CN100370242C - Process for simultaneous determination of stained element content in gray glass utilizing plasma emission spectrometer - Google Patents
Process for simultaneous determination of stained element content in gray glass utilizing plasma emission spectrometer Download PDFInfo
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Abstract
The present invention provides a method for simultaneously measuring the contents of stained elements in gray glass by utilizing an inductively coupled plasma emission spectrometer, which comprises the steps that silicon in gray glass is eliminated by hydrofluoric acid; the salinity of a test solution is reduced, and thereby, the clogging of a torch tube, the increase of the washing frequency of the torch tube and the reduction of the service life of the torch tube when the torch tube is tested by a machine can be avoided; the appropriate concentration and the acidity of the sample after the sample is processed are determined. The present invention adopts an analysis spectrum line in the processes of analysis and measurement that the wavelength of Fe is 261.187 nm; the wavelength of Ni is 216.555 nm; the wavelength of Co is 230.786 nm; the wavelength of Se is 196.026 nm. The instrument has the operation parameters that the flow of atomized gas is 0.75 L/min; the flow of auxiliary gas is 1.5 L/min; the power of a radio frequency generator is 0.9KW; the speed of a pump is 15 rpm; the speed of plasma gas is 15 L/min; the stab time is 15s; the sample uptake time is 30s; the rinse time of an atomizer is 10s. The method of the present invention has the characteristics of simple and convenient operation, high speed, high accuracy and good stability.
Description
Affiliated technical field
The invention belongs to test and analysis technology, what relate generally to is a kind of method of utilizing plasma emission spectrometer to measure coloring element content in the grey glass simultaneously.Coloring element is Fe, Co, Ni, Se.
Background technology
In the production of coloured glass, iron, cobalt, nickel, trace element selenium play the vital role of regulating glass colour, be the main small powder that to control well in the serial coloured glass production of mass colouring, and the height of iron content directly affect the performance index such as transmittance of glass in the glass.Therefore, the mensuration of these micro-coloring elements is the key factors that concern glass colour quality quality in the glass.Because the content of these coloring elements in glass is lower, moreover in handling the sample process, the selenium in the glass is very easy to volatilization, accurately measures comparatively difficulty.Also do not measure at present the national standard of the method for iron in the glass, cobalt, nickel, selenium, the mensuration of the micro-coloring element in the general grey glass of existing glass enterprise is that iron, cobalt, nickel, selenium colorimetric estimation are handled, carried out respectively to sample respectively.Also do not have at present a kind of to analyze the method for the content that obtains iron, cobalt, nickel, selenium simultaneously with a glass solution.The content that analyzes iron, cobalt, nickel, the selenium in the grey glass must carry out several method, plurality of processes just can be finished.These method troublesome poerations, analysis time is long, workload is big, the mensuration of finishing all coloring elements in the gray glass sample must be carried out many loaded down with trivial details processes and just can be finished, must need between 3 days/man-hour at the soonest, also need many kinds of reagent in the analytic process, chemical reagent is also needed a series of activities such as preparation.
Inductive coupling plasma emission spectrograph can be measured more than 70 kind of metallic element, is widely used in fields such as metallurgy, geology, environment, oil, chemical industry and material, can carry out qualitative, sxemiquantitative, quantitative test.But inductive coupling plasma emission spectrograph aspect the mensuration of glass industry coloring element in glass also beyond example.Though, limit can be subjected to various factors when being applied to a certain field because a kind of instrument and equipment has some function.Equally, utilize the micro-coloring element in the plasma emission spectrometer mensuration glass, (1), at first, sample will carry out acidity what state or the like the situation what kind of handles, adopts what reagent, sample should be processed into which type of concentration, solution all can influence precision of test result, because handle the reagent difference of using in the sample process, the element of introducing is just different, and the interference of generation is also just different.The concentration difference of solution, the influence between element are also just different, and the solution concentration that is disposed is low more, and the interference between element is also just more little, but weighing error is also just bigger simultaneously, and analytical error is also bigger, and this two aspect just in time is a contradiction.Be exactly in addition, selenium volatilizees easily, and the selenium minimizing of dealing with improperly in the remaining solution that also can make after the selenium volatilization causes handling causes the result inaccurate.Therefore, aspect sample preparation, specifically should claim how many samples, be diluted to which kind of degree, should utilize which kind of disposal route can obtain minimum interference, bigger line strength and less background, and have that the bigger range of linearity etc. needs could to determine through the consideration of every aspects and experiment.(2) moreover, the selection of instrument condition is also very important, at each element, the spectral line that instrument provides has tens, adopts which bar spectral line, does not adopt which bar spectral line, the result who is measured differs greatly, because there is very big interference between spectral line, not only exists between the different spectral lines of identity element and disturb, and also have serious disturbance between the spectral line of different elements.In addition, the operating parameter of instrument all has a scope, and the optional scope that instrument provides is very wide, but specific to certain sample of test, certain element, its only conditional parameter need can be determined through a large amount of experiments.(3) and method after setting up, the accuracy of specimen can satisfy production requirement also needs do a large amount of check and correction experiments or reclaim experiment.Or the like these work loaded down with trivial details, take brain, need a large amount of failed experiments do the basis, therefore, also do not have producer to do a large amount of work in this respect at present.Also do not utilize at present plasma emission spectrometer to measure the ready-made method of coloring element iron, cobalt, nickel, selenium in the glass.The method of testing iron in the grey glass that present float glass process produces, cobalt, nickel, Se content does not simultaneously also have at present.
Summary of the invention
Purpose of the present invention promptly is to propose a kind of plasma emission spectrometer that utilizes to measure coloring element analysis on Content method in the grey glass simultaneously.
The assay method that the present invention proposes is:
The processing of sample: what kind of sample will carry out and handle, adopt acidity what state or the like the situation that what reagent, sample should be processed into which type of concentration, solution all should be to obtain minimum interference, bigger line strength and less background, and having the bigger range of linearity for according to experimentizing and selecting, the improper meeting of the disposal route of sample directly influences precision of test result.Because handle the reagent difference of using in the sample process, the element of introducing is just different, and the interference of generation is also just different.The concentration difference of solution, the influence between element are also just different, and the solution concentration that is disposed is low more, and the interference between element is also just more little, but weighing error is also just bigger simultaneously, and analytical error is also bigger, and this two aspect just in time is a contradiction.Therefore, aspect sample preparation, specifically should claim how many samples, be diluted to which kind of degree, should utilize which kind of disposal route can obtain minimum interference, bigger line strength and less background, and have that the bigger range of linearity etc. needs could to determine through the consideration of every aspects and experiment.
We at first catch up with silicon to handle to it for the micro-coloring element in the glass, reduce the salinity of test solution, to avoid when last machine the is tested torch pipe being resulted in blockage, increase the wash number of torch pipe, the serviceable life of reducing the torch pipe.Be determined by experiment suitable concn and acidity after sample is handled, caught up with use higher boiling acid perchloric acid in the silicon process with hydrofluorite, the residue after will catching up with silicon leaches in the process of volumetric flask, uses hydrochloric acid.
Being about to through being ground to by the aperture is that the smoked glass sample of 0.08mm sieve accurately takes by weighing 0.5-0.9 gram (being accurate to ± 0.0001 gram) and places the platinum ware, use water-wet, add 1ml-2ml perchloric acid and 5-10ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette, in order to the silicon in the glass of rushing; And to sample by the above-mentioned steps re-treatment once, the temperature that raises gradually is not to there being Bai Yanzhi, with the silicon in the glass of further rushing; After being cooled to room temperature, add 4-20ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, be diluted with water to scale, make 2%≤acidity≤10%;
Prepare blank test solution: in the platinum ware, add the reagent of and equivalent identical, do moving into the 100ml volumetric flask after the processing identical, be diluted with water to scale, make 2%≤acidity≤10% with sample with the said sample processing procedure;
The preparation of standard solution: accurately take by weighing 0.5-0.9 gram clear float glass in the platinum ware, the reagent that adds and equivalent identical with the said sample processing procedure, move into the 100ml volumetric flask after doing the processing identical with sample, in volumetric flask, add Fe, Co, Ni, Se standard solution respectively, water is settled to graticule, thereby obtain the standard solution identical, 2%≤acidity≤10% with matrix of samples;
The selection of analysis spectral line: the corresponding every kind of element of analytical instrument provides tens spectral lines, adopt different spectral lines, the result who is measured differs greatly, because there is very big interference between spectral line, not only exist between the different spectral lines of identity element and disturb, and also have serious disturbance between the spectral line of different elements.The intensity of different spectral lines is also different.After the selection spectral line will compare through observation (analysis has or not spectral line to disturb), the contrast of line strength data, the background intensity data to the spectrogram shape, investigate the signal-to-background ratio value situation of each spectral line again and taken all factors into consideration, applicable cases spectral line preferably will can be determined by experiment.
Therefore, select the spectral line aspect, should consider that line strength considers to disturb and the signal-to-background ratio situation again.Article one spectral line that provides for instrument not necessarily is exactly suitable spectral line, and also being needs experiment and select and can determine.For example: the selection of (1) Co spectral line: Co II 238.892 spectral lines (article one spectral line that instrument provides), its intensity is 27322.5, and intensity level is the highest, and having Fe II 238.863 intensity is 8360.0 interference, should not adopt.Co II 228.615 spectral lines, its intensity are 6936.5, and it exists, and Ni I 228.613 intensity are 1.1, Ni II 228.708 intensity are 623.6 interference, and because of containing nickel in the grey glass, so this spectral line is not all right.Co II230.786 spectral line, its intensity is 21829.0, it exists that Ni II 230.778 intensity are 76, Si II 230.786 intensity are 0.2, the interference of Co II 230.751, Ni I 230.735, Fe II 230.731, but its interference strength is relatively very low, so can use.Co II 237.863 spectral lines, its intensity are 15306.0, and there is the interference of Fe II237.855, Fe II 237.900 in it, and its interference strength is higher relatively.Co II 231.160 spectral lines, its intensity are 13310.5, and it exists, and Fe II 231.203 intensity are 21.0, the interference of Ni I 231.234, Co II 231.256, and its interference strength is higher relatively.Co II 236.379 spectral lines, its intensity are 9708.5, and it exists, and Fe II 236.386 intensity are 34.5, W II 236.346 intensity are 166.1 interference.Or the like.Co II 230.786 spectral lines are more suitable as can be known from above selection.
(2) selection of nickel spectral line
Ni II 231.604 spectral lines, its intensity are 9024.1, it exists, and Co II 231.575 intensity are 5.1, Co I 231.616 intensity are 13.8, Co I 231.685 intensity be 17.5 interference.Ni II 216.555 spectral lines, its intensity are 6350.0, and it exists, and Mo II 216.580 intensity are 51.4, As I 216.552 intensity are 25.3 interference.Ni II 221.648 spectral lines, its intensity are 7884.3, and it exists, and Si I 221.667 intensity are 1144.4, Co II 221.729 intensity are 31.8 interference.Ni II 230.299 spectral lines, its intensity are 10393.1, and it exists, and Si I 230.306 intensity are 70.3, Cu I 230.312 intensity are 110.2 interference.Or the like these, though all there is interference, Ni II 216.555 spectral line resultant effects are better.
(3) selection of Fe spectral line
Fe II 238.204 spectral lines, its intensity is 41015.0, it exists that Ru II 238.201 intensity are 763.6, Co II 238.232 intensity are 84.0, Co II 238.176 intensity are 1159.0 interference, the interference of cobalt is comparatively serious, therefore, during the ICP of iron measures in grey glass, can not use Fe II 238.204 spectral lines.Intensity is the interference that there is Co I 259.920 in 27160.0 Fe II 259.940 spectral lines, Fe II 234.350 spectral lines, its intensity is 15400.0, it exists that Ni II 234.349 intensity are 155.1, Ni II 234.395, Co II334.322 intensity are 6.2, Fe II 234.396 intensity are 1400.0 interference, because of there being nickel in the grey glass in a large number, therefore can not select Fe II 234.350 spectral lines.Intensity is 10719.4 Fe II 239.563 spectral lines, have that W II 239.573 intensity are 28.1, Co II 239.551 intensity are 34.1 interference.Fe II 261.187 spectral lines though its intensity is not high, are 8669.2, and there is not the interference of a large amount of ions that exist in the grey glass such as aluminium calcium magnesium cobalt nickel in it, have therefore selected Fe II 261.187 spectral lines at last.
(4) selection of selenium spectral line
Se I 196.026 spectral lines, its intensity are 288.1, and there is intensity in it is that 5.6 Fe I 196.061, intensity are interference 3.9, Co I 196.095, but the signal-to-background ratio of Se I 196.026 spectral lines is all bigger than other spectral lines, so we have selected it.Intensity is 161.2 Se I 203.985 spectral lines, and having intensity is the interference of 18.6 Mn II 203.998, though do not contain Mn in the grey glass, the signal-to-background ratio of this spectral line is lower, therefore non-selected it.Other spectral line: intensity is that 27.8 Se I 185.457 spectral lines, intensity are that 36.1 spectral lines such as SeI 206.279 all exist the too low problem of intensity, therefore, comprehensive above factor, we have finally selected the analysis spectral line of Se I 196.026 spectral lines as the ICP test of grey glass.
For the micro-coloring element in the grey glass, by big quantitative analysis experiment, we have selected following optimal wavelength; See chart 1:
| Element | Fe | Co | Ni | Se |
| Wavelength (nm) | 261.187 | 230.786 | 216.555 | 196.026 |
The selection of Instrument operation parameter:
The operating parameter of instrument all has a scope, and the optional scope that instrument provides is very wide, but specific to certain class sample of test, certain element, its only conditional parameter need can be determined through a large amount of experiments.The behavior of volatilization-atomization in the ICP discharge of the flash-over characteristic of ICP, analyte-excite-ionization, disturbed condition etc., all closely related with ICP discharge operation parameter.These parameters mainly are high frequency power, carrier gas flux etc.Because these relationship between parameters exist conflicting situation,, the flow of plasma (orifice) gas melts if crossing the low torch pipe that will cause.So we have carried out properly selecting to Instrument operation parameter with the method for experiment.What at first should consider when selecting is that less non-spectrum disturbs and the bigger ability that detects (bigger line strength and less background), and has the bigger range of linearity, secondly should take into account as much as possible most units are have analysis condition preferably.Compromise condition when being the sequential scanning analysis.
High frequency power has different influences to detecting ability with disturbing effect, increases effect, and temperature raises, and electron density also increases, and line strength may strengthen, but background enhanced more very.Therefore, signal-to-background ratio will occur along with the increase of power reducing after the maximum value, perhaps reduce always, and spectral line excitation energy is low more to be reduced more very.Adopting lower power, is favourable for reducing detection limit sometimes, and still, when low-power, disturbing effect is more serious.In order to reduce this interference, should adopt bigger power, obviously, this reducing may be to be cost with the loss that detects, and therefore, will consider to detect ability and disturbing effect simultaneously to the selection of high frequency power.In addition, high frequency power may cause the fusing of torch pipe.Therefore, to properly select high frequency power.
The influence of carrier gas flux: increase carrier gas flux, make sample suck speed and increase, thereby the amount of analyte that enters in the plasma increases, and spectral line is strengthened, and help the formation of ICP annular channel structure.But excessive carrier gas flux will make diluted sample, and analyte mean residence time in the ICP passage shortens, and temperature reduces, and electron-ion continuous spectrum background reduces, and analyte line strength also reduces, also directly impact analysis result.
Exemplified the signal-to-background ratio situation (chart 2) of each spectral line of solution under different radio-frequency signal generator power, atomization gas flow situation below:
| Change instrument condition | Signal-to-background ratio (SBR) under the element spectral line wavelength (nm) | |||||
| Numbering | Radio-frequency signal generator power | The atomization gas flow | Fe | Co | Ni | Se |
| 1 | KW | L/min | 261.187 | 230.786 | 216.555 | 196.026 |
| 2 | 0.9 | 0.75 | 33.848 | 6.19 | 4.74 | 0.385 |
| 3 | 1.2 | 0.75 | 27.153 | 6.062 | 4.76 | 0.225 |
| 4 | 1.3 | 0.75 | 23.368 | 5.206 | 4.057 | 0.202 |
| 5 | 1.3 | 0.70 | 18.579 | 4.003 | 3.205 | 0.212 |
| 6 | 1.0 | 0.9 | 7.214 | 1.619 | 1.306 | 0.836 |
Annotate: going up in the table is for 1-5 number when coloured glass is mixed with Co, Ni, Se to be respectively 0.55,0.5,0.16 (ppm), Fe2O3 is 0.31% solution, the situation of the signal-to-background ratio of each spectral line of solution under different radio-frequency signal generator power, atomization gas flow situation; Be for No. 6 coloured glass be mixed with that Co, Fe, Ni, Se are respectively 0.9,8.1,0.6, signal-to-background ratio situation during the solution of 0.5ppm.Though No. 6 content is than 1-5 number all high (except the iron), because of its atomization gas flow causes its SBR value lower than 1-5 number on the contrary more greatly.Or the like these, passed through the macromethod experiment, the Instrument operation parameter that we select is as follows; See chart 3:
| Atomization gas flow (L/min) | Secondary air amount (L/min) | Radio-frequency signal generator power (KW) | Pump speed (rpm) | Plasma (orifice) gas (Plasma) | Stabilization time (Stab time) | Sample promotes the time (Sample Uptake) | Atomizer scavenging period (Rinse Time) | The duplicate measurements number of times |
| 0.75 | 1.5 | 0.9 | 15 | 15L/min | 15s | 30s | 10s | 3 |
The elimination of disturbing:
Because the high temperature of plasma, chemistry disturbs less in the analysis of the micro-coloring element in the glass.The Physical Interference that the difference that causes atomizer to promote efficient because of surface tension, viscosity, density and salt etc. causes, we utilize matrix to mate and eliminate, and promptly add coloring element and do standard specimen and eliminate in the substrate glass that does not contain element to be measured.Disturb as for spectrum, we select by changing wavelength, the change sample weighting amount carries out suitable control to sample concentration and overcomes.
The deduction of background
Because the background that parasitic light, the low intensive molecule of bands of a spectrum broadening are launched continuously, the ghost line of grating etc. produces, consider the influence of higher concentration element to measuring, we seek the optimization setting of method by selecting only mensuration wavelength, optimization instrument parameter.Utilize computer operation software, select the Fitted background to correct and carry out background deduction.
The working curve linear relationship of method and the experiment of method accuracy
(1) detection limit test and working curve linear relationship situation
Blank sample is carried out continuous ten times mensuration, obtain the detection limit of this method with the standard deviation (SD) average on duty three of 10 tests.Chart 4:
| The sample composition | Fe | Co | Ni | Se |
| Wavelength (nm) | 261.187 | 230.786 | 216.555 | 196.026 |
| Related coefficient | 0.999910 | 0.999758 | 0.999109 | 0.999985 |
| Working curve | Y＝9287.08x+1886.2 | Y＝15081.5x+89.4455 | Y＝12708.7x+159.852 | Y783.825x+1.09631 |
| Detection limit (%) | 3.09×10 -3 | 3.66×10 -5 | 6.15×10 -5 | 4.2×10 -4 |
(2) precision experiment
To the micro-coloring element sample replication in the same glass 11 times, the precision of method the results are shown in down chart 5.
Chart 5: the precision of method (n=11, %)
| The sample composition | Fe | Co | Ni | Se |
| Extreme difference | 0.00211 | 0.000109 | 0.00006 | 0.00030 |
| Mean value | 0.1719 | 0.003043 | 0.0030 | 0.0012 |
| SD | 0.001055 | 0.000034 | 0.000032 | 0.00012 |
| RSD | 0.61379 | 1.1 | 1.05 | 28.03 |
(3) recovery experiment
Sample is carried out mark-on reclaim experiment, the results are shown in chart 6.
Chart 6: reclaim experimental result
| Sample number into spectrum | Fe | Co | Ni | Se | |
| 1# | Add scalar (ppm) | 8.10 | 0.90 | 0.60 | 0.50 |
| Measured value (ppm) | 8.10 | 0.903 | 0.63 | 0.43 | |
| The recovery (%) | 99.33 | 100.33 | 105.0 | 86.00 | |
| 2# | Add scalar (%) | 0.32 | 0.0061 | 0.0055 | 0.0018 |
| Measured value (%) | 0.32 | 0.0063 | 0.0057 | 0.0019 | |
| The recovery (%) | 100.00 | 103.28 | 103.64 | 105.56 | |
| 3# | Add scalar (ppm) | 29.016 | 0.55 | 0.50 | 0.15 |
| Measured value (ppm) | 29.079 | 0.55 | 0.50 | 0.16 | |
| The recovery (%) | 100.22 | 100.0 | 100.00 | 106.67 | |
| 4# | Add scalar (ppm) | 36.0 | 0.50 | 0.20 | 0.12 |
| Measured value (ppm) | 36.214 | 0.51 | 0.20 | 0.11 | |
| The recovery (%) | 100.59 | 102.0 | 100.00 | 91.67 | |
By chart 6 as can be known: the recovery of each element can satisfy the analysis requirement substantially between 86.00% to 106.67%.
Assay method of the present invention and colourimetry contrast situation
Be to utilize the method set up to the analysis result of the present invention of the coloring element in the glass of several manufacturer production and the analysis result contrast verification of colourimetry below:
| The sample composition | Fe | Co | Ni | Se | |
| 1# | The icp analysis result | 0.40 | 0.0067 | 0.0032 | / |
| The colorimetric analysis result | 0.39 | 0.0069 | 0.0027 | ||
| 2# | The icp analysis result | 0.34 | 0.0059 | 0.0050 | 0.0018 |
| The colorimetric analysis result | 0.35 | 0.0055 | 0.0055 | 0.0022 | |
| 3# | The icp analysis result | 0.40 | 0.0055 | 0.0020 | 0.0012 |
| The colorimetric analysis result | 0.38 | 0.0058 | 0.0024 | 0.0010 | |
| 4# | The icp analysis result | 0.40 | 0.0057 | 0.0071 | 0.0012 |
| The colorimetric analysis result | 0.41 | 0.0057 | 0.0069 | 0.0009 | |
| 5# | The icp analysis result | 0.34 | 0.0054 | 0.0002 | 0.0011 |
| The colorimetric analysis result | 0.34 | 0.0055 | 0.0001 | 0.0015 | |
The present invention passes through the selection of analysis condition, the experiments such as elimination of interference, employing matrix coupling, set up the analytical approach of utilizing the inductively coupled plasma emission spectrometer to measure elements such as micro-coloring element Fe in the glass, Co, Ni, Se simultaneously, the complexity of the content conventional test methodologies of Fe, Co, Ni, Se in the grey glass, loaded down with trivial details property have been overcome, that this method has is easy, characteristics fast and accurately, and stability is preferably arranged.
Embodiment
Embodiment 1:
1, the explanation of relevant determination and analysis process:
This method is applicable to the micro-coloring element Determination on content in the coloured glass (the various samples that comprise similar glass ingredient).
The used balance of analytic process should be accurate to 0.0001 gram.Balance and counterweight should regularly be examined and determine, and take by weighing sample and should be accurate to 0.0002 gram.
Volumetric flask, transfer pipet used in the analytic process should be proofreaied and correct.
Analytical sample should be dried 1 hour in 105-110 ℃ of baking oven, was cooled to weighing after the room temperature in exsiccator.
Used water should be distilled water or deionized water in the standard specimen definite value process; Agents useful for same should be to be analyzed pure or top grade is pure; And to do blank assay.
2, key instrument and reagent
VISTA-PRO composes direct-reading inductive coupling plasma emission spectrograph (U.S. VARIAN company) entirely; The computing machine that has the vista analysis software; HP Laser Jet 6L Pro printer.Sand-bath electric hot plate hydrochloric acid (1+1), HF (70%), that perchloric acid agents useful for same such as (1+1) is top grade is pure, and water is distilled water.
3, determination and analysis process:
Is 75 μ m sieves by the aperture with agate mortar extremely with smoked glass sample porphyrize, is stored in the measuring cup, in order to the usefulness of weighing.Sample in the measuring cup is put in sample sack, in thermostatic drying chamber, more than 1 hour, puts into exsiccator then, be cooled to room temperature, to treat weighing in 105-110 ℃ of oven dry.
Accurately take by weighing 0.50 gram (being accurate to ± 0.0001 gram) sample and in the platinum ware, use water-wet, add 1.0ml perchloric acid and 6ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette (silicon in the glass of rushing).Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette (silicon in the glass of further rushing is not in case catch up with clean).Cooling adds 4ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, be diluted with water to scale, acidity is 2%.
The preparation of blank test solution
In the platinum ware, add 1.0ml perchloric acid and 6ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette.Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette.Cooling adds 4ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, be diluted with water to scale.Acidity is 2%.
The preparation of standard solution
Standard solution one: accurately take by weighing 0.5 gram (being accurate to ± 0.0001 gram) clear float glass and in the platinum ware, add 1.0ml perchloric acid and 6ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette.Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette.Cooling adds 4ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, add Fe, Co, Ni, Se standard solution 0,0.9,0.5,0.5ml that concentration is 100ppm respectively, be diluted with water to scale, shake up, obtain that Fe, Co, Ni, Se concentration are respectively 5,0.9,0.5, the 0.5ppm standard solution.Acidity is 2%.
Standard solution two: accurately take by weighing 0.5 gram (being accurate to ± 0.0001 gram) clear float glass and in the platinum ware, add 1.0ml perchloric acid and 6ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette.Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette.Cooling adds 4ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, add Fe, Co, Ni, Se standard solution 1,0.5,0.3,0.2ml that concentration is 100ppm respectively, be diluted with water to scale, shake up, obtain that Fe, Co, Ni, Se concentration are respectively 6,0.5,0.3, the 0.2ppm standard solution.Acidity is 2%.
Standard solution three: accurately take by weighing 0.5 gram (being accurate to ± 0.0001 gram) clear float glass and in the platinum ware, add 1.0ml perchloric acid and 6ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette.Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette.Cooling adds 4ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, add Fe, Co, Ni, Se standard solution 3,0.3,0.7,0.7ml that concentration is 100ppm respectively, be diluted with water to scale, shake up, obtain that Fe, Co, Ni, Se concentration are respectively 8,0.3,0.7, the 0.7ppm standard solution.Acidity is 2%.
Analysis spectral line is selected:
| Element | Fe | Co | Ni | Se |
| Wavelength (nm) | 261.187 | 230.786 | 216.555 | 196.026 |
Instrument operation parameter is selected:
| Atomization gas flow (L/min) | Secondary air amount (L/min) | Radio-frequency signal generator power (KW) | Pump speed (rpm) | Plasma (orifice) gas (Plasma) | Stabilization time (Stab time) | The sample load rises the time (Sample Uptake) | Atomizer scavenging period (Rinse Time) | The duplicate measurements number of times |
| 0.75 | 1.5 | 0.9 | 15 | 15L/min | 15s | 30s | 10s | 3 |
Last machine is measured
Under the instrument condition of work of selecting, measure blank solution and standard solution, instrument is set up typical curve automatically, measures sample solution then under same condition of work, and instrument calculates the percentage composition of micro-coloring element in the ash discharge glass automatically.
Embodiment 2:
The determination and analysis process
Is 75 μ m sieves by the aperture with agate mortar extremely with smoked glass sample porphyrize, is stored in the measuring cup, in order to the usefulness of weighing.Sample in the measuring cup is put in sample sack, in thermostatic drying chamber, more than 1 hour, puts into exsiccator then, be cooled to room temperature, to treat weighing in 105-110 ℃ of oven dry.
Accurately take by weighing 0.70 gram (being accurate to ± 0.0001 gram) sample and in the platinum ware, use water-wet, add 1.5ml perchloric acid and 7ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette (silicon in the glass of rushing).Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette (silicon in the glass of further rushing is not in case catch up with clean).Cooling adds 8ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, be diluted with water to scale, acidity is 4%.
The preparation of blank test solution:
In the platinum ware, add 1.5ml perchloric acid and 7ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette.Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette.Cooling adds 8ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, be diluted with water to scale.Acidity is 4%.
The preparation of standard solution:
Standard solution one: accurately take by weighing 0.7 gram (being accurate to ± 0.0001 gram) clear float glass and in the platinum ware, add 1.5ml perchloric acid and 7ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette.Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette.Cooling adds 8ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, add Fe, Co, Ni, Se standard solution 0,0.8,0.7,0.6ml that concentration is 100ppm respectively, be diluted with water to scale, shake up, obtain that Fe, Co, Ni, Se concentration are respectively 7,0.8,0.7, the 0.6ppm standard solution.Acidity is 4%.
Standard solution two: accurately take by weighing 0.7 gram (being accurate to ± 0.0001 gram) clear float glass and in the platinum ware, add 1.5ml perchloric acid and 7ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette.Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette.Cooling adds 8ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, add Fe, Co, Ni, Se standard solution 2,1.0,0.5,0.4ml that concentration is 100ppm respectively, be diluted with water to scale, shake up, obtain that Fe, Co, Ni, Se concentration are respectively 9,1.0,0.5, the 0.4ppm standard solution.Acidity is 4%.
Standard solution three: accurately take by weighing 0.7 gram (being accurate to ± 0.0001 gram) clear float glass and in the platinum ware, add 1.5ml perchloric acid and 7ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette.Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette.Cooling adds 8ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, add Fe, Co, Ni, Se standard solution 4,0.4,0.3,0.2ml that concentration is 100ppm respectively, be diluted with water to scale, shake up, obtain that Fe, Co, Ni, Se concentration are respectively 11,0.4,0.3, the 0.2ppm standard solution.Acidity is 4%.
Other analysis spectral line, operating parameter and condition are identical with embodiment 1.
Embodiment 3:
The determination and analysis process:
Is 75 μ m sieves by the aperture with agate mortar extremely with smoked glass sample porphyrize, is stored in the measuring cup, in order to the usefulness of weighing.Sample in the measuring cup is put in sample sack, in thermostatic drying chamber, more than 1 hour, puts into exsiccator then, be cooled to room temperature, to treat weighing in 105-110 ℃ of oven dry.
Accurately take by weighing 0.90 gram (being accurate to ± 0.0001 gram) sample and in the platinum ware, use water-wet, add 2.0ml perchloric acid and 10ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette (silicon in the glass of rushing).Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette (silicon in the glass of further rushing is not in case catch up with clean).Cooling adds 16ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, be diluted with water to scale.Acidity is 8%.
The preparation of blank test solution
In the platinum ware, add 2.0ml perchloric acid and 10ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette.Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette.Cooling adds 16ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, be diluted with water to scale.Acidity is 8%.
The preparation of standard solution
Standard solution one: accurately take by weighing 0.9 gram (being accurate to ± 0.0001 gram) clear float glass and in the platinum ware, add 2.0ml perchloric acid and 10ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette.Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette.Cooling adds 16ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, add Fe, Co, Ni, Se standard solution 5,0.8,0.2,0.2ml that concentration is 100ppm respectively, be diluted with water to scale, shake up, obtain that Fe, Co, Ni, Se concentration are respectively 14,0.8,0.2, the 0.2ppm standard solution.Acidity is 8%.
Standard solution two: accurately take by weighing 0.9 gram (being accurate to ± 0.0001 gram) clear float glass and in the platinum ware, add 2.0ml perchloric acid and 10ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette.Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette.Cooling adds 16ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, add Fe, Co, Ni, Se standard solution 0,0.6,0.4,0.6ml that concentration is 100ppm respectively, be diluted with water to scale, shake up, obtain that Fe, Co, Ni, Se concentration are respectively 9,0.6,0.4, the 0.6ppm standard solution.Acidity is 8%.
Standard solution three: accurately take by weighing 0.9 gram (being accurate to ± 0.0001 gram) clear float glass and in the platinum ware, add 2.0ml perchloric acid and 10ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette.Re-treatment once, the temperature that raises is gradually driven to the greatest extent white cigarette.Cooling adds 16ml hydrochloric acid (1+1) and suitable quantity of water, heating for dissolving.After the cooling, move into the 100ml volumetric flask, add Fe, Co, Ni, Se standard solution 2,0.2,0.6,0.8ml that concentration is 100ppm respectively, be diluted with water to scale, shake up, obtain that Fe, Co, Ni, Se concentration are respectively 11,0.2,0.6, the 0.8ppm standard solution.Acidity is 8%.
Other analysis spectral line, operating parameter and condition are identical with embodiment 1.
Claims (1)
1. method of utilizing plasma emission spectrometer to measure coloring element content in the grey glass simultaneously is characterized in that:
A, sample processing procedure are: will be that the smoked glass sample of 0.08mm sieve accurately takes by weighing the 0.5-0.9 gram and places the platinum ware through being ground to by the aperture, use water-wet, add 1ml-2ml perchloric acid and 5-10ml hydrofluorite, on low-temperature furnace, be evaporated to and emit white cigarette, in order to the silicon in the glass of rushing; And to sample by the above-mentioned steps re-treatment once, the temperature that raises gradually is not to there being Bai Yanzhi, with the silicon in the glass of further rushing; After being cooled to room temperature, add 1+1 hydrochloric acid and the suitable quantity of water of 4-20ml, heating for dissolving; After the cooling, move into the 100ml volumetric flask, be diluted with water to scale, make 2%≤acidity≤10%;
Prepare blank test solution: in the platinum ware, add the reagent of and equivalent identical, do moving into the 100ml volumetric flask after the processing identical, be diluted with water to scale, make 2%≤acidity≤10% with sample with the said sample processing procedure;
The preparation of standard solution: take by weighing 0.5-0.9 gram clear float glass respectively in the platinum ware, the reagent that adds and equivalent identical with the said sample processing procedure, move into the 100ml volumetric flask after doing the processing identical with sample, in volumetric flask, add Fe, Co, Ni, Se standard solution respectively, water is settled to graticule, thereby obtain and the essentially identical standard solution of sample, 2%≤acidity≤10%;
B, analysis spectral line are: Fe wavelength 261.187nm, Ni wavelength 216.555nm, Co wavelength 230.786nm, Se wavelength 196.026nm;
C, Instrument operation parameter are: atomization gas flow 0.75L/min, secondary air amount 15L/min, radio-frequency signal generator power 0.9KW, pump speed 15rpm, plasma (orifice) gas 15L/min, stabilization time 15s, sample promotes time 30s, atomizer scavenging period 10s, duplicate measurements number of times 3;
D, the machine of going up are measured: under the instrument condition of work of selecting, measure blank solution and standard solution, instrument is set up typical curve automatically, measures sample solution then under same condition of work, and instrument calculates the percentage composition of trace element in the ash discharge glass automatically.
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