CN117907562B - Method for simultaneously detecting contents of multiple elements in coating - Google Patents
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
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Abstract
The invention relates to the technical field of detection, in particular to a method for simultaneously detecting the contents of various elements in a coating, which comprises the following steps: 1) Pretreating a sample to be tested; 2) Glow discharge spectrometry; 3) Standardization treatment; 4) And (5) quantitatively converting. The method can realize quantitative detection of trace elements with the content of 0.001 g/m 2 order of magnitude or below, greatly improves the detection precision, can obtain the quality of various elements at the same time, has the detection result free from the interference of trace elements in a matrix, simplifies the detection steps, avoids a large amount of experimental errors, and can realize the purposes of batch detection and accurate detection.
Description
Technical Field
The invention relates to the technical field of detection, in particular to a method for simultaneously detecting the contents of various elements in a coating.
Background
Tin plate is widely used in the field of food packaging due to its bright and attractive appearance and excellent corrosion resistance and welding properties. However, in the production process of the tin plate, lead and tin are deposited at close potentials, so that trace lead impurities often exist in the tin plate, and the Pb element content in the tin plate of food is required to be not higher than 100 ppm. In addition, in order to improve the corrosion resistance, oxidation resistance and adhesion of tin plate, the tin plate is usually subjected to one-step chromate passivation, and the Cr content in the passivation layer is closely related to the finished product coating performance. Therefore, accurate determination of Cr and Pb contents in the plated tin plate is very necessary.
Chinese patent document CN108760654a discloses a method for rapidly determining the content of lead element in a tin plate coating, however, the pretreatment steps of the graphite furnace atomic absorption spectrometry adopted by the method are complicated, the experimental condition requirements are high, the precision cannot be ensured, the matrix interference is large, and the background absorption needs to be corrected by adding a suitable matrix improver and using a matrix solution containing no element to be detected. Chinese patent document CN107290374a discloses a method for detecting lead content in a plating layer of a cold-rolled tin-plated steel plate, but the adopted fluorescence spectrometer is inevitably affected by lead in a substrate during measurement, and the accuracy of measuring the lead content in the plating layer is limited.
Glow discharge atomic emission spectrometry is a spectroscopic analysis technique developed based on the principle of inert gas discharge at low pressure. The method is suitable for solid analysis, can strip samples layer by layer, and is an ideal analysis means for plating analysis. However, the glow discharge mass spectrometer can only perform qualitative analysis, the trend of the lead content along with the thickness is obtained, and the real data of the lead content cannot be obtained. The chinese patent document CN111426642a discloses a method for measuring the plating layer distribution and the element quality of the galvanized sheet by using a direct current glow discharge atomic emission spectrometry, which is mainly used for obtaining a curve of percentage content of each element in the sheet versus depth, and if the obtained relative content-depth distribution curve is to be converted into an element quality detection result, a normalization process (that is, it is converted by a sputtering rate) is required, however, it does not indicate how to normalize data by the sputtering rate conversion and convert the relative content into the element quality, so how to quantitatively analyze the content of trace elements in the plating layer by using the glow discharge atomic emission spectrometry is still a problem to be solved. In addition, the method needs to adopt standard samples with determined concentration to carry out drift correction every day, the standard curves of all elements are corrected regularly, the operation is still complex and complicated, the galvanized quantity of the galvanized sheet is measured, the zinc element content in the galvanized sheet is high, the detection of the order of magnitude is realized by the traditional methods such as a chemical method, an ICP method and the like, the high-precision detection can be realized, and whether the trace elements with the content of the order of magnitude of 0.001 g/m 2 or below can be detected or not can not be known according to the implementation scheme.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the existing glow discharge atomic emission spectrometry lacks a method for quantitatively analyzing the content of trace elements in a coating, so as to provide a method for simultaneously detecting the content of multiple elements in the coating.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for simultaneously detecting the contents of a plurality of elements in a plating layer, comprising:
1) Pretreating a sample to be tested;
2) Glow discharge spectrometry: performing element depth analysis on the pretreated sample to be detected by adopting a glow discharge spectrometer, and obtaining a distribution curve of the relative content of each element from the surface to the matrix;
3) And (3) standardization treatment: detecting the content of a certain high-content easily-detected element in a sample to be detected by adopting an electrochemical method to obtain an electrolysis E-t curve of the sample to be detected, setting the last two inflection points of the electrolysis E-t curve to be t 1 and t 2 respectively, and converting the content m of the high-content easily-detected element in a unit area plating layer by using Faraday's law: m=10000× [ t 1+2/3(t2-t1) ]×m×j/(n×f); wherein t 1＜t2, M is the content of high-content easily-detected elements in the unit area plating layer, M is the molar mass of the high-content easily-detected elements, J is the electrolysis current density, n is the electron transfer number, and F is the Faraday constant;
4) Quantitative conversion: setting the sputtering depth of a point with high content and easy detection of the relative content of the element reduced to 1% as h; and integrating the element curves in the integration interval of [0, h ] to obtain the relative content of each element, and converting the relative content of each element according to the proportional relation between the content of the high-content easily-detected element and the relative content of each element obtained by the standardized treatment.
Preferably, the sample to be tested is a tinplate coating; each element in the tinning plate coating is Sn, cr, pb and Fe; the tin plate coating has high content and is easy to detect element Sn.
Preferably, the pretreatment comprises: and carrying out infiltration treatment, washing, drying and cutting treatment on the sample to be tested.
Preferably, the impregnating compound adopted in the impregnating treatment is weak alkali salt; the weak alkali salt is generated by weak acid and strong alkali, and has weak alkalinity;
And/or the concentration of the impregnating compound adopted in the impregnating treatment is 80-90 g/L;
And/or, the temperature of the infiltration treatment is 40-50 ℃;
and/or the duration of the infiltration treatment is 3-4 min.
Preferably, the washing agent used for the washing is water;
and/or, the drying treatment adopts cold air drying;
and/or, the cutting process cuts the sample to be tested into 30 mm multiplied by 30 mm small samples.
Preferably, the weak base salt is carbonate or/and phosphate;
and/or the concentration of the impregnating compound is 85 g/L.
Preferably, the weak base salts are carbonates and phosphates;
and/or, the carbonate is sodium carbonate;
And/or, the phosphate is sodium phosphate.
Preferably, when the weak alkali salt is carbonate and phosphate, the mass ratio of carbonate to phosphate is 8:9.
Preferably, the sputtering ion source in the glow discharge spectrometry is an argon cluster ion source;
and/or the sputtering rate of the sputtering ion source in the glow discharge spectrum measurement is 1-10 mu m/min.
Preferably, the electrochemical method is chronopotentiometry;
and/or the electrolyte adopted in the electrochemical method is acid liquor;
and/or the electrolytic current density employed in the electrochemical process is 0.008-0.010A/cm 2.
In the present invention, the reason why the sputtering depth is calculated at the point where the relative content of the high content and easily detected element (e.g., sn element in the tin plate plating layer) is reduced to 1% in the quantitative conversion step is that the content of other trace elements (e.g., cr and Pb elements in the tin plate plating layer) is significant, and for convenience of description and calculation, the present invention is generally calculated at this depth. In practical verification, for the tin plate in the invention, if the relative content of the high-content and easily-detected element is calculated to be lower than 1%, if the relative content of the high-content and easily-detected element in the matrix is higher than 1%, curves of Pb and Cr which are integrated into the matrix can possibly interfere with the result, but the relative content of the high-content and easily-detected element Sn in the matrix of the tin plate in the invention is calculated to be lower than 1%, so that the accuracy of the detection result can be effectively ensured by adopting the depth to calculate.
In the invention, the type and concentration of the acid liquid are selected and determined according to the type of the sample to be detected. When the sample to be measured is a tinning plate coating, the tin content is detected in the standardized treatment, the electrolyte adopted in the electrochemical method is hydrochloric acid, the concentration of the acid is 1.5-2.0 mol/L, and the tin content m Sn：mSn=10000×[t1+2/3(t2-t1)]×MSn xJ/(n xF) in the unit area coating is converted by Faraday's law;
10000 is the area conversion unit, namely the conversion of square meters and square centimeters; m Sn is the Sn content per unit area, and the converted unit is g/m 2;MSn, which is the molar mass of Sn, and is 119 g/mol; j is the electrolysis current density, here 0.008A/cm 2; n is the electron transfer number, here 2; f is Faraday constant, 96485C/mol.
Setting the sputtering depth of a point at which the relative content of Sn element is reduced to 1% as h; then, integrating Cr, pb and Sn element curves obtained by glow discharge spectrometry in an integration interval of [0, h ] to obtain the relative content of each element:
；/>；/>；
Wherein, alpha Cr、αPb、αSn is the relative content integral result of Cr, pb and Sn elements in the integral interval of [0, h ]; w Cr、wPb、wSn is the relative content of Cr, pb and Sn elements respectively; and finally, according to the proportion relation between the Sn element content (m Sn) obtained in the standardized treatment and the integral result of the relative contents of Cr, pb and Sn elements, simultaneously converting to obtain the contents m Cr and m Pb：mCr=mSn×αCr/αSn;mPb=mSn×αPb/αSn of the Cr and Pb elements in the plating layer in unit area.
The technical scheme of the invention has the following advantages:
1. A method for simultaneously detecting the contents of a plurality of elements in a plating layer, comprising: 1) Pretreating a sample to be tested; 2) Glow discharge spectrometry: performing element depth analysis on the pretreated sample to be detected by adopting a glow discharge spectrometer, and obtaining a distribution curve of the relative content of each element from the surface to the matrix; 3) And (3) standardization treatment: detecting the content of a certain high-content easily-detected element in a sample to be detected by adopting an electrochemical method to obtain an electrolysis E-t curve of the sample to be detected, setting the last two inflection points of the electrolysis E-t curve to be t 1 and t 2 respectively, and converting the content m of the high-content easily-detected element in a unit area plating layer by using Faraday's law: m=10000× [ t 1+2/3(t2-t1) ]×m×j/(n×f); wherein t 1＜t2, M is the content of high-content easily-detected elements in the unit area plating layer, M is the molar mass of the high-content easily-detected elements, J is the electrolysis current density, n is the electron transfer number, and F is the Faraday constant; 4) Quantitative conversion: setting the sputtering depth of a point with high content and easy detection of the relative content of the element reduced to 1% as h; and integrating the element curves in the integration interval of [0, h ] to obtain the relative content of each element, and converting the relative content of each element according to the proportional relation between the content of the high-content easily-detected element and the relative content of each element obtained by the standardized treatment. The prior art detects the content of the element with high content and easy detection, but the detection means of the element with lower content in the coating is relatively immature, the detection limit is high and the deviation is large, the invention does not need to directly detect the element with lower content in the coating, only needs to measure the coating by glow discharge spectrum to obtain the percentage change curve of each element relative to the depth, carries out integral treatment on the curve, takes the integral proportion of the percentage content of each element relative to the depth as the proportion of each element mass, uses an electrochemical method (the precision is 0.001 g/m 2) to detect the quality of the element with high content and easy detection in the coating, and obtaining the element mass with extremely low content in the coating through conversion of mass proportion relation of each element. The method can realize quantitative detection of trace elements with the content of 0.0001 g/m 2 by means of integral conversion, greatly improves the detection precision, can obtain the quality of various elements at the same time, has the detection result free from interference of trace elements in a matrix, simplifies the detection step, avoids a large amount of experimental errors, and can realize the purposes of batch detection and accurate detection.
2. Compared with the traditional methods such as a chemical method and an ICP method, the method for simultaneously detecting the content of various elements in the coating has the advantages of lower detection cost and operation difficulty, higher detection efficiency and suitability for industrial batch detection.
3. In the pretreatment of the invention, in order to remove DOS oil, foreign matter pollution, fingerprints and adsorbed water vapor on the surface of the sample to be tested and improve the test precision, weak alkali salt is adopted as the impregnating compound, so that the surface of the sample to be tested is cleaned, and meanwhile, the buffer effect can be realized, the pH value fluctuation of the solution during the impregnation is small and can be repeatedly used, and the pretreatment is simple, the solution is low in cost, nontoxic and harmless, and the operation difficulty is low.
4. When the glow discharge spectrometry is adopted to carry out the depth analysis on the pre-treated sample to be detected, the argon cluster ion source sputtering can effectively avoid the excessive oxidation of the sample to be detected in the sputtering process, and the method is simple in operation and high in accuracy.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the drawings needed in the embodiments or the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing a glow discharge spectrum (full spectrum) of the detection of Cr and Pb contents in plating of a tin plate according to example 4 of the present invention;
FIG. 2 is a graph showing a glow discharge spectrum (partially enlarged A in FIG. 1) of the detection of Cr and Pb contents in plating of a tin plate according to example 4 of the present invention;
FIG. 3 is a graph of the chronograph potential E-t of the Cr and Pb contents in the plating layer of the tin plate according to example 4 of the present invention.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a method for simultaneously detecting contents of multiple elements in a plating layer, wherein a detection sample is a tin plate with a theoretical tin plating amount of 5.6 g/m 2 (i.e. a tin plate with a theoretical tin plating amount of 5.6 g/m 2 is produced in theory, but the actual tin plating amount can fluctuate up and down), and the detection of contents of Cr and Pb in the plating layer is carried out, and the specific implementation process and the detection result are shown in table 1, and the method comprises the following steps:
1) Pretreatment: adopting a mixed solution of Na 2CO3、Na3PO4 as an impregnating compound to carry out impregnating treatment on the tinned plate, wherein the concentration of Na 2CO3 in the impregnating compound is 40 g/L, the concentration of Na 3PO4 is 45 g/L, the temperature of the impregnating treatment is 45 ℃, the impregnating time is 3 min, the tinned plate is cleaned by clear water, and is dried by cold air, and cut into 30 multiplied by 30 mm samples;
2) Glow discharge spectrometry: taking an argon cluster ion source (GCIB) as a sputtering ion source, wherein the sputtering rate is 2 mu m/min, carrying out element depth analysis on the pretreated sample by adopting a glow discharge spectrometer, and detecting elements as Sn, cr, pb and Fe to obtain a distribution curve of the relative content of each element from the surface to a matrix;
3) And (3) standardization treatment: carrying out Sn content detection on the same batch of small samples by using an electrochemical method; the test method selects a chronopotentiometric method, electrolyte is an HCl solution with the molar concentration of 2 mol/L, the electrolysis current density is 0.008A/cm 2, an electrolysis E-t curve of a sample is obtained, the last two inflection points of the set curve are t 1 and t 2 respectively, wherein t 1＜t2 is t 1 is 88.343 s, and t 2 is 132.512 s in the embodiment; converting Sn content m Sn：mSn=10000×[t1+2/3(t2-t1)]×MSn ×J/(n×F) in the plating layer per unit area by Faraday's law, wherein 10000 is the area conversion unit, namely the conversion of square meters and square centimeters; m Sn is the Sn content per unit area, and the converted unit is g/m 2;MSn, which is the molar mass of Sn, and is 119 g/mol; j is the electrolysis current density, here 0.008A/cm 2; n is the electron transfer number, here 2; f is Faraday constant, 96485C/mol. The conversion gave m Sn as 5.81 g/m 2.
4) Quantitative conversion: setting the sputtering depth of a point at which the relative content of Sn element decreases to 1% to be h, h= 2.098; then, integrating Cr, pb and Sn element curves obtained by glow discharge spectrometry in an integration interval of [0, h ] to obtain the relative content of each element:
；/>；/>；
Wherein, alpha Cr、αPb、αSn is the relative content integral result of Cr, pb and Sn elements in the integral interval of [0, h ]; w Cr、wPb、wSn is the relative content of Cr, pb and Sn elements respectively; and finally, according to the proportion relation between the Sn element content (m Sn) obtained in the standardized treatment and the integral result of the relative contents of Cr, pb and Sn elements, simultaneously converting to obtain the contents m Cr and m Pb：mCr=mSn×αCr/αSn;mPb=mSn×αPb/αSn of the Cr and Pb elements in the plating layer in unit area. In the present embodiment ,αSn=1.047012,αCr=0.001021,αPb=0.000105,mCr=5.67mg/m2,mPb=0.58mg/m2.
Example 2
The embodiment provides a method for simultaneously detecting contents of multiple elements in a plating layer, wherein a detection sample is a tin plate with a theoretical tin plating amount of 4.0 g/m 2 in a large steel factory for detecting contents of Cr and Pb in the plating layer, the specific implementation process and the determination result are shown in table 1, and the method comprises the following steps:
1) Pretreatment: adopting a mixed solution of Na 2CO3、Na3PO4 as an impregnating compound to carry out impregnating treatment on the tinned plate, wherein the concentration of Na 2CO3 in the impregnating compound is 40 g/L, the concentration of Na 3PO4 is 45 g/L, the temperature of the impregnating treatment is 50 ℃, the impregnating time is 3 min, the tinned plate is cleaned by clear water, and is dried by cold air, and cut into 30 multiplied by 30 mm samples;
2) Glow discharge spectrometry: taking an argon cluster ion source (GCIB) as a sputtering ion source, wherein the sputtering rate is 2 mu m/min, carrying out element depth analysis on the pretreated sample by adopting a glow discharge spectrometer, and detecting elements as Sn, cr, pb and Fe to obtain a distribution curve of the relative content of each element from the surface to a matrix;
3) And (3) standardization treatment: carrying out Sn content detection on the same batch of small samples by using an electrochemical method; the test method selects a chronopotentiometric method, wherein electrolyte is an HCl solution with the molar concentration of 2 mol/L, the electrolysis current density is 0.008A/cm 2, an electrolysis E-t curve of a sample is obtained, the last two inflection points of the set curve are t 1 and t 2 respectively, t 1＜t2 is set, in the embodiment, t 1 is 60.97 s, and t 2 is 91.46 s; converting Sn content m Sn：mSn=10000×[t1+2/3(t2-t1)]×MSn ×J/(n×F) in the plating layer per unit area by Faraday's law, wherein 10000 is the area conversion unit, namely the conversion of square meters and square centimeters; m Sn is the Sn content per unit area, and the converted unit is g/m 2;MSn, which is the molar mass of Sn, and is 119 g/mol; j is the electrolysis current density, here 0.008A/cm 2; n is the electron transfer number, here 2; f is Faraday constant, 96485C/mol. The conversion gave m Sn as 4.01 g/m 2.
4) Quantitative conversion: setting the sputtering depth of a point at which the relative content of Sn element decreases to 1% to be h, h= 1.764; then, integrating Cr, pb and Sn element curves obtained by glow discharge spectrometry in an integration interval of [0, h ] to obtain the relative content of each element:
；/>；/>；
Wherein, alpha Cr、αPb、αSn is the relative content integral result of Cr, pb and Sn elements in the integral interval of [0, h ]; w Cr、wPb、wSn is the relative content of Cr, pb and Sn elements respectively; and finally, according to the proportion relation between the Sn element content (m Sn) obtained in the standardized treatment and the integral result of the relative contents of Cr, pb and Sn elements, simultaneously converting to obtain the contents m Cr and m Pb：mCr=mSn×αCr/αSn;mPb=mSn×αPb/αSn of the Cr and Pb elements in the plating layer in unit area. In the present embodiment ,αSn=0.972072,αCr=0.000981,αPb=0.000093,mCr=4.05mg/m2,mPb=0.38mg/m2.
Example 3
The embodiment provides a method for simultaneously detecting contents of multiple elements in a plating layer, wherein a detection sample is a tin plate with a theoretical tin plating amount of 2.8 g/m 2 in a large steel factory for detecting contents of Cr and Pb in the plating layer, and a specific implementation process and a detection result are shown in a table 1, and the method comprises the following steps:
1) Pretreatment: adopting a mixed solution of Na 2CO3、Na3PO4 as an impregnating compound to carry out impregnating treatment on the tinned plate, wherein the concentration of Na 2CO3 in the impregnating compound is 40 g/L, the concentration of Na 3PO4 is 45 g/L, the temperature of the impregnating treatment is 40 ℃, the impregnating time is 3 min, the tinned plate is cleaned by clear water, and is dried by cold air, and cut into 30 multiplied by 30 mm samples;
2) Glow discharge spectrometry: taking an argon cluster ion source (GCIB) as a sputtering ion source, wherein the sputtering rate is 2 mu m/min, carrying out element depth analysis on the pretreated sample by adopting a glow discharge spectrometer, and detecting elements as Sn, cr, pb and Fe to obtain a distribution curve of the relative content of each element from the surface to a matrix;
3) And (3) standardization treatment: carrying out Sn content detection on the same batch of small samples by using an electrochemical method; the test method selects a chronopotentiometric method, electrolyte is an HCl solution with the molar concentration of 2 mol/L, the electrolysis current density is 0.008A/cm 2, an electrolysis E-t curve of a sample is obtained, the last two inflection points of the set curve are t 1 and t 2 respectively, wherein t 1＜t2 is t 1 in the embodiment, 44.70 s is t 2 is 67.04 s; converting Sn content m Sn：mSn=10000×[t1+2/3(t2-t1)]×MSn ×J/(n×F) in the plating layer per unit area by Faraday's law, wherein 10000 is the area conversion unit, namely the conversion of square meters and square centimeters; m Sn is the Sn content per unit area, and the converted unit is g/m 2;MSn, which is the molar mass of Sn, and is 119 g/mol; j is the electrolysis current density, here 0.008A/cm 2; n is the electron transfer number, here 2; f is Faraday constant, 96485C/mol. The conversion gave m Sn as 2.94 g/m 2.
4) Quantitative conversion: setting the sputtering depth of the point at which the relative content of Sn element decreases to 1% to be h, h=1.365; then, integrating Cr, pb and Sn element curves obtained by glow discharge spectrometry in an integration interval of [0, h ] to obtain the relative content of each element:
；/>；/>；
Wherein, alpha Cr、αPb、αSn is the relative content integral result of Cr, pb and Sn elements in the integral interval of [0, h ]; w Cr、wPb、wSn is the relative content of Cr, pb and Sn elements respectively; and finally, according to the proportion relation between the Sn element content (m Sn) obtained in the standardized treatment and the integral result of the relative contents of Cr, pb and Sn elements, simultaneously converting to obtain the contents m Cr and m Pb：mCr=mSn×αCr/αSn;mPb=mSn×αPb/αSn of the Cr and Pb elements in the plating layer in unit area. In the present embodiment ,αSn=0.726012,αCr=0.001014,αPb=0.000073,mCr=4.11mg/m2,mPb=0.30mg/m2.
Example 4
The embodiment provides a method for simultaneously detecting contents of multiple elements in a plating layer, wherein a detection sample is a tin plate with a theoretical tin plating amount of 2.0 g/m 2 in a large steel factory for detecting contents of Cr and Pb in the plating layer, and a specific implementation process and a detection result are shown in a table 1, and the method comprises the following steps:
1) Pretreatment: adopting a mixed solution of Na 2CO3、Na3PO4 as an impregnating compound to carry out impregnating treatment on the tinned plate, wherein the concentration of Na 2CO3 in the impregnating compound is 40 g/L, the concentration of Na 3PO4 is 45 g/L, the temperature of the impregnating treatment is 45 ℃, the impregnating time is 3 min, the tinned plate is cleaned by clear water, and is dried by cold air, and cut into 30 multiplied by 30 mm samples;
2) Glow discharge spectrometry: taking an argon cluster ion source (GCIB) as a sputtering ion source, wherein the sputtering rate is2 mu m/min, performing element depth analysis on the pretreated sample by adopting a glow discharge spectrometer, and detecting elements such as Sn, cr, pb and Fe to obtain a distribution curve of the relative content of each element from the surface to a matrix, as shown in figures 1 and 2;
3) And (3) standardization treatment: carrying out Sn content detection on the same batch of small samples by using an electrochemical method; the test method selects a chronopotentiometric method, wherein electrolyte is HCl solution with the molar concentration of 2 mol/L, the electrolysis current density is 0.008A/cm 2, an electrolysis E-t curve of a sample is obtained, as shown in FIG. 3, the last two inflection points of the set curve are t 1 and t 2 respectively, wherein t 1＜t2, in the embodiment, t 1 is 32.322 s, and t 2 is 46.495 s; converting Sn content m Sn：mSn=10000×[t1+2/3(t2-t1)]×MSn ×J/(n×F) in the plating layer per unit area by Faraday's law, wherein 10000 is the area conversion unit, namely the conversion of square meters and square centimeters; m Sn is the Sn content per unit area, and the converted unit is g/m 2;MSn, which is the molar mass of Sn, and is 119 g/mol; j is the electrolysis current density, here 0.008A/cm 2; n is the electron transfer number, here 2; f is Faraday constant, 96485C/mol. The conversion gave m Sn as 2.06 g/m 2.
4) Quantitative conversion: setting the sputtering depth of the point at which the relative content of Sn element decreases to 1% to be h, h=1.154; then, integrating Cr, pb and Sn element curves obtained by glow discharge spectrometry in an integration interval of [0, h ] to obtain the relative content of each element:
；/>；/>；
Wherein, alpha Cr、αPb、αSn is the relative content integral result of Cr, pb and Sn elements in the integral interval of [0, h ]; w Cr、wPb、wSn is the relative content of Cr, pb and Sn elements respectively; and finally, according to the proportion relation between the Sn element content (m Sn) obtained in the standardized treatment and the integral result of the relative contents of Cr, pb and Sn elements, simultaneously converting to obtain the contents m Cr and m Pb：mCr=mSn×αCr/αSn;mPb=mSn×αPb/αSn of the Cr and Pb elements in the plating layer in unit area. In the present embodiment ,αSn=0.662711,αCr=0.001322,αPb=0.000074,mCr=4.11mg/m2,mPb=0.23mg/m2.
TABLE 1
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (9)
1. A method for simultaneously detecting the contents of a plurality of elements in a coating, comprising:
1) Pretreating a sample to be tested;
2) Glow discharge spectrometry: performing element depth analysis on the pretreated sample to be detected by adopting a glow discharge spectrometer, and obtaining a distribution curve of the relative content of each element from the surface to the matrix;
3) And (3) standardization treatment: detecting the content of a certain high-content easily-detected element in a sample to be detected by adopting an electrochemical method to obtain an electrolysis E-t curve of the sample to be detected, setting the last two inflection points of the electrolysis E-t curve to be t 1 and t 2 respectively, and converting the content m of the high-content easily-detected element in a unit area plating layer by using Faraday's law: m=10000× [ t 1+2/3(t2-t1) ]×m×j/(n×f); wherein t 1＜t2, M is the content of high-content easily-detected elements in the unit area plating layer, M is the molar mass of the high-content easily-detected elements, J is the electrolysis current density, n is the electron transfer number, and F is the Faraday constant;
4) Quantitative conversion: setting the sputtering depth of a point with high content and easy detection of the relative content of the element reduced to 1% as h; integrating the element curves in the integration interval of [0, h ] to obtain the relative content of each element, and converting the relative content of each element according to the proportional relation between the content of the high-content easily-detected element and the relative content of each element obtained by standardized treatment;
The sample to be tested is a tinning plate coating; each element in the tinning plate coating is Sn, cr, pb and Fe; the tin plate coating has high content and is easy to detect element Sn; according to the proportional relation between the Sn element content m Sn obtained in the standardized treatment and the integral result of the relative contents of Cr, pb and Sn elements in the quantitative conversion, the contents m Cr and m Pb：mCr=mSn×αCr/αSn;mPb=mSn×αPb/αSn of Cr and Pb elements in the plating layer in unit area are obtained through conversion; wherein, alpha Cr、αPb、αSn is the integral result of the relative content of Cr, pb and Sn elements in the [0, h ] integral interval.
2. The method of claim 1, wherein the pre-processing comprises: and carrying out infiltration treatment, washing, drying and cutting treatment on the sample to be tested.
3. The method according to claim 2, wherein the impregnating compound used in the impregnating treatment is a weak alkali salt;
And/or the concentration of the impregnating compound adopted in the impregnating treatment is 80-90 g/L;
And/or, the temperature of the infiltration treatment is 40-50 ℃;
and/or the duration of the infiltration treatment is 3-4 min.
4. The method according to claim 2, wherein the washing agent used for the washing is water;
and/or, the drying treatment adopts cold air drying;
and/or, the cutting process cuts the sample to be tested into 30 mm multiplied by 30 mm small samples.
5. A method according to claim 3, wherein the weak base salt is a carbonate or/and a phosphate;
and/or the concentration of the impregnating compound is 85 g/L.
6. The method of claim 5, wherein the weak base salts are carbonates and phosphates;
and/or, the carbonate is sodium carbonate;
And/or, the phosphate is sodium phosphate.
7. The method according to claim 6, wherein when the weak alkali salt is carbonate and phosphate, the mass ratio of carbonate to phosphate is 8:9.
8. The method of claim 1, wherein the sputter ion source in the glow discharge spectrometry is an argon cluster ion source;
and/or the sputtering rate of the sputtering ion source in the glow discharge spectrum measurement is 1-10 mu m/min.
9. The method of claim 1, wherein the electrochemical method is chronopotentiometry;
and/or the electrolyte adopted in the electrochemical method is acid liquor;
and/or the electrolytic current density employed in the electrochemical process is 0.008-0.010A/cm 2.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004061121A (en) * | 2002-07-24 | 2004-02-26 | Nippon Light Metal Co Ltd | Standard sample for surface analysis and its manufacturing method |
| CN105628854A (en) * | 2015-12-31 | 2016-06-01 | 中国科学院上海硅酸盐研究所 | Analysis device and method for detecting multiple anions simultaneously |
| CN106546573A (en) * | 2015-09-17 | 2017-03-29 | 鞍钢股份有限公司 | Lead, the method for cadmium content in a kind of quick detection galvanized steel plain sheet coating |
| CN106645095A (en) * | 2017-02-13 | 2017-05-10 | 首钢总公司 | Method for measuring contents of silicon and aluminum in aluminum silicon plate plating |
| CN106770620A (en) * | 2016-11-21 | 2017-05-31 | 汕头大学 | The method that technology determines elemental composition depth profile in film is dissected with sputter depth |
| CN107314999A (en) * | 2017-06-20 | 2017-11-03 | 重庆邮电大学 | Liquid cathode Glow Discharge Spectrometry method based on multiple linear regression method |
| CN108760654A (en) * | 2018-04-28 | 2018-11-06 | 首钢京唐钢铁联合有限责任公司 | A kind of method of lead element content in quick measurement tin plate coating |
| WO2019088229A1 (en) * | 2017-11-01 | 2019-05-09 | 新日鐵住金株式会社 | Electrolytically sn-plated steel sheet |
| CN111426642A (en) * | 2020-03-31 | 2020-07-17 | 本钢板材股份有限公司 | Method for determining galvanized sheet coating distribution and element quality by direct current glow discharge atomic emission spectrometry |
| CN111595650A (en) * | 2020-06-09 | 2020-08-28 | 本钢板材股份有限公司 | Detection method for simultaneously determining contents of multiple elements in steel for galvanizing and galvanized steel sheet |
| CN112782257A (en) * | 2019-11-07 | 2021-05-11 | 上海梅山钢铁股份有限公司 | Method for detecting passive film component content of cold-rolled electrolytic tin-plated steel plate |
| CN114295603A (en) * | 2022-01-13 | 2022-04-08 | 鞍钢股份有限公司 | Method for simultaneously determining contents of multiple elements in aluminum alloy |
| CN115656013A (en) * | 2022-09-14 | 2023-01-31 | 首钢集团有限公司 | Method for detecting preferential corrosion phase in high-aluminum zinc aluminum magnesium coating |
| CN115980021A (en) * | 2023-02-01 | 2023-04-18 | 河钢股份有限公司 | Method for detecting content of lead element in coating of cold-rolled tin-plated steel plate |
| CN116026810A (en) * | 2023-01-19 | 2023-04-28 | 青岛澳康质量检测技术有限公司 | Method for detecting copper content in antifouling paint based on radio frequency glow discharge spectrometer and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11474042B2 (en) * | 2016-09-08 | 2022-10-18 | Agnes OBUCHOWSKA | Apparatus for analyzing the elemental composition of a liquid sample and methods of using the same |
-
2024
- 2024-03-19 CN CN202410309835.9A patent/CN117907562B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004061121A (en) * | 2002-07-24 | 2004-02-26 | Nippon Light Metal Co Ltd | Standard sample for surface analysis and its manufacturing method |
| CN106546573A (en) * | 2015-09-17 | 2017-03-29 | 鞍钢股份有限公司 | Lead, the method for cadmium content in a kind of quick detection galvanized steel plain sheet coating |
| CN105628854A (en) * | 2015-12-31 | 2016-06-01 | 中国科学院上海硅酸盐研究所 | Analysis device and method for detecting multiple anions simultaneously |
| CN106770620A (en) * | 2016-11-21 | 2017-05-31 | 汕头大学 | The method that technology determines elemental composition depth profile in film is dissected with sputter depth |
| CN106645095A (en) * | 2017-02-13 | 2017-05-10 | 首钢总公司 | Method for measuring contents of silicon and aluminum in aluminum silicon plate plating |
| CN107314999A (en) * | 2017-06-20 | 2017-11-03 | 重庆邮电大学 | Liquid cathode Glow Discharge Spectrometry method based on multiple linear regression method |
| WO2019088229A1 (en) * | 2017-11-01 | 2019-05-09 | 新日鐵住金株式会社 | Electrolytically sn-plated steel sheet |
| CN108760654A (en) * | 2018-04-28 | 2018-11-06 | 首钢京唐钢铁联合有限责任公司 | A kind of method of lead element content in quick measurement tin plate coating |
| CN112782257A (en) * | 2019-11-07 | 2021-05-11 | 上海梅山钢铁股份有限公司 | Method for detecting passive film component content of cold-rolled electrolytic tin-plated steel plate |
| CN111426642A (en) * | 2020-03-31 | 2020-07-17 | 本钢板材股份有限公司 | Method for determining galvanized sheet coating distribution and element quality by direct current glow discharge atomic emission spectrometry |
| CN111595650A (en) * | 2020-06-09 | 2020-08-28 | 本钢板材股份有限公司 | Detection method for simultaneously determining contents of multiple elements in steel for galvanizing and galvanized steel sheet |
| CN114295603A (en) * | 2022-01-13 | 2022-04-08 | 鞍钢股份有限公司 | Method for simultaneously determining contents of multiple elements in aluminum alloy |
| CN115656013A (en) * | 2022-09-14 | 2023-01-31 | 首钢集团有限公司 | Method for detecting preferential corrosion phase in high-aluminum zinc aluminum magnesium coating |
| CN116026810A (en) * | 2023-01-19 | 2023-04-28 | 青岛澳康质量检测技术有限公司 | Method for detecting copper content in antifouling paint based on radio frequency glow discharge spectrometer and application |
| CN115980021A (en) * | 2023-02-01 | 2023-04-18 | 河钢股份有限公司 | Method for detecting content of lead element in coating of cold-rolled tin-plated steel plate |
Non-Patent Citations (1)
| Title |
|---|
| 辉光放电发射光谱法测定钢板镀锌层中铅镉铬;于媛君 等;冶金分析;20151008;35(09);1-7 * |
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