CN109991304A - A method of measurement high-voltage electricity sub-light foil surface layer different-thickness lead content - Google Patents
A method of measurement high-voltage electricity sub-light foil surface layer different-thickness lead content Download PDFInfo
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Abstract
The present invention relates to field of material testing, and in particular to a method of measurement high-voltage electricity sub-light foil surface layer different-thickness lead content.The present invention is skimmed high-voltage electricity sub-light foil surface layer different-thickness using electrolysis method, and the lead content between the different-thickness that light foil is skimmed is calculated in the lead content after different-thickness of being skimmed respectively with ICP-MS measurement light foil.Compared with existing ion microprobe and glow discharge mass spectroscopy test method, the lead content of its surface layer different-thickness of energy Accurate Determining of the present invention, and also it is easy to operate, cost of determination is low.
Description
Technical field
The present invention relates to field of material testing, and in particular to a kind of measurement high-voltage electricity sub-light foil surface layer different-thickness lead content
Method.
Background technique
High-voltage electricity sub-light foil is as rafifinal through a kind of aluminium foil made from the processes such as founding, rolling and annealing, through electrification
It learns corrosion and formation process obtains Waste Acid From Hua Cheng Foil, Waste Acid From Hua Cheng Foil is the critical elements of aluminium electrolutic capacitor.Usual high-voltage electricity sub-light foil table
Layer contains a certain amount of lead, and when carrying out electrochemical corrosion, nearby there are a large amount of dislocations and primary batteries for the lead particle on light foil surface layer
Effect, so that lead particle easily becomes the starting point of hair engaging aperture, to draw the corrosion of electroluminescent foil.Due to lead foil surface layer content and
Hair engaging aperture density and uniformity coefficient when distribution situation will affect corrosion, and then influence the ratio of the Waste Acid From Hua Cheng Foil obtained after corrosion chemical conversion
Hold.Therefore, the lead content of high-voltage electricity sub-light foil surface layer different-thickness is measured extremely important with control.
The prior art generally uses ion microprobe or glow discharge mass spectroscopy to carry out the lead content on light foil surface layer
Analysis.But ion microprobe and glow discharge mass spectroscopy can only carry out qualitative analysis, and what is obtained is lead content with thickness
Variation tendency is unable to get the truthful data of lead content.And both instrument prices are expensive, common laboratory does not have the measurement
Condition.
Lead contains in Chinese patent CN103364482 micro-wave digestion Inductively coupled plasma mass spectrometry measurement medicinal aluminum foil
Amount, what is obtained is the lead content of aluminium foil entirety, cannot obtain the lead content of aluminium foil surface layer different-thickness, thus directly use this method without
Method measures the lead content on high-voltage electricity sub-light foil surface layer.Because Inductively coupled plasma mass spectrometry (ICP-MS) is to sample extension rate
Limitation, it is only 0.002-0.05ppb that high-voltage electricity sub-light foil, which polishes test solution lead content made of rear, and this method
Lead element detection is limited to 0.09ppb, and lower than its detection limit, therefore this method can not be used to measure high-voltage electricity sub-light foil surface layer difference
The lead content of thickness.
The method cost that the prior art detects high-voltage electricity sub-light foil surface layer lead content is very high, and without standard measure, therefore having must
A kind of method for developing lead content that can quantitative, inexpensive, easily measure high-voltage electricity sub-light foil surface layer different-thickness.
Summary of the invention
The object of the present invention is to provide a kind of methods for measuring high-voltage electricity sub-light foil surface layer different-thickness lead content.This method
The lead content of its surface layer different-thickness of energy Accurate Determining, and it is easy to operate, and cost of determination is low.
In order to achieve the above objectives, the technical solution of use are as follows: a kind of measurement high-voltage electricity sub-light foil surface layer different-thickness lead contains
The method of amount, comprising:
1), the polishing treatment of sample: high-voltage electricity sub-light foil to be measured is cut into the identical n item of forming shape, is divided after decontamination annealing
Not carry out electrobrightening, keep polishing electric current and polishing area it is constant, successively increase polishing time, obtain different-thickness of skimming
Light chaff；Wherein, the thickness A of skimming of first light chaff1It is 0, nth light chaff is skimmed with a thickness of An, n >=2；
2), the preparation of standard solution: weighing the low lead aluminium foil 0.1g of lead content < 10ppb, with aqua regia dissolution, and with ultrapure
Water dilutes to obtain 500g solution；Again with acquired solution by the lead standard solution of 100ppb be diluted to respectively lead content be 0,0.1,0.2,
0.5, the standard solution of 1ppb；
3), the preparation of test solution: the polishing position D of step 1) nth light chaff is cutnG, with aqua regia dissolution, and
It is diluted to obtain E with ultrapure waternG test solution；
4) test solution of standard solution, step 3) preparation that step 2) is prepared is measured respectively with ICP-MS, is used
Calibration curve method carries out quantitative and introduces Internal standard correction methods online, obtains the content of lead in test solution；
5) thickness A that nth light chaff is skimmed, is calculated according to formula 1n；
An=10000*Tn* I*M/ (ρ * F*S*2) formula 1
In formula 1:
ρ-aluminium density is 2.7g/cm3；
Tn-nth light chaff polishing time, unit s；
I-polishing electric current, unit A；
M-aluminium molal weight is 27g/mol；
S-polishing area, unit cm2；
F-Faraday constant is 96485C/mol；
The thickness A skimmed of nth light chaff is calculated to obtain according to formula 2nThe thickness A skimmed with (n-1)th light chaffn-1Between
Lead content ωn；
ωn=[(A-An-1*2)*En-1*Cn-1/Dn-1-(A-An*2)*En*Cn/Dn]/[(An-1-An) * 2] formula 2
In formula 2:
A-light foil original thickness, unit are μm；
An-1The thickness that-the (n-1)th light chaff is skimmed, unit are μm；
AnThe thickness that-nth light chaff is skimmed, unit are μm；
Dn-1The sampling quality at-the (n-1)th light chaff polishing position, unit g；
En-1The quality of the test solution of-the (n-1)th light chaff polishing position sampling preparation, unit g；
Dn- nth light chaff polishes the sampling quality at position, unit g；
En- nth light chaff polishes the quality of the test solution of position sampling preparation, unit g；
Cn-1The lead content of the test solution of-the (n-1)th light chaff polishing position sampling preparation, unit g/g；
Cn- nth light chaff polishes the lead content of the test solution of position sampling preparation, unit g/g.
It is in its five face (left and right side, bottom surface, front and back sides) while to carry out to the polishing of high-voltage electricity sub-light chaff, due to light
For foil with a thickness of micron order, the area of light chaff left and right side and bottom surface is too small relative to front and back sides, influences less, therefore counts on result
It is approximately considered the part that light chaff is skimmed when calculation and is all located at tow sides.
Preferably, the method for the described measurement high-voltage electricity sub-light foil surface layer different-thickness lead content, described in step 1)
Polish electric current 0.1-10A, the polishing time 1-60s.
Preferably, the method for the described measurement high-voltage electricity sub-light foil surface layer different-thickness lead content, described in step 1)
Polishing fluid is the mixed liquor of perchloric acid and ethyl alcohol.
Preferably, the method for the described measurement high-voltage electricity sub-light foil surface layer different-thickness lead content, described in step 1)
Polishing fluid is dehydrated alcohol and azeotropic the perchloric acid mixed liquor that 9:l is formed by volume.
Preferably, the method for the measurement high-voltage electricity sub-light foil surface layer different-thickness lead content, which is characterized in that step
It is rapid 3) described in Dn be 0.018-0.022g, the chloroazotic acid be 2mL, the test solution quality En be 90-110g.
Preferably, the method for the measurement high-voltage electricity sub-light foil surface layer different-thickness lead content, described in step 4)
ICP-MS measurement operating condition it is as follows:
Analytical model: collisionless reaction gas mode
Radio-frequency power: 1500w plasma gas flow velocity: 15L/min
Flow rate of carrier gas: 0.76L/min compensation gas flow velocity: 0.36L/min
It is atomized room temperature: 2 DEG C of wriggling revolution speeds: 0.1rp s
Stablize the time: 20s sample promotes the time: 15s
Acquisition mode: mass spectrogram sampling depth: 6.0mm
The time of integration: 1.2s determines peak type taken point number: 3
Repeated sampling number: 3 scannings/number of repetition: 10.
Preferably, the method for the measurement high-voltage electricity sub-light foil surface layer different-thickness lead content, described in step 4)
ICP-MS measurement, test before sucking step 2) in lead content be 1ppb standard solution, instrument is tuned, will be tuned
Monitoring quality is changed to208Pb, and will208The sensitivity of Pb is adjusted to maximum value.
Preferably, the method for the measurement high-voltage electricity sub-light foil surface layer different-thickness lead content, step 4) is into for examination
When product solution, 20s takes out sample introduction needle before reading is completed, and is put into rinse solution.
Preferably, the method for the measurement high-voltage electricity sub-light foil surface layer different-thickness lead content, further includes walking as follows
It is rapid: by the low lead aluminium foil of lead content < 10ppb with aqua regia dissolution, 500g solution being diluted to obtain with ultrapure water；And it will with acquired solution
The lead standard solution of 100ppb is diluted to the solution that lead content is 0.001,0.002,0.005,0.01ppb respectively, uses ICP-MS
Lead content is measured, the recovery of standard addition of lead is calculated；The rate of recovery be considered as between 70-130% can accurate quantitative analysis, taking accurately to determine
The minimum content of amount is final quantitative limit, obtains the quantitative limit of measuring method.It is further preferred that the step is before step 4)
It carries out.
Preferably, the method for the measurement high-voltage electricity sub-light foil surface layer different-thickness lead content, further includes walking as follows
It is rapid: to take the standard solution prepared in step 2) to measure lead content with ICP-MS, calculate the relative standard of measurement result in triplicate
Deviation.It is further preferred that the step carries out before step 4).
Preferably, the method for the measurement high-voltage electricity sub-light foil surface layer different-thickness lead content, further includes walking as follows
It is rapid: by the method in step 3), to prepare 6 parts of parallel samples and measured with ICP-MS, calculate average value and the relative standard of lead content
Deviation.It is further preferred that the step carries out before step 4).
Preferably, the method for the measurement high-voltage electricity sub-light foil surface layer different-thickness lead content, further includes walking as follows
It is rapid: the polishing position 0.02g of step 1) any bar light chaff is cut, with 2mL aqua regia dissolution, and is diluted to 100g with ultrapure water,
9 parts of parallel test solutions are prepared, the lead of 0.1,0.1,0.1,0.2,0.2,0.2,0.3,0.3,0.3g100ppb is separately added into
Standard solution measures its lead content with ICP-MS instrument, calculate detection method average recovery of standard addition.It is further preferred that
The step carries out before step 4).
Preferably, the method for the measurement high-voltage electricity sub-light foil surface layer different-thickness lead content, further includes walking as follows
It is rapid: take step 1) any bar light chaff, weigh it and polish position 0.02g, parallel 9 parts of preparation, be separately added into 0.1,0.1,0.1,
0.2, the lead standard solution of 0.2,0.2,0.3,0.3,0.3g 100ppb, adds chloroazotic acid 2mL, is heated to sample and is completely dissolved,
Then it cools down, being diluted to solution gross mass with ultrapure water is 100g, measures its lead content with ICP-MS respectively, calculates to obtain pre-treatment
The average recovery of standard addition of method.It is further preferred that the step carries out after the average recovery of standard addition of detection method.
The invention has the benefit that
1) it, is skimmed the light foil of high-voltage electricity sub-light foil surface layer different-thickness using electrobrightening, is skimmed not with ICP-MS measurement
The lead content of light foil after stack pile subtracts each other to obtain the lead content between the different-thickness, and light can not be measured with ICP-MS by overcoming
The defect of foil surface layer lead content.
2), using aqua regia dissolution's light foil, conventional microwave resolution is avoided largely with acid and repeatedly transfer bring pollution.
3) it, is tuned for lead element, it will208The sensitivity of Pb is adjusted to maximum value, and quantitative limit makes down to 0.002ppb
Its testing requirements that can satisfy electronic light foil surface layer lead content.
4) detection method, is assessed to the detectability of low lead content sample by calculating lead recovery of standard addition, is obtained
Quantitative limit more precise and reliable.
Term definition
The invention is intended to cover all replacement, modification and equivalent technical solutions, they are included in as claim is fixed
In the scope of the invention of justice.Those skilled in the art will appreciate that many and similar or equivalent method and material described herein
It can be used in the practice present invention.The present invention is not limited to method described herein and material.In document, patent and the class combined
One or more or contradict in the case where (including but not limited to defined in terms, term different from the application like material
Using, described technology etc.), it is subject to the application.
It will further be appreciated that certain features of the invention, be it is clearly visible, carry out in a number of independent embodiments
Description, but can also provide in combination in a single embodiment.Conversely, various features of the invention, for brevity,
It is described, but can also be provided individually or with any appropriate sub-portfolio in a single embodiment.
Unless otherwise stated, all scientific and technical terminologies used in the present invention have with those skilled in the art of the invention's
It is generally understood identical meaning.All patents of the present invention and public publication are integrally incorporated this hair by reference
It is bright.
Specific embodiment
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to following preferred implementation side
Formula.It should be pointed out that for those skilled in the art on the basis of the inventive concept, several deformations for making and
It improves, belongs to protection scope of the present invention.Raw material used in embodiment can be obtained through commercial channels.
Embodiment 1
Instrument and reagent used in the embodiment of the present invention:
Agilent 8800s icp ms, a ten thousandth electronic balance, electric hot plate, ultrapure water machine, directly
Galvanic electricity source, electrolytic buffing attachment, Muffle furnace, 100mL PFA beaker, FEP bottles of 50mL, (FEP bottles and PFA are burnt FEP bottles of 500mL
Cup nitric acid reflow treatment).
Chloroazotic acid, the lead standard solution of Merck 100ppb, dehydrated alcohol (analysis is pure), azeotropic perchloric acid (analysis is pure),
100ppb's209Bi mixing inner mark solution, low lead aluminium foil (Pb content < 10ppb), high-voltage electricity sub-light foil to be measured.
Wherein 1:3 is live by volume by secondary sub- boiling purifying, the concentrated nitric acid of Pb content < 0.01ppb and concentrated hydrochloric acid for chloroazotic acid
It is formulated；The 100ppm lead element standard solution mother liquor that the lead standard solution of 100ppb is produced by Merck & Co., Inc. dilutes；
The 10ppm mixing inner mark solution mother liquor that mixing inner mark solution is produced by agilent company dilutes.
Table 1, instrument parameter setting
As described below is a specific embodiment of the invention.
1, the polishing treatment of sample: the high-voltage electricity sub-light foil to be measured of 125 μ m-thicks is cut into the strip of 9 10*3cm, is gone
After degreasing, anneal 3h at 500 DEG C, is then flattened with smooth glass, places into 500 DEG C of annealing 6h in Muffle furnace；With nothing
Water-ethanol and the azeotropic perchloric acid mixed liquor that 9:l is formed by volume are as electrolytic polishing liquid, and the light foil of annealing is as sun
Pole, stainless steel plate carry out electrobrightening as cathode, to the 2*3cm of light foil lower half portion, and polishing electric current is 2.32A, when polishing
Between be respectively 0 (not polishing), 1,2,5,10,15,20,25,30s, after the completion of polishing, clean up, dry, obtain skimming not
The light chaff of stack pile, thickness results of skimming are shown in Table 4.
2, the preparation of standard solution: taking the low lead aluminium foil of 0.1g, and 10mL aqua regia dissolution is added, is diluted to obtain 500g with ultrapure water
Solution.Take the lead standard solution of appropriate 100ppb in 50mLFEP bottles, with above-mentioned low lead aluminium foil solution be diluted to lead content be 0,
0.1, the standard solution of 0.2,0.5,1ppb.
Since the memory effect that the standard solution of high-content generates can remain the long period in instrument sampling system, to rear
The detection of continuous test sample interferes, and lead content is extremely low in test sample, therefore the lead content range of standard solution correspondingly selects
The 0.1-1ppb of low concentration.
3, the preparation of test solution: each 0.02g in polishing position of 9 light chafves in step 1 is cut, 100mLPFA is placed in
In beaker, 2mL chloroazotic acid is added, in being heated to being completely dissolved on electric hot plate, cooling is diluted to 100g with ultrapure water, obtains by throwing
The test solution for going the light chaff of different-thickness to prepare.
Main solute is the alchlor that aluminium is transformed in test solution, to meet instrument in test solution
The requirement (< 0.2%) of solubles content, sampling amount selects 0.02g, and dilutes 5000 times, so that soluble matter trichlorine in test sample
The content for changing aluminium is 0.1%.
Since aluminium foil is sheet, the very little inconvenient sampling of 0.02g mass, actual sampling and weighing operating process are had centainly
Error, therefore sampling quality range is set to 0.02 ± 10%g, the test solution mass range that ultrapure water dilutes is
100 ± 10%g.Actual sampling quality DnWith test solution quality EnIt is shown in Table 4.
Experiment discovery, the effect of aqua regia dissolution's aluminium foil is best, and the reagent that can obtain high-purity (prepares the nitre that chloroazotic acid is used
Acid and hydrochloric acid Pb content are below 0.01ppb), it is less than 0.0002ppb by the reagent blank after the dilution of this experimental program, is lower than instrument
Device detection limit, and because lead element mass number is larger, the elements such as chlorine, nitrogen for introducing in chloroazotic acid will not cause matter to the detection of lead element
Spectrum interference.When chloroazotic acid is 2mL, sample can be completely dissolved, then not all right when less, in order to reduce reagent blank, need to be used to the greatest extent
The acid that may lack, therefore acid adding amount selects 2mL.Electronic light foil purity is 99.99% or more, and using when aqua regia dissolution, there is no insoluble
Object.And conventional micro-wave digestion need to be readily incorporated pollution largely with acid and multiple transfer sample.
Volumetric flask not acid corrosion-resistant, and repeatedly transfer sample is readily incorporated pollution, therefore select, use quantitative with PFA beaker
One step dilutes in place.
4, instrument is lighted a fire, and after the completion of preheating, instrument parameter such as table 1 is arranged, and sucks the standard that lead content in step 2 is 1ppb
Solution is tuned instrument, optimizes without using the global sensitivity of recommendation, and tuning monitoring quality manual is changed to208Pb, and
It will208The sensitivity of Pb is adjusted to maximum value, ignores the sensitivity of other elements；Internal standard sample feeding pipe is put into mixing inner mark solution, and
It is whole during the test to keep, to correct systematic error and monitoring instrument state.
5, standard solution is linear: the lead standard solution of different content in aspiration step 2 is measured with ICP-MS, obtains lead
Standard working curve；Related coefficient is 0.9998, and the linear relationship of description standard curve is good.
Because sample channel is longer, test solution when normal pump speeds in pipeline needs 25s to get to plasma, for contracting
Short sample injection time is alleviated sampling spiroid and interception taper hole blocking, sample feeding pipe is cut most short.It is found in test process, when sample mentions
When the liter time is 14s, sample reaches exactly to plasma, therefore sample promotes selection of time 15s, stablizes selection of time 20s, is reading
It counts up into preceding 20s and sample introduction needle taking-up is put into rinse solution, detection will not influence using the measure, can also substantially alleviate taper hole
Blocking.
6, system suitability: the test solution for taking the light chaff that polishing time is 0 in step 3 to prepare is surveyed with ICP-MS
Fixed, obtaining the internal standard rate of recovery is 98.2%, and system suitability is good, continuously into after 50 needle test solutions, the internal standard rate of recovery
82.6%, instrument state is stablized, and sampling spiroid does not occur and intercepts the phenomenon that cone blocking plug causes sensitivity to decline.
7, quantitative limit: taking the low lead aluminium foil of 0.1g to be placed in 500mLFEP bottles, and 10mL aqua regia dissolution is added, is diluted with ultrapure water
To 500g, take the lead standard solution of appropriate 100ppb in 50mLFEP bottles, with above-mentioned low lead aluminium foil solution by lead standard solution
It is diluted to the solution that lead content is 0.001,0.002,0.005,0.01ppb respectively, measures its lead content using ICP-MS, calculates
The recovery of standard addition of lead, the results are shown in Table 2.Retain the rate of recovery after the content of 70-130%, excluding outlier, quantitative limit is chosen
Can accurate quantitative analysis minimum content, obtain quantifying for detection method and be limited to 0.002ppb.
8, Precision Experiment: to take lead content in step 2 be 0.1,0.2, the standard solution sample introduction of 0.5ppb three times, use ICP-
MS measures lead content, calculates the relative standard deviation of testing result, respectively 1.5%, 1.6%, 1.2%, the essence of illustration method
Density is good.
9, it repeated experiment: takes the light chaff that polishing time is 0 to prepare 6 parts of parallel samples by step 3, is measured with ICP-MS
Lead content, calculating lead content average value are 0.241ppb, and the repeatability of relative standard deviation 1.9%, illustration method is good.
10, detection method recovery of standard addition is tested: taking polishing time is 0 light chaff 0.02g, is placed in 100mLPFA beaker
In, 2mL chloroazotic acid is added, prepares 9 parts of parallel samples, in being heated to being completely dissolved on electric hot plate, cooling is diluted to ultrapure water
100g measures lead content with ICP-MS, calculates average recovery rate value, the results are shown in Table 3, respectively 100.3%, 99.2%,
98.7%, illustrate that the detection method rate of recovery is good, the testing result obtained using the detection method is accurate.
11, pre-treating method recovery of standard addition is tested: taking 9 parts of polishing times is 0 each 0.02g of light chaff, is placed in
In 100mLPFA beaker, be separately added into 0.1,0.1,0.1,0.2,0.2,0.2,0.3,0.3, the lead standard of 0.3g 100ppb it is molten
Liquid adds chloroazotic acid 2mL, is heated to sample and is completely dissolved, and cooling, being diluted to solution gross mass with ultrapure water is 100g, uses
ICP-MS measures lead content, calculates average recovery rate, the results are shown in Table 3, respectively 97.4%, 98.7%, 98.3%, with detection side
Method recovery of standard addition is consistent, illustrates that the pretreatment mode rate of recovery of this measuring method is good, almost without lead in pretreatment process
Element loss.
12, the thickness A that n-th of smooth chaff is skimmed is calculated according to formula 1n, the results are shown in Table 4；
An=10000*Tn* I*M/ (ρ * F*S*2) formula 1
In formula 1:
ρ-aluminium density, unit 2.7g/cm3；
TnThe polishing time of-nth light chaff, unit s；
I-polishing electric current, unit A；
M-aluminium molal weight is 27g/mol；
S-polishing area, unit cm2；
F-Faraday constant is 96485C/mol；
The thickness A that nth light chaff is skimmed is calculated according to formula 2nThe thickness A skimmed with (n-1)th light chaffn-1Between
Lead content ωn, the lead content of its different-thickness is obtained, the results are shown in Table 4；
ωn=[(A-An-1*2)*En-1*Cn-1/Dn-1-(A-An*2)*En*Cn/Dn]/[(An-1-An) * 2] formula 2
In formula:
A-light foil original thickness, unit are μm；
An-1The thickness that-the (n-1)th light chaff is skimmed, unit are μm；
AnThe thickness that-nth light chaff is skimmed, unit are μm；
Dn-1The sampling quality at-the (n-1)th light chaff polishing position, unit g；
En-1The quality of the test solution of-the (n-1)th light chaff polishing position sampling preparation, unit g；
Dn- nth light chaff polishes the sampling quality at position, unit g；
En- nth light chaff polishes the quality of the test solution of position sampling preparation, unit g；
Cn-1The lead content of the test solution of-the (n-1)th light chaff polishing position sampling preparation, unit g/g；
Cn- nth light chaff polishes the lead content of the test solution of position sampling preparation, unit g/g；
It is in its five face (left and right side, bottom surface, front and back sides) while to carry out to the polishing of high-voltage electricity sub-light chaff, due to light
For foil with a thickness of micron order, the area of light chaff left and right side and bottom surface is too small relative to front and back sides, influences less, therefore counts on result
It is approximately considered the part that light chaff is skimmed when calculation and is all located at tow sides.
2 quantitative limit experimental data of table
| Number | Mark-on content (ppb) | It surveys content (ppb) | Matrix content (ppb) | The rate of recovery | Whether pass through |
| 1 | 0.0010 | 0.0026 | 0.0020 | 63.2% | Do not pass through |
| 2 | 0.0020 | 0.0037 | 0.0020 | 83.4% | Pass through |
| 3 | 0.0050 | 0.0073 | 0.0020 | 106.2% | Pass through |
| 4 | 0.0100 | 0.0116 | 0.0020 | 96.2% | Pass through |
3 recovery of standard addition experimental data of table
The calculated result of 4 high voltage electronic aluminum foil different-thickness lead content of table
| Number | Tn(s) | An(um) | Dn(g) | En(g) | Cn(ppb) | ωn(ppb) |
| 1 | 0 | 0 | 0.0215 | 100.0524 | 0.2611 | N/A |
| 2 | 1 | 0.2 | 0.0182 | 100.2912 | 0.1388 | 141230 |
| 3 | 2 | 0.4 | 0.0201 | 100.2321 | 0.1133 | 62794 |
| 4 | 5 | 1 | 0.0198 | 100.2989 | 0.0622 | 26160 |
| 5 | 10 | 2 | 0.0206 | 100.0234 | 0.0210 | 13186 |
| 6 | 15 | 3 | 0.0189 | 100.0142 | 0.0098 | 3073 |
| 7 | 20 | 4 | 0.0211 | 100.0561 | 0.0063 | 1337 |
| 8 | 25 | 5 | 0.0203 | 100.1237 | 0.0057 | 145 |
| 9 | 30 | 6 | 0.0196 | 100.1023 | 0.0049 | 141 |
By the data of table 2-4 it is found that measurement high-voltage electricity sub-light foil surface layer different-thickness lead content provided by the present invention
Method, quantitative limit is low, and precision is good, reproducible, as a result accurately.
Claims (10)
1. a kind of method for measuring high-voltage electricity sub-light foil surface layer different-thickness lead content characterized by comprising
1), the polishing treatment of sample: cutting the identical n item of forming shape for high-voltage electricity sub-light foil to be measured, after decontamination annealing respectively into
Row electrobrightening keeps polishing electric current and polishing area constant, successively increases polishing time, the light foil for the different-thickness that obtains skimming
Item；Wherein, the thickness A of skimming of first light chaff1It is 0, nth light chaff is skimmed with a thickness of An, n >=2；
2), the preparation of standard solution: weighing the low lead aluminium foil 0.1g of lead content < 10ppb, with aqua regia dissolution, and it is dilute with ultrapure water
Release to obtain 500g solution；Again with acquired solution by the lead standard solution of 100ppb be diluted to respectively lead content be 0,0.1,0.2,0.5,
The standard solution of 1ppb；
3), the preparation of test solution: the polishing position D of step 1) nth light chaff is cutnG, with aqua regia dissolution, and with super
Pure water dilutes to obtain EnG test solution；
4) test solution of the standard solution, step 3) preparation that, take step 2) to prepare respectively carries out ICP-MS measurement, using mark
Directrix curve method carries out quantitative and introduces Internal standard correction methods online, obtains the content of lead in test solution；
5) thickness A that nth light chaff is skimmed, is calculated according to formula 1n；
An=10000*Tn* I*M/ (ρ * F*S*2) formula 1
In formula 1:
ρ-aluminium density is 2.7g/cm3；
TnThe polishing time of-nth light chaff, unit s；
I-polishing electric current, unit A；
M-aluminium molal weight is 27g/mol；
S-polishing area, unit cm2；
F-Faraday constant is 96485C/mol；
The thickness A skimmed of nth light chaff is calculated to obtain according to formula 2nThe thickness A skimmed with (n-1)th light chaffn-1Between lead content
ωn；
ωn=[(A-An-1*2)*En-1*Cn-1/Dn-1-(A-An*2)*En*Cn/Dn]/[(An-1-An) * 2] formula 2
In formula 2:
A-light foil original thickness, unit are μm；
An-1The thickness that-the (n-1)th light chaff is skimmed, unit are μm；
AnThe thickness that-nth light chaff is skimmed, unit are μm；
Dn-1The sampling quality at-the (n-1)th light chaff polishing position, unit g；
En-1The quality of the test solution of-the (n-1)th light chaff polishing position sampling preparation, unit g；
Dn- nth light chaff polishes the sampling quality at position, unit g；
En- nth light chaff polishes the quality of the test solution of position sampling preparation, unit g；
Cn-1The lead content of the test solution of-the (n-1)th light chaff polishing position sampling preparation, unit g/g；
Cn- nth light chaff polishes the lead content of the test solution of position sampling preparation, unit g/g.
2. the method for measurement high-voltage electricity sub-light foil surface layer different-thickness lead content as described in claim 1, which is characterized in that step
It is rapid 1) described in polishing electric current be 0.1-10A, polishing time 1-60s.
3. the method for measurement high-voltage electricity sub-light foil surface layer different-thickness lead content as described in claim 1, which is characterized in that step
It is rapid 3) described in DnFor 0.018-0.022g, the chloroazotic acid is 2mL, the test solution quality EnFor 90-110g.
4. the method for measurement high-voltage electricity sub-light foil surface layer different-thickness lead content as described in any one of claims 1-3, special
Sign is that the operating condition of the measurement of ICP-MS described in step 4) is as follows:
Analytical model: collisionless reaction gas mode
5. the method for measurement high-voltage electricity sub-light foil surface layer different-thickness lead content as claimed in claim 4, which is characterized in that step
It is rapid 4) described in ICP-MS measurement, test before sucking step 2) in lead content 1ppb standard solution, instrument is adjusted
It is humorous, tuning monitoring quality is changed to208Pb, and will208The sensitivity of Pb is adjusted to maximum value.
6. the method for measurement high-voltage electricity sub-light foil surface layer different-thickness lead content as described in claim 1, which is characterized in that institute
The method of stating further includes following steps: by the low lead aluminium foil of lead content < 10ppb with aqua regia dissolution, with ultrapure water dilute 500g is molten
Liquid；And with acquired solution by the lead standard solution of 100ppb be diluted to respectively lead content be 0.001,0.002,0.005,
The solution of 0.01ppb measures its lead content with ICP-MS, calculates recovery of standard addition；Recovery of standard addition is between 70-130%
Be considered as can accurate quantitative analysis, take can accurate quantitative analysis minimum content be final quantitative limit, obtain the quantitative limit of measuring method.
7. the method for measurement high-voltage electricity sub-light foil surface layer different-thickness lead content as described in claim 1, which is characterized in that institute
The method of stating further includes following steps: taking the standard solution prepared in step 2) to measure lead content with ICP-MS, calculates in triplicate
Obtain the relative standard deviation of measurement result.
8. the method for measurement high-voltage electricity sub-light foil surface layer different-thickness lead content as described in claim 1, which is characterized in that institute
The method of stating further includes following steps: by the preparation of the test solution described in step 3), the parallel test solution of 6 parts of preparation is used
ICP-MS measures its lead content, calculate lead content average value and relative standard deviation.
9. the method for measurement high-voltage electricity sub-light foil surface layer different-thickness lead content as claimed in claim 3, which is characterized in that institute
The method of stating further includes following steps: the polishing position 0.02g for cutting step 1) any bar light chaff is used in combination with 2mL aqua regia dissolution
Ultrapure water is diluted to 100g, prepares 9 parts of parallel test solutions, be separately added into 0.1,0.1,0.1,0.2,0.2,0.2,0.3,
0.3,0.3g content is the lead standard solution of 100ppb, measures its lead content with ICP-MS, calculate detection method average plus
Mark the rate of recovery.
10. the method for measurement high-voltage electricity sub-light foil surface layer different-thickness lead content as claimed in claim 9, which is characterized in that
The method also includes following steps: the polishing position 0.02g of step 1) any bar light chaff is cut, parallel 9 parts of preparation, respectively
0.1,0.1,0.1,0.2,0.2,0.2,0.3,0.3, the lead standard solution that 0.3g content is 100ppb is added, it is molten with 2mL chloroazotic acid
Solution, and being diluted to solution quality with ultrapure water is 100g, measures its lead content respectively with ICP-MS, calculates to obtain pre-treating method
Average recovery of standard addition.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111077267A (en) * | 2020-01-14 | 2020-04-28 | 东莞东阳光科研发有限公司 | Method for measuring lead content in electronic optical foil |
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| CN102539517A (en) * | 2010-12-24 | 2012-07-04 | 北京有色金属研究总院 | Layer-by-layer analysis method for surface layer of copper alloy material |
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| CN111077267A (en) * | 2020-01-14 | 2020-04-28 | 东莞东阳光科研发有限公司 | Method for measuring lead content in electronic optical foil |
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