titer a, described working curve titer b, described working curve titer c and described working curve titer d to its concentration value and obtain method linear equation, then measure titanium sponge liquid to be measured and obtain its each spectral line of emission intensity, inductively coupled plasma atomic emission spectrometer can calculate the percentage composition of nine kinds of impurity elements described in titanium sponge automatically according to described working curve;
Carry out continuous 10 times to described blank working curve titer to measure, the standard deviation mean value measured with 10 times is multiplied by 3 and obtains detection limit;
To the relative standard deviation that titanium sponge liquid replication to be measured obtains for 10 times;
The linear equation that above-mentioned selected each analysis spectral line is corresponding, related coefficient, detection limit, relative standard deviation gather as follows
:
Line wavelength/nm linear equation related coefficient detection limit/% relative standard deviation/%
As 193.696 Y=3545x +87.9 0.999779 0.000134 8.70
As188.979 Y=2269x+241.1 0.999287 0.000331 14.66
Sb217.582 Y=11040x+410.5 0.999873 0.000057 15.55
Sn242.170 Y=4657x+264.3 0.999592 0.000240 15.00
Sn189.927 Y=4583x+468.2 0.999219 0.000127 5.81
Cr283.563 Y=380400x+20712.1 0.999838 0.000016 1.22
Cu327.393 Y=498300x+47297.4 0.999499 0.000008 1.96
Cu224.700 Y=50560x+8450.7 0.998410 0.000018 1.20
V292.464 Y=148400x-148.0 1.00000 0.000021 7.24
V292.402 Y=278100x+93069.3 0.995154 0.000005 0.70
Ni231.604 Y=83580x-21.0 1.00000 0.000017 4.25
Ni232.003 Y=37680x+39.4 0.999987 0.000026 14.91
Zn206.200 Y=54600x+1651.3 0.999906 0.000014 1.06
Zn213.857 Y=190100x+8407.6 0.999625 0.000007 0.74
Zn202.548 Y=79940x+2754.0 0.999859 0.000005 0.66
Nb309.418 Y=423800x+60566.6 0.996553 0.000020 0.51
Nb269.706 Y=111100x+18726.3 0.996539 0.000014 0.48
Owing to adopting technical scheme described above, the present invention has following superiority:
1, the nine kinds of impurity elements of Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb in titanium sponge can be carried out analysis mensuration by analytical approach of the present invention on inductive coupling plasma emission spectrograph simultaneously, simple to operate, analyze fast;
2, analytical approach result of the present invention is accurate, be easy to grasp, accuracy is high, effect is good, after the running parameter of inductively coupled plasma atomic emission spectrometer and analysis spectral line obtain determining, carry out mensuration to each working curve titer can defining method linear equation, then titanium sponge liquid to be measured is carried out analyzing just energy measure and calculation and go out the percentage composition of Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb nine kinds of impurity elements in titanium sponge, save analysis time, research and production needs can be met.
3, detection limit of the present invention is lower, and precision is high, accurately can detect the percentage composition of Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb nine kinds of impurity elements in titanium sponge.
4, GB that analytical approach of the present invention is perfect and ASTM standard can not the problems of Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb nine kinds of impurity contents in Simultaneously test titanium sponge, for the quality grade dividing titanium sponge provides reference frame.
5, all related coefficients of the present invention are all more than 0.995, meet the requirement that conventional method related coefficient is not less than 0.995, all detection limits of the present invention, all below 0.00040%, can meet the needs that micro-trace elements detects, relative standard deviation of the present invention is due to As in titanium sponge liquid to be measured, Sb, Sn, the content of Ni is extremely low, except As188.979nm, Sb217.582nm, Sn242.170nm, Ni232.003nm tetra-analysis spectral line relative standard deviations are below 20%, the relative standard deviation of other element spectral line is all below 10%, meet general Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb microscratch analysis method relative standard deviation is not more than the requirement of 20%, show that the present invention can meet Sn in titanium sponge, As, Sb, Cr, Cu, V, Ni, Zn, the mensuration of Nb nine kinds of impurity element percentage compositions needs.
6, through recovery test, prove that assay method of the present invention is feasible.
Embodiment
The present invention is a kind of analytical approach for nine kinds of impurity element percentage compositions in titanium sponge, described nine kinds of impurity elements really refer to for Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb, GB that this direction method is perfect and ASTM standard can not the problems of Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb percentage composition in Simultaneously test titanium sponge, for the quality grade dividing titanium sponge provides reference frame, have simple to operate, analyze fast, result is accurate, be easy to grasp, the features such as accuracy is high, and effect is good.
The reagent used in analytical approach of the present invention and test articles for use mainly contain hydrofluorite, nitric acid, distilled water, hydrochloric acid, sulfuric acid, high purity titanium, purity Metal Tin, arsenic trioxide, high purity antimony, High Pure Chromium, high purity copper, high purity vanadium metal, high purity nickel, high purity zinc, High-purity Niobium, King beaker, plastics volumetric flask, beaker, electric furnace, volumetric flask, and the tester used is inductively coupled plasma atomic emission spectrometer.
Analytical approach of the present invention is as follows:
Take 1.0000g purity be the high purity titanium of 99.99% and be placed in the King beaker of 250mL, with adding the hydrochloric acid of 15mL mass concentration 36.0 ~ 38.0% after a small amount of distilled water flushing King beaker again, dropwise being added in King beaker by the hydrofluorite of 5 ~ 10mL mass concentration >=40.0% makes high purity titanium be dissolved, instill in King beaker again after high purity titanium dissolves 1 ~ 4mL mass concentration 65.0 ~ 68.0% nitric acid make it clarify and be cooled to room temperature to move in the plastics volumetric flask of 100mL again, clean King beaker at least three times with distilled water and pour in plastics volumetric flask and be settled to the titanium based sols that 100mL prepares titaniferous 10mg/mL.
Take the high-purity Sn of 1.0000g and be placed in 250mL beaker and add the hydrochloric acid that 100.00mL mass concentration is 36.0 ~ 38.0%, beaker is placed in and electric furnace carries out heating and boil Sn is dissolved, dissolve the complete beaker that takes off be cooled to room temperature and move in 1000mL volumetric flask, be settled to 1000mL with distilled water cleaning beaker at least three times pouring in volumetric flask and prepare Sn standard reserving solution containing Sn1mg/mL.
Take 1.3203g arsenic trioxide and be placed in 250mL beaker and add the hydrochloric acid that 50.00mL mass concentration is 36.0 ~ 38.0%, beaker is placed in and electric furnace carries out heating and boil arsenic trioxide is dissolved, dissolve the complete beaker that takes off be cooled to room temperature and move in 1000mL volumetric flask, be settled to 1000mL with distilled water cleaning beaker at least three times pouring in volumetric flask and prepare As standard reserving solution containing As1mg/mL.
Take the high-purity Sb of 1.0000g and be placed in 250mL beaker and add 15.00mL mass concentration be 36.0 ~ 38.0% hydrochloric acid and 5.00mL mass concentration be the nitric acid of 65.0 ~ 68.0%, beaker is placed in and electric furnace carries out heating and boil Sb is dissolved, dissolve complete taking off after beaker is cooled to room temperature and add the hydrochloric acid that 35.00mL mass concentration is 36.0 ~ 38.0% again, move into afterwards in 1000mL volumetric flask, pour in volumetric flask and be settled to 1000mL with distilled water cleaning beaker at least three times and prepare Sb standard reserving solution containing Sb1mg/mL.
Take the high-purity Cr of 1.000g and be placed in 250mL beaker and add the hydrochloric acid that 50.00mL mass concentration is 36.0 ~ 38.0%, beaker is placed in and electric furnace carries out heating and boil Cr is dissolved, dissolve the complete beaker that takes off be cooled to room temperature and move in 1000mL volumetric flask, be settled to 1000mL with distilled water cleaning beaker at least three times pouring in volumetric flask and prepare Cr standard reserving solution containing Cr1mg/mL.
Take the high-purity Cu of 1.0000g and be placed in 250mL beaker and add 50.00mL distilled water and 50.00mL mass concentration is the nitric acid of 65.0 ~ 68.0%, beaker is placed in and electric furnace carries out heating and boil Cu is dissolved, dissolve the complete beaker that takes off be cooled to room temperature and move in 1000mL volumetric flask, be settled to 1000mL with distilled water cleaning beaker at least three times pouring in volumetric flask and prepare Cu standard reserving solution containing Cu1mg/mL.
In like manner, 1000mL can also be prepared respectively with reference to said process: the V standard reserving solution containing V1mg/mL, the Ni standard reserving solution containing Ni1mg/mL and the Zn standard reserving solution containing Zn1mg/mL.
Take 1.0000g high-purity N b and be placed in 250mL King beaker and dropwise add the hydrofluorite of 5.00mL mass concentration >=40.0%, dropwise add the nitric acid that 2.00mL mass concentration is 65.0 ~ 68.0% again, dissolve complete until Nb and move into when being cooled to room temperature in 1000mL volumetric flask, clean King beaker at least three times with distilled water and pour in volumetric flask and be settled to 1000mL, move in plastic bottle the Nb standard reserving solution prepared containing Nb1mg/mL afterwards.
Sn standard reserving solution described in 10.00mL be placed in 100mL volumetric flask and add the hydrochloric acid that 10.00mL mass concentration is 36.0 ~ 38.0%, in volumetric flask, then adding distilled water be settled to the Sn titer that 100mL prepares stanniferous 100 μ g/mL.
In like manner, each 100mL can also be prepared with reference to said process: the As titer containing As100 μ g/mL, the Sb titer containing Sb100 μ g/mL, the Cr titer containing Cr100 μ g/mL, the Cu titer containing Cu100 μ g/mL, the V titer containing V100 μ g/mL, the Ni titer containing Ni100 μ g/mL, the Zn titer containing Zn100 μ g/mL and the Nb titer containing Nb100 μ g/mL.
Described Sn standard reserving solution, described As standard reserving solution, described Sb standard reserving solution, described Cr standard reserving solution, described Cu standard reserving solution, described V standard reserving solution, described Ni standard reserving solution, described Zn standard reserving solution and described Nb standard reserving solution are respectively pipetted 1.00mL together to be joined in the plastics volumetric flask of 100mL, add 10.00mL mass concentration again at the hydrochloric acid of 36.0 ~ 38.0%, be settled to 100mL with distilled water and prepare the mixing mark liquid A being respectively 10 μ g/mL containing described nine kinds of impurity elements.
Mixing mark liquid A described in 10.00mL be placed in 100mL plastics volumetric flask and add 10mL mass concentration at the hydrochloric acid of 36.0 ~ 38.0%, in plastics volumetric flask, then adding distilled water be settled to 100mL and prepare the mixing mark liquid that described nine kinds of impurity elements are respectively 1 μ g/mL.
By 4.00 ~ 8.00mL mass concentration 95.0% ~ 98.0% sulfuric acid join and add distilled water and be about in the 100mL plastics volumetric flask of 30mL, to be cooledly to room temperature, be settled to 100mL with distilled water prepare the blank working curve titer of 0.00 μ g/mL.
The mixing mark liquid of 1.00 ~ 8.00mL and the titanium based sols of 10.00 mL are together joined in 100mL plastics volumetric flask, add again 4.00 ~ 8.00mL mass concentration 95.0 ~ 98.0% sulfuric acid, after being cooled to room temperature, being settled to 100mL with distilled water and preparing the working curve titer a being respectively 0.01 ~ 0.08 μ g/mL containing described nine kinds of impurity elements.
Get described Sn titer, described As titer, described Sb titer, described Cr titer, described Cu titer, described V titer, described Ni titer, described Zn titer, each 1.00 ~ 3.00mL of described Nb titer and 10.00 mL titanium based sols together join in 100mL plastics volumetric flask, add the sulfuric acid that 4.00 ~ 8.00mL mass concentration is 95.0 ~ 98.0% again, to be cooledly to room temperature, be settled to 100mL with distilled water prepare the working curve titer b being respectively 1.00 ~ 3.00 μ g/mL containing described nine kinds of impurity elements.
Get described Sn titer, described As titer, described Sb titer, described Cr titer, described Cu titer, described V titer, described Ni titer, described Zn titer, each 4.00 ~ 8.00mL of described Nb titer and 10.00 mL titanium based sols together join in 100mL plastics volumetric flask, add the sulfuric acid that 4.00 ~ 8.00mL mass concentration is 95.0 ~ 98.0% again, to be cooledly to room temperature, be settled to 100mL with distilled water prepare the working curve titer c being respectively 4.00 ~ 8.00 μ g/mL containing described nine kinds of impurity elements.
The titanium based sols getting described Sn standard reserving solution and each 1.00 ~ 2.00mL of described Cu standard reserving solution and 10.00 mL together joins in 100mL plastics volumetric flask, add the sulfuric acid that 4.00 ~ 8.00mL mass concentration is 95.0 ~ 98.0% again, to be cooledly to room temperature, be settled to 100mL with distilled water prepare the working curve titer d being 10.00 ~ 20.00 μ g/mL containing Sn and Cu.
the preparation method of titanium sponge liquid to be measured is:take the titanium sponge of 0.0900 ~ 0.3000g and be placed in the dual-purpose bottle of 100mL, with distilled water flushing bottle wall, add the sulfuric acid that 4.00 ~ 8.00mL mass concentration is 95.0 ~ 98.0%, after titanium sponge heating for dissolving, drip 1 ~ 5 mass concentration be again the nitric acid of 65.0 ~ 68.0% and with distilled water flushing bottle wall, take off dual-purpose bottle time tranquil until limpid by the above-mentioned solution heated in dual-purpose bottle, liquid level and after being cooled to room temperature, be settled to 100mL and prepare titanium sponge liquid to be measured.
The running parameter determination scope of inductively coupled plasma atomic emission spectrometer is as follows:
Inductive coupling plasma emission spectrograph optimum working parameter scope: power: 1.00 ~ 1.35KW; Plasma flow amount: 14 ~ 16L/min; Assisted gas flow: 0.15 ~ 0.40L/min; Atomization gas flow: 0.60 ~ 0.85L/min; Sample wash flow: 1.3 ~ 1.6 mL/min; Light stability time delay: 15 ~ 23s; Sample promotes time: 15 ~ 21s; The sample wash time: 5 ~ 20s; Duplicate measurements number of times: 1 ~ 3 time;
Time from element spectral line table, select many spectral lines of Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb element in advance, scan respectively described blank working curve titer, described working curve titer a, described working curve titer b, described working curve titer c, described working curve titer d and titanium sponge liquid to be measured respectively with selected spectral line, the interference result that scanning produces is summarized as follows:
Sn189.927 nm analysis spectral line is subject to the interference of Os189.950 nm, Ti189.975 nm and W189.987 nm;
Sn242.170 nm analysis spectral line is subject to the interference of Ti242.130 nm;
As197.197 nm analysis spectral line is subject to the interference of Ti197.200 nm and W197.313 nm;
As193.696 nm analysis spectral line is subject to the interference of Cr193.696 nm, V193.684 nm, Fe193.668 nm and Fe193.619 nm;
As188.979 nm analysis spectral line is subject to the interference of As188.984 nm;
Sb217.582 nm analysis spectral line is subject to the interference of Zr217.582 nm, Re217.621 nm and Ni217.515 nm;
Sb231.146 nm analysis spectral line is subject to the interference of V231.146 nm, Nb231.146 nm, Nb231.168 nm, Ni231.223 nm, Ag231.241 nm and Ni231.096 nm;
Cr283.563 nm analysis spectral line is subject to the interference of U283.557 nm and Ti283.660 nm;
Cr 267.716 nm analysis spectral line is subject to the interference of Mn267.785 nm;
Cu327.393 nm analysis spectral line is subject to the interference of Co327.393 nm, Ce327.393 nm, Ti327.405 nm, Ti327.440 nm, Nb327.479 nm Th327.507 nm, Ti327.529 nm and Sm327.348 nm;
Cu224.700 nm analysis spectral line is subject to the interference of Mo224.711 nm and Sn224.606 nm;
V292.464 nm analysis spectral line is subject to the interference of Zr292.464 nm, Fe292.399 and U292.350 nm;
V310.230 nm analysis spectral line is subject to the interference of Fe310.214 nm, Fe310.236 nm, Gd310.255 nm, Ti310.298 nm, Cr310.347 nm and Ti310.153 nm;
V292.402 analysis spectral line is subject to the interference of Si292.401 nm, Rh292.402 nm, W292.354 nm, V292.464 nm and Ti292.292 nm;
Ni231.604 nm analysis spectral line is subject to the interference of Ta231.604 nm and Ti231.598 nm;
Ni231.003 nm analysis spectral line is subject to the interference of Nb232.024 nm, Ni231.976 nm and Zr232.080 nm;
Zn206.200nm analysis spectral line is subject to the interference of V206.200 nm, Os206.169 nm and V206.156 nm;
Zn213.857nm analysis spectral line is subject to the interference of Hf213.857 nm, Ti213.836 nm, Ti213.925 nm and Ti213.787 nm;
Zn202.548nm analysis spectral line is subject to the interference of Cu202.548 nm, Nb202.531 nm and Os202.512 nm;
Nb309.418nm analysis spectral line is subject to the interference of V309.419 nm, Sn309.469 nm, Cr309.549 nm and V309.310 nm;
Nb269.706nm analysis spectral line is subject to the interference of Ta269.830 nm and Mn269.596 nm.
Can differentiate out in conjunction with spectrogram situation, annoyance level, Interference Peaks, the test comparison situation of signal-to-background ratio situation and each working curve titer containing described nine kinds of impurity elements, the analysis spectral line that final selected following spectral line is nine kinds of impurity elements described in titanium sponge:
Sn-242.170nm and Sn-189.927nm;
As-193.696nm and As-188.979nm;
Sb—217.582nm；
Cr—283.563nm；
Cu-327.393nm and Cu-224.700nm;
V-292.464nm and V-292.402nm;
Ni-231.604nm and Ni-232.003nm;
Zn-206.200nm, Zn-213.857nm and Zn-202.548nm;
Nb-309.418nm and Nb-269.706nm.
The Physical Interference existed in measuring described nine kinds of impurities analysis adopts Matrix phase to eliminate, and adopts peg method to eliminate to its spectra1 interfer-, and the background correction point adopted above-mentioned selected each analysis spectral line is as follows:
Sn242.170nm background correction point is: BGC
1for-0.075nm, BGC
2for+0.039nm;
Sn189.927nm background correction point is: BGC
1for-0.033nm, BGC
2for+0.069nm;
As193.696nm background correction point is: BGC
1for-0.048nm, BGC
2for+0.063nm;
As188.979nm background correction point is: BGC
1for-0.043nm, BGC
2for+0.069nm;
Sb217.582nm background correction point is: BGC
1for-0.089nm, BGC
2for+0.020nm;
Cr283.563nm background correction point is: BGC
1for-0.063nm, BGC
2for+0.043nm;
Cu327.393nm background correction point is: BGC
1for-0.070nm, BGC
2for+0.070nm;
Cu 224.700nm background correction point is: BGC
1for-0.065nm, BGC
2for+0.071nm;
V292.464nm background correction point is: BGC
1for-0.030nm, BGC
2for+0.091nm;
V 292.402nm background correction point is: BGC
1for-0.064nm, BGC
2for+0.103nm;
Ni231.604nm background correction point is: BGC
1for-0.056nm, BGC
2for+0.039nm;
Ni 232.003nm background correction point is: BGC
1for-0.078nm, BGC
2for+0.048nm;
Zn206.200nm background correction point is: BGC
1for-0.079nm, BGC
2for+0.043nm;
Zn213.857nm background correction point is: BGC
1for-0.039nm, BGC
2for+0.045nm;
Zn202.548nm background correction point is: BGC
1for-0.067nm, BGC
2for+0.023nm;
Nb309.418nm background correction point is: BGC
1for-0.095nm, BGC
2for+0.071nm;
Nb269.706nm background correction point is: BGC
1for-0.050nm, BGC
2for+0.029nm.
Establish corresponding working curve according to the spectral line of emission intensity level of described blank working curve titer, described working curve titer a, described working curve titer b, described working curve titer c and described working curve titer d to its concentration value and obtain method linear equation, then measure titanium sponge liquid to be measured and obtain its each spectral line of emission intensity, inductively coupled plasma atomic emission spectrometer can calculate the percentage composition of nine kinds of impurity elements described in titanium sponge automatically according to described working curve.
Carry out continuous 10 times to described blank working curve titer to measure, the standard deviation mean value measured with 10 times is multiplied by 3 and obtains detection limit.
To the relative standard deviation that titanium sponge liquid replication to be measured obtains for 10 times.
The linear equation that above-mentioned selected each analysis spectral line is corresponding, related coefficient, detection limit, relative standard deviation gather as follows
:
Line wavelength/nm linear equation related coefficient detection limit/% relative standard deviation/%
As 193.696 Y=3545x +87.9 0.999779 0.000134 8.70
As188.979 Y=2269x+241.1 0.999287 0.000331 14.66
Sb217.582 Y=11040x+410.5 0.999873 0.000057 15.55
Sn242.170 Y=4657x+264.3 0.999592 0.000240 15.00
Sn189.927 Y=4583x+468.2 0.999219 0.000127 5.81
Cr283.563 Y=380400x+20712.1 0.999838 0.000016 1.22
Cu327.393 Y=498300x+47297.4 0.999499 0.000008 1.96
Cu224.700 Y=50560x+8450.7 0.998410 0.000018 1.20
V292.464 Y=148400x-148.0 1.00000 0.000021 7.24
V292.402 Y=278100x+93069.3 0.995154 0.000005 0.70
Ni231.604 Y=83580x-21.0 1.00000 0.000017 4.25
Ni232.003 Y=37680x+39.4 0.999987 0.000026 14.91
Zn206.200 Y=54600x+1651.3 0.999906 0.000014 1.06
Zn213.857 Y=190100x+8407.6 0.999625 0.000007 0.74
Zn202.548 Y=79940x+2754.0 0.999859 0.000005 0.66
Nb309.418 Y=423800x+60566.6 0.996553 0.000020 0.51
Nb269.706 Y=111100x+18726.3 0.996539 0.000014 0.48
Above-mentioned related coefficient, all more than 0.995, illustrates very well linear.Above-mentioned detection limit, all below 0.00040%, illustrates that detection limit is very low, can meet the needs that micro-trace elements detects.Relative standard deviation of the present invention due to As, Sb, Sn, Ni content in titanium sponge solution to be measured extremely low, except As188.979nm, Sb217.582nm, Sn242.170nm, Ni232.003nm tetra-spectral line relative standard deviations are below 20%, other element spectral line relative standard deviation is all below 10%, illustrate that precision of the present invention is better, show that the present invention can meet the mensuration needs of nine kinds of impurity element percentage compositions described in titanium sponge.
Said process is that the percentage composition measuring nine kinds of impurity elements described in titanium sponge provides the foundation condition and groundwork parameter, once establish the method for measuring of nine kinds of impurity element percentage compositions described in the titanium sponge under selected parameter in inductively coupled plasma atomic emission spectrometer, when testing, only need after instrument start stablizes 10 minutes, open the assay method of nine kinds of impurity element percentage compositions described in set up titanium sponge, to described blank working curve titer, described working curve titer a, described working curve titer b, described working curve titer c and described working curve titer d measures, obtain the new assay method linear equation under new test mode, then the spectral line of emission intensity of titanium sponge solution to be measured is measured, so just calculated the percentage composition of nine kinds of impurity elements described in titanium sponge by inductively coupled plasma atomic emission spectrometer by assay method linear equation, do not need to carry out parameter and condition selection again, save minute, the whole upper machine analytical test time can complete in 4 hours, if add the titanium based sols in early stage, described nine kinds of impurity element standard reserving solutions, described nine kinds of impurity element titers, the time that the preparation of described nine kinds of impurity element working curve titers etc. are all, the analysis completing nine kinds of impurity element percentage compositions described in a titanium sponge sample measures and can complete in 24 hours, research and production needs can be met.
It is emphasized that:
1, for the titanium sponge of same quality, no matter the value taken within the scope of 0.0900g ~ 0.3000g, the described nine kinds of impurity element percentage compositions calculated by inductively coupled plasma atomic emission spectrometer are unique, two kinds of titanium sponge solution to be measured prepared respectively by the titanium sponge such as simultaneously taking 0.0900g or 0.3000g same quality, described in two kinds of titanium sponge solution to be measured, the percentage composition reference value of nine kinds of impurity elements is all Sn0.0051%, As 0.00033%, Sb 0.00041%, Cr 0.0010%, Cu 0.0074%, V 0.00060%, Ni 0.00020%, Zn 0.011%, Nb0.0090%.
2, for the titanium sponge of different quality, even if the value taken within the scope of 0.0900g ~ 0.3000g is equal, but be unequal by described nine kinds of impurity element percentage compositions that inductively coupled plasma atomic emission spectrometer calculates, the titanium sponge such as taking the first quality of 0.2999g or the titanium sponge of the second quality taking 0.2999g, prepare first quality titanium sponge solution to be measured or second quality titanium sponge solution to be measured, described in the titanium sponge of then first quality, the percentage composition reference value of nine kinds of impurity elements is Sn 0.0051%, As 0.0033%, Sb 0.00041%, Cr 0.0010%, Cu 0.0074%, V 0.00060%, Ni 0.00020%, Zn 0.011%, Nb0.0090%., and the percentage composition reference value of nine kinds of impurity elements described in the titanium sponge of second quality is Sn0.020%, As 0.0023%, Sb 0.0031%, Cr 0.010%, Cu 0.014%, V 0.0030%, Ni 0.0050%, Zn 0.011%, Nb0.0050%.
But anyway, the relative standard deviation obtained for 10 times titanium sponge solution replication to be measured all below 20%.
It can thus be appreciated that, related coefficient of the present invention meets the requirement that conventional method related coefficient is not less than 0.995 more than 0.995, detection limit of the present invention is below 0.00040%, the needs that micro-trace elements detects can be met, relative standard deviation of the present invention is below 20%, meet the requirement that general Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb micro-trace elements analytical approach relative standard deviation is not more than 20%, show that the present invention can meet the mensuration needs of nine kinds of impurity element percentage compositions described in titanium sponge.
recovery test
Described nine kinds of impurity element standard solution are added in the titanium sponge solution to be measured detecting described nine kinds of impurity contents, calculate the recovery of described nine kinds of impurity elements between 90 ~ 120% by recovery test, prove that direction of the present invention method is feasible.
Can obviously be found out by above-mentioned analysis: analytical approach of the present invention is prepared by titanium based sols, each standard reserving solution preparation of described nine kinds of impurity elements, each titer preparation of described nine kinds of impurity elements, the mixing mark liquid preparation of 1 μ g/mL is respectively containing described nine kinds of impurity elements, determine the blank working curve titer preparation of 0.00 μ g/mL, prepared by the working curve titer a being respectively 0.01 ~ 0.08 μ g/mL containing described nine kinds of impurity elements, prepared by the working curve titer b being respectively 1.00 ~ 3.00 μ g/mL containing described nine kinds of impurity elements, prepared by the working curve titer c being respectively 4.00 ~ 8.00 μ g/mL containing described nine kinds of impurity elements, the molten d preparation of working curve standard of 10.00 ~ 20.00 μ g/mL is containing Sn and Cu, under the running parameter prerequisite determining inductively coupled plasma atomic emission spectrometer, above-mentioned five kinds of working curve titers and titanium sponge liquid to be measured are scanned respectively, select each analysis spectral line of described nine kinds of impurity elements and background correction is carried out to it, the spectral line of emission intensity of above-mentioned five kinds of working curve titers and its concentration value are set up working curve and obtains method linear equation, the titanium sponge prepared liquid to be measured is measured, inductively coupled plasma atomic emission spectrometer can calculate the percentage composition of nine kinds of impurity elements described in titanium sponge automatically.
Claims (1)
1. the analytical approach of nine kinds of impurity element percentage compositions in Simultaneously test titanium sponge, described nine kinds of impurity elements really refer to for Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb, the reagent used in this analytical approach and test articles for use mainly contain hydrofluorite, nitric acid, distilled water, hydrochloric acid, sulfuric acid, high purity titanium, purity Metal Tin, arsenic trioxide, high purity antimony, High Pure Chromium, high purity copper, high purity vanadium metal, high purity nickel, high purity zinc, High-purity Niobium, King beaker, plastics volumetric flask, beaker, electric furnace, volumetric flask, the tester used is inductively coupled plasma atomic emission spectrometer, and this analytical approach is prepared by titanium based sols, each standard reserving solution preparation of described nine kinds of impurity elements, each titer preparation of described nine kinds of impurity elements, be respectively the mixing mark liquid preparation of 1 μ g/mL containing described nine kinds of impurity elements, determine the blank working curve titer preparation of 0.00 μ g/mL, prepared by the working curve titer a being respectively 0.01 ~ 0.08 μ g/mL containing described nine kinds of impurity elements, prepared by the working curve titer b being respectively 1.00 ~ 3.00 μ g/mL containing described nine kinds of impurity elements, prepared by the working curve titer c being respectively 4.00 ~ 8.00 μ g/mL containing described nine kinds of impurity elements, the molten d preparation of working curve standard of 10.00 ~ 20.00 μ g/mL is containing Sn and Cu, under the running parameter prerequisite determining inductively coupled plasma atomic emission spectrometer, above-mentioned five kinds of working curve titers and titanium sponge liquid to be measured are scanned respectively, select each analysis spectral line of described nine kinds of impurity elements and background correction is carried out to it, the spectral line of emission intensity of above-mentioned five kinds of working curve titers and its concentration value are set up working curve and obtains method linear equation, measure the titanium sponge prepared liquid to be measured, inductively coupled plasma atomic emission spectrometer can calculate the percentage composition of nine kinds of impurity elements described in titanium sponge automatically, it is characterized in that: above-mentioned each correlated process is described below:
Prepared by titanium based sols
Take 1.0000g purity be the high purity titanium of 99.99% and be placed in the King beaker of 250mL, the hydrochloric acid that 15.00mL mass concentration is 36.0 ~ 38.0% is added again with after a small amount of distilled water flushing King beaker, dropwise being added in King beaker by the hydrofluorite of 5.00 ~ 10.00mL mass concentration >=40.0% makes high purity titanium be dissolved, instill in King beaker again after high purity titanium dissolves 1.00 ~ 4.00mL mass concentration be 65.0 ~ 68.0% nitric acid make it clarify and be cooled to room temperature to move in the plastics volumetric flask of 100mL again, clean King beaker at least three times with distilled water and pour in plastics volumetric flask and be settled to the titanium based sols that 100mL prepares titaniferous 10mg/mL,
Each standard reserving solution preparation of described nine kinds of impurity elements
Take the high-purity Sn of 1.0000g and be placed in 250mL beaker and add the hydrochloric acid that 100.00mL mass concentration is 36.0 ~ 38.0%, beaker is placed in and electric furnace carries out heating and boil Sn is dissolved, dissolve the complete beaker that takes off be cooled to room temperature and move in 1000mL volumetric flask, be settled to 1000mL with distilled water cleaning beaker at least three times pouring in volumetric flask and prepare Sn standard reserving solution containing Sn1mg/mL;
Take 1.3203g arsenic trioxide and be placed in 250mL beaker and add the hydrochloric acid that 50.00mL mass concentration is 36.0 ~ 38.0%, beaker is placed in and electric furnace carries out heating and boil arsenic trioxide is dissolved, dissolve the complete beaker that takes off be cooled to room temperature and move in 1000mL volumetric flask, be settled to 1000mL with distilled water cleaning beaker at least three times pouring in volumetric flask and prepare As standard reserving solution containing As1mg/mL;
Take the high-purity Sb of 1.0000g and be placed in 250mL beaker and add 15.00mL mass concentration be 36.0 ~ 38.0% hydrochloric acid and 5.00mL mass concentration be the nitric acid of 65.0 ~ 68.0%, beaker is placed in and electric furnace carries out heating and boil Sb is dissolved, dissolve complete taking off after beaker is cooled to room temperature and add the hydrochloric acid that 35.00mL mass concentration is 36.0 ~ 38.0% again, move into afterwards in 1000mL volumetric flask, pour in volumetric flask and be settled to 1000mL with distilled water cleaning beaker at least three times and prepare Sb standard reserving solution containing Sb1mg/mL;
Take the high-purity Cr of 1.000g and be placed in 250mL beaker and add the hydrochloric acid that 50.00mL mass concentration is 36.0 ~ 38.0%, beaker is placed in and electric furnace carries out heating and boil Cr is dissolved, dissolve the complete beaker that takes off be cooled to room temperature and move in 1000mL volumetric flask, be settled to 1000mL with distilled water cleaning beaker at least three times pouring in volumetric flask and prepare Cr standard reserving solution containing Cr1mg/mL;
Take the high-purity Cu of 1.0000g and be placed in 250mL beaker and add 50.00mL distilled water and 50.00mL mass concentration is the nitric acid of 65.0 ~ 68.0%, beaker is placed in and electric furnace carries out heating and boil Cu is dissolved, dissolve the complete beaker that takes off be cooled to room temperature and move in 1000mL volumetric flask, be settled to 1000mL with distilled water cleaning beaker at least three times pouring in volumetric flask and prepare Cu standard reserving solution containing Cu1mg/mL;
In like manner, 1000mL can also be prepared respectively with reference to above-mentioned Cu standard reserving solution: the V standard reserving solution containing V1mg/mL, the Ni standard reserving solution containing Ni1mg/mL and the Zn standard reserving solution containing Zn1mg/mL;
Take 1.0000g high-purity N b and be placed in 250mL King beaker and dropwise add the hydrofluorite of 5.00mL mass concentration >=40.0%, dropwise add the nitric acid that 2.00mL mass concentration is 65.0 ~ 68.0% again, dissolve complete until Nb and move into when being cooled to room temperature in 1000mL volumetric flask, clean King beaker at least three times with distilled water and pour in volumetric flask and be settled to 1000mL, move in plastic bottle the Nb standard reserving solution prepared containing Nb1mg/mL afterwards;
Each titer preparation of described nine kinds of impurity elements
Sn standard reserving solution described in 10.00mL be placed in 100mL volumetric flask and add the hydrochloric acid that 10.00mL mass concentration is 36.0 ~ 38.0%, in volumetric flask, then adding distilled water be settled to the Sn titer that 100mL prepares stanniferous 100 μ g/mL;
In like manner, each 100mL can also be prepared with reference to said process: the As titer containing As100 μ g/mL, the Sb titer containing Sb100 μ g/mL, the Cr titer containing Cr100 μ g/mL, the Cu titer containing Cu100 μ g/mL, the V titer containing V100 μ g/mL, the Ni titer containing Ni100 μ g/mL, the Zn titer containing Zn100 μ g/mL and the Nb titer containing Nb100 μ g/mL;
The mixing mark liquid preparation of 1 μ g/mL is respectively containing described nine kinds of impurity elements
Described Sn standard reserving solution, described As standard reserving solution, described Sb standard reserving solution, described Cr standard reserving solution, described Cu standard reserving solution, described V standard reserving solution, described Ni standard reserving solution, described Zn standard reserving solution and described Nb standard reserving solution are respectively pipetted 1.00mL together to be joined in the plastics volumetric flask of 100mL, add the hydrochloric acid that 10.00mL mass concentration is 36.0 ~ 38.0% again, be settled to 100mL with distilled water and prepare the mixing mark liquid A being respectively 10 μ g/mL containing described nine kinds of impurity elements;
Mixing mark liquid A described in 10.00mL is placed in 100mL plastics volumetric flask and adds the hydrochloric acid that 10mL mass concentration is 36.0 ~ 38.0%, in plastics volumetric flask, then adds distilled water be settled to 100mL and prepare the mixing mark liquid being respectively 1 μ g/mL containing described nine kinds of impurity elements;
The blank working curve titer preparation of 0.00 μ g/mL
By 4.00 ~ 8.00mL mass concentration 95.0% ~ 98.0% sulfuric acid join and add distilled water and be about in the 100mL plastics volumetric flask of 30mL, to be cooledly to room temperature, be settled to 100mL with distilled water prepare the blank working curve titer of 0.00 μ g/mL;
Prepared by the working curve titer a being respectively 0.01 ~ 0.08 μ g/mL containing described nine kinds of impurity elements
The mixing mark liquid of 1.00 ~ 8.00mL and the titanium based sols of 10.00mL are together joined in 100mL plastics volumetric flask, add again 4.00 ~ 8.00mL mass concentration 95.0 ~ 98.0% sulfuric acid, after being cooled to room temperature, being settled to 100mL with distilled water and preparing the working curve titer a being respectively 0.01 ~ 0.08 μ g/mL containing described nine kinds of impurity elements;
Prepared by the working curve titer b being respectively 1.00 ~ 3.00 μ g/mL containing described nine kinds of impurity elements
Get described Sn titer, described As titer, described Sb titer, described Cr titer, described Cu titer, described V titer, described Ni titer, described Zn titer, described Nb titer each 1.00 ~ 3.00mL and 10.00mL titanium based sols together join in 100mL plastics volumetric flask, add the sulfuric acid that 4.00 ~ 8.00mL mass concentration is 95.0 ~ 98.0% again, to be cooledly to room temperature, be settled to 100mL with distilled water prepare the working curve titer b being respectively 1.00 ~ 3.00 μ g/mL containing described nine kinds of impurity elements;
Prepared by the working curve titer c being respectively 4.00 ~ 8.00 μ g/mL containing described nine kinds of impurity elements
Get described Sn titer, described As titer, described Sb titer, described Cr titer, described Cu titer, described V titer, described Ni titer, described Zn titer, described Nb titer each 4.00 ~ 8.00mL and 10.00mL titanium based sols together join in 100mL plastics volumetric flask, add the sulfuric acid that 4.00 ~ 8.00mL mass concentration is 95.0 ~ 98.0% again, to be cooledly to room temperature, be settled to 100mL with distilled water prepare the working curve titer c being respectively 4.00 ~ 8.00 μ g/mL containing described nine kinds of impurity elements;
The molten d preparation of working curve standard of 10.00 ~ 20.00 μ g/mL is containing Sn and Cu
The titanium based sols getting described Sn standard reserving solution and described Cu standard reserving solution each 1.00 ~ 2.00mL and 10.00mL together joins in 100mL plastics volumetric flask, add the sulfuric acid that 4.00 ~ 8.00mL mass concentration is 95.0 ~ 98.0% again, to be cooledly to room temperature, be settled to 100mL with distilled water prepare the working curve titer d being 10.00 ~ 20.00 μ g/mL containing Sn and Cu;
The preparation of titanium sponge liquid to be measured
Take the titanium sponge of 0.0900 ~ 0.3000g and be placed in the dual-purpose bottle of 100mL, with distilled water flushing bottle wall, add the sulfuric acid that 4.00 ~ 8.00mL mass concentration is 95.0 ~ 98.0%, after titanium sponge heating for dissolving, drip 1 ~ 5 mass concentration be again the nitric acid of 65.0 ~ 68.0% and with distilled water flushing bottle wall, take off dual-purpose bottle time tranquil until limpid by the above-mentioned solution heated in dual-purpose bottle, liquid level and after being cooled to room temperature, be settled to 100mL and prepare titanium sponge liquid to be measured;
The running parameter of inductively coupled plasma atomic emission spectrometer is determined and analysis spectral line is determined
The running parameter determination scope of inductively coupled plasma atomic emission spectrometer is as follows:
Inductive coupling plasma emission spectrograph optimum working parameter scope: power: 1.00 ~ 1.35KW; Plasma flow amount: 14 ~ 16L/min; Assisted gas flow: 0.15 ~ 0.40L/min; Atomization gas flow: 0.60 ~ 0.85L/min; Sample wash flow: 1.3 ~ 1.6mL/min; Light stability time delay: 15 ~ 23s; Sample promotes time: 15 ~ 21s; The sample wash time: 5 ~ 20s; Duplicate measurements number of times: 1 ~ 3 time;
Many spectral lines of Sn, As, Sb, Cr, Cu, V, Ni, Zn, Nb element are selected in advance from element spectral line table, scan respectively described blank working curve titer, described working curve titer a, described working curve titer b, described working curve titer c, described working curve titer d and titanium sponge liquid to be measured respectively with selected spectral line, the interference result that scanning produces is summarized as follows:
Sn189.927nm analysis spectral line is subject to the interference of Os189.950nm, Ti189.975nm and W189.987nm;
Sn242.170nm analysis spectral line is subject to the interference of Ti242.130nm;
As197.197nm analysis spectral line is subject to the interference of Ti197.200nm and W197.313nm;
As193.696nm analysis spectral line is subject to the interference of Cr193.696nm, V193.684nm, Fe193.668nm and Fe193.619nm;
As188.979nm analysis spectral line is subject to the interference of As188.984nm;
Sb217.582nm analysis spectral line is subject to the interference of Zr217.582nm, Re217.621nm and Ni217.515nm;
Sb231.146nm analysis spectral line is subject to the interference of V231.146nm, Nb231.146nm, Nb231.168nm, Ni231.223nm, Ag231.241nm and Ni231.096nm;
Cr283.563nm analysis spectral line is subject to the interference of U283.557nm and Ti283.660nm;
Cr 267.716nm analysis spectral line is subject to the interference of Mn267.785nm;
Cu327.393nm analysis spectral line is subject to the interference of Co327.393nm, Ce327.393nm, Ti327.405nm, Ti327.440nm, Nb327.479nm, Th327.507nm, Ti327.529nm and Sm327.348nm;
Cu224.700nm analysis spectral line is subject to the interference of Mo224.711nm and Sn224.606nm;
V292.464nm analysis spectral line is subject to the interference of Zr292.464nm, Fe292.399nm and U292.350nm;
V310.230nm analysis spectral line is subject to the interference of Fe310.214nm, Fe310.236nm, Gd310.255nm, Ti310.298nm, Cr310.347nm and Ti310.153nm;
V292.402nm analysis spectral line is subject to the interference of Si292.401nm, Rh292.402nm, W292.354nm, V292.464nm and Ti292.292nm;
Ni231.604nm analysis spectral line is subject to the interference of Ta231.604nm and Ti231.598nm;
Ni231.003nm analysis spectral line is subject to the interference of Nb232.024nm, Ni231.976nm and Zr232.080nm;
Zn206.200nm analysis spectral line is subject to the interference of V206.200nm, Os206.169nm and V206.156nm;
Zn213.857nm analysis spectral line is subject to the interference of Hf213.857nm, Ti213.836nm, Ti213.925nm and Ti213.787nm;
Zn202.548nm analysis spectral line is subject to the interference of Cu202.548nm, Nb202.531nm and Os202.512nm;
Nb309.418nm analysis spectral line is subject to the interference of V309.419nm, Sn309.469nm, Cr309.549nm and V309.310nm;
Nb269.706nm analysis spectral line is subject to the interference of Ta269.830nm and Mn269.596nm;
Can differentiate out in conjunction with spectrogram situation, annoyance level, Interference Peaks, the test comparison situation of signal-to-background ratio situation and each working curve titer containing described nine kinds of impurity elements, the analysis spectral line that final selected following spectral line is nine kinds of impurity elements described in titanium sponge:
Sn-242.170nm and Sn-189.927nm;
As-193.696nm and As-188.979nm;
Sb—217.582nm；
Cr—283.563nm；
Cu-327.393nm and Cu-224.700nm;
V-292.464nm and V-292.402nm;
Ni-231.604nm and Ni-232.003nm;
Zn-206.200nm, Zn-213.857nm and Zn-202.548nm;
Nb-309.418nm and Nb-269.706nm;
Analyze the interference correction measured
The Physical Interference existed in measuring described nine kinds of impurities analysis adopts Matrix phase to eliminate, and adopts peg method to eliminate to its spectra1 interfer-, and the background correction point adopted above-mentioned selected each analysis spectral line is as follows:
Sn242.170nm background correction point is: BGC
1for-0.075nm, BGC
2for+0.039nm;
Sn189.927nm background correction point is: BGC
1for-0.033nm, BGC
2for+0.069nm;
As193.696nm background correction point is: BGC
1for-0.048nm, BGC
2for+0.063nm;
As188.979nm background correction point is: BGC
1for-0.043nm, BGC
2for+0.069nm;
Sb217.582nm background correction point is: BGC
1for-0.089nm, BGC
2for+0.020nm;
Cr283.563nm background correction point is: BGC
1for-0.063nm, BGC
2for+0.043nm;
Cu327.393nm background correction point is: BGC
1for-0.070nm, BGC
2for+0.070nm;
Cu 224.700nm background correction point is: BGC
1for-0.065nm, BGC
2for+0.071nm;
V292.464nm background correction point is: BGC
1for-0.030nm, BGC
2for+0.091nm;
V 292.402nm background correction point is: BGC
1for-0.064nm, BGC
2for+0.103nm;
Ni231.604nm background correction point is: BGC
1for-0.056nm, BGC
2for+0.039nm;
Ni 232.003nm background correction point is: BGC
1for-0.078nm, BGC
2for+0.048nm;
Zn206.200nm background correction point is: BGC
1for-0.079nm, BGC
2for+0.043nm;
Zn213.857nm background correction point is: BGC
1for-0.039nm, BGC
2for+0.045nm;
Zn202.548nm background correction point is: BGC
1for-0.067nm, BGC
2for+0.023nm;
Nb309.418nm background correction point is: BGC
1for-0.095nm, BGC
2for+0.071nm;
Nb269.706nm background correction point is: BGC
1for-0.050nm, BGC
2for+0.029nm;
Method linear equation, detection limit and relative standard deviation
Establish corresponding working curve according to the spectral line of emission intensity level of described blank working curve titer, described working curve titer a, described working curve titer b, described working curve titer c and described working curve titer d to its concentration value and obtain method linear equation, then measure titanium sponge liquid to be measured and obtain its each spectral line of emission intensity, inductively coupled plasma atomic emission spectrometer can calculate the percentage composition of nine kinds of impurity elements described in titanium sponge automatically according to described working curve;
Carry out continuous 10 times to described blank working curve titer to measure, the standard deviation mean value measured with 10 times is multiplied by 3 and obtains detection limit;
To the relative standard deviation that titanium sponge liquid replication to be measured obtains for 10 times;
The linear equation that above-mentioned selected each analysis spectral line is corresponding, related coefficient, detection limit, relative standard deviation gather as follows:
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| CN105372230A (en) * | 2015-09-30 | 2016-03-02 | 遵宝钛业有限公司 | Method for measuring tin in titanium tetrachloride through ICP-AES |
| CN107490571A (en) * | 2017-09-28 | 2017-12-19 | 新疆新鑫矿业股份有限公司阜康冶炼厂 | Method and system based on impurity element in ICP emission spectrometry electrolytic nickels |
| CN108627499A (en) * | 2018-04-13 | 2018-10-09 | 中航金属材料理化检测科技有限公司 | A kind of assay method of Boron in Titanium Alloy content |
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