CN104764792A - Determination method for solid-solution niobium content of steel - Google Patents
Determination method for solid-solution niobium content of steel Download PDFInfo
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Abstract
The invention discloses a determination method for the solid-solution niobium content of steel. The determination method comprises the following steps: soaking a steel sample in water and hydrochloric acid, then washing the steel sample, flushing the steel sample with ethanol, drying the steel sample and weighing the dried steel sample so as to obtain the mass m1 of the steel sample before electrolysis; with the steel sample as a positive electrode, stainless steel as a negative electrode and a mixed solution of potassium chloride and citric acid as an electrolyte, electrolyzing the electrolyte to extract solid-solution niobium in the steel sample so as to obtain a solution of the steel sample; washing out electrolysis residue on the steel sample, flushing the steel sample with ethanol, drying the steel sample and weighing the dried steel sample so as to obtain the mass m2 of the steel sample after electrolysis; with caesium as an internal standard element, determining the mass of the solid-solution niobium m in the solution of the steel sample and the mass of solid-solution niobium m0 in a blank solution by using an inductively coupled plasma mass spectrometer; and calculating the content of the solid-solution niobium in steel according to the equation that W<Nb>% is equal to (m-m0)/(m1-m2) * 100. The method provided by the invention can effectively extract solid-solution niobium in steel and has the advantages of short analysis time and high measuring precision.
Description
Technical field
The present invention relates to technical field of analytical chemistry, specifically, relate to the assay method of solid solution content of niobium in a kind of steel.
Background technology
Niobium has prevention grain growth, suppresses deformed austeaite recrystallization and produce the effects such as significant sedimentation effect in steel, thus obtains a wide range of applications in steel.Niobium is microalloy element very important in Hi-Stren steel, the precipitation of niobium and solid solution on slab quality quality and steel performance excellent have obviously affect, the formulation of production technology and performing should separate out in steel fully understanding microalloy element and solid solution rule basis on, give full play to the effect of controlled rolling and controlled cooling, guarantee the effect farthest playing microalloy element, therefore, in Accurate Determining steel, solid solution niobium has important practical significance.
In the report of existing niobium steel research, about method disclosed in " in microalloy steel with nb the quantitative measurement of solid solution niobium and non-solid solution niobium and application " that the Quantitative research method of niobium mainly contains that chemical analysis, spectrographic method, electrolysis precipitation precipitated phase sizing technique and University On The Mountain Of Swallows's journal publish.Vague generalization Epidemiological Analysis and spectrographic method are mainly for the macroanalysis measuring niobium in steel.At present, Cao Yabin etc. adopt stannous chloride, concentrated hydrochloric acid and distilled water mix reagent to dissolve solid solution niobium in steel, and ICP-OES measures; Iodo-alcohol is adopted to dissolve in practical metallurgical analysis, evaporate to dryness iodine, alcohol, spectrphotometric method for measuring.Above-mentioned two kinds of methods can measure for the solid solution niobium of high-load, but because solid solution content of niobium in steel is often very low, two kinds of methods are all difficult to Accurate Determining.
Summary of the invention
Technical matters to be solved by this invention is to provide the assay method of solid solution content of niobium in a kind of steel, adopt electrolytic separation obtain solid solution niobium, measured by icp ms ICP-MS, Monitoring lower-cut be low, accuracy and precision all high.
Technical scheme of the present invention is as follows:
An assay method for solid solution content of niobium in steel, comprising: steel sample is soaked afterwash in water and hydrochloric acid, alcohol flushing, the quality m of the described steel sample before obtaining electrolysis of weighing after drying
1; Using described steel sample as anode, using stainless steel as negative electrode, using the mixed solution of potassium chloride and citric acid as electrolytic solution, electrolysis makes described electrolytic solution extract solid solution niobium in described steel sample, obtains the solution of described steel sample; Wash away the electrolysis residue on described steel sample, alcohol flushing, dry, the quality m of the described steel sample after obtaining electrolysis of weighing
2; Take caesium as internal standard element, adopt icp ms to measure the quality m of the solid solution niobium in the solution of described steel sample, and the quality m of solid solution niobium in blank solution
0; Following formula is adopted to obtain solid solution content of niobium in steel
Further: in described electrolytic solution, the mass percentage of potassium chloride is 0.9% ~ 1.1%, in described electrolytic solution, the mass percentage of citric acid is 1% ~ 1.5%.
Further: the volume of described electrolytic solution is 250mL.
Further: the electric current of described electrolysis is 0.5A ~ 1A, the time of described electrolysis is 5min ~ 30min, and the temperature of described electrolysis is room temperature.
Further: when mass percentage≤0.010% of solid solution niobium in described steel sample, described electrolysis time is 20 ~ 30min; As the mass percentage > 0.010% of solid solution niobium in described steel sample, described electrolysis time is 5 ~ 10min.
Further: when mass percentage≤0.010% of solid solution niobium in described steel sample, the solution of the described steel sample after electrolysis 20 ~ 30min is directly loaded into the test solution as solid solution niobium in described icp ms; As the mass percentage > 0.010% of solid solution niobium in described steel sample, the solution of the described steel sample after electrolysis 5 ~ 10min is directly loaded into the test solution as solid solution niobium in described icp ms.
Further: described employing icp ms measures the quality m of the solid solution niobium in the solution of described steel sample, and the quality m of solid solution niobium in blank solution
0process comprise the steps: to take 8 parts of 0.1000g pure iron respectively in 250mL beaker, add 10mL water respectively, 10mL density is the nitric acid dissolution in low temperature of 1.42g/mL, solution after dissolving is moved in 8 100mL volumetric flasks respectively, respectively add the solution of 1g potassium chloride and 1.3g citric acid water, pipette the niobium standard solution 0.00mL of 0.1 μ g/mL respectively, 0.50mL, 2.00mL, 5.00mL, 10.00mL, the niobium standard solution 10.00mL of 1.0 μ g/mL, 20.00mL, 50.00mL is in each volumetric flask, use water constant volume, take caesium as internal standard element, employing plasma mass spectrometry measures.With the massfraction of niobium for horizontal ordinate, intensity is ordinate, drawing curve; Icp ms is adopted to measure the intensity of the solid solution niobium in the solution of described steel sample, and the intensity of solid solution niobium in blank solution; On described working curve, the quality m of the solid solution niobium in the solution of corresponding described steel sample is obtained according to the intensity of the solid solution niobium in the intensity of the solid solution niobium in the solution of described steel sample, described blank solution, and the quality m of solid solution niobium in described blank solution
0.
Further: described steel sample is the columnar samples of diameter 8mm ~ 10mm, long 80mm ~ 100mm.
Further: in described process of being soaked in water and hydrochloric acid by steel sample, the time of described immersion is 10min ~ 20min.
Further: in described process of being soaked in water and hydrochloric acid by steel sample, the volume of described water is 20 ~ 30mL, and the density of described hydrochloric acid is 1.19g/mL, and the volume of described hydrochloric acid is 20 ~ 30mL.
Further: described steel sample is surperficial atresia, flawless steel sample.
Technique effect of the present invention is as follows:
Method of the present invention effectively can extract the solid solution niobium in steel by electrolytic solution electrolysis, coordinate icp ms to measure the content of solid solution niobium, analysis time is short, measuring accuracy is high and environmental protection.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
In steel of the present invention, the concrete steps of the assay method of solid solution content of niobium are as follows:
Step S1: steel sample is soaked afterwash in water and hydrochloric acid, alcohol flushing, weighs after drying and obtains the quality m of steel sample before electrolysis
1.
Above-mentioned steel sample is surperficial atresia, flawless steel sample, can be observed by the groove digging certain depth in steel sample distance a distance, top.Above-mentioned steel sample is preferably the columnar samples of diameter 8mm ~ 10mm, long 80mm ~ 100mm.
The density of above-mentioned hydrochloric acid is preferably 1.19g/mL.The volume of water is 20 ~ 30mL, and be preferably 25mL, the volume of hydrochloric acid is 20 ~ 30mL, is preferably 25mL.The time of soaking is 10min ~ 20min.The object of this step is the rust in order to remove on steel sample.
Step S2: using steel sample as anode, using stainless steel as negative electrode, using the mixed solution of potassium chloride and citric acid as electrolytic solution, electrolysis makes electrolytic solution extract solid solution niobium in steel sample, obtains the solution of steel sample.
Wherein, in above-mentioned electrolytic solution, the mass percentage of potassium chloride is 0.9% ~ 1.1%, and the mass percentage of citric acid is 1% ~ 1.5%.The volume of electrolytic solution is preferably 250mL.The electric current of electrolysis is 0.5A ~ 1A, and the time of electrolysis is 5min ~ 30min, and the temperature of electrolysis is room temperature.Wherein, when mass percentage≤0.010% of solid solution niobium in steel sample, electrolysis time is 20 ~ 30min; As the mass percentage > 0.010% of solid solution niobium in steel sample, electrolysis time is 5 ~ 10min.
Step S3: wash away the electrolysis residue on steel sample, alcohol flushing, dry, weigh and obtain the quality m of steel sample after electrolysis
2.
Step S4: take caesium as internal standard element, adopts icp ms to measure the quality m of the solid solution niobium in the solution of steel sample, and the quality m of solid solution niobium in blank solution
0.
Wherein, the process of step S4 specifically comprises again following step:
Step S41: take 8 parts of 0.1000g pure iron respectively in 250mL beaker, add 10mL water respectively, nitric acid dissolution in low temperature that 10mL density is 1.42g/mL, solution after dissolving is moved in 8 100mL volumetric flasks respectively, respectively add the solution of 1g potassium chloride and 1.3g citric acid water, pipette niobium standard solution 0.00mL, 0.50mL, 2.00mL, 5.00mL, 10.00mL of 0.1 μ g/mL respectively, niobium standard solution 10.00mL, 20.00mL, 50.00mL of 1.0 μ g/mL are in each volumetric flask, use water constant volume, take caesium as internal standard element, adopt plasma mass spectrometry to measure.With the massfraction of niobium for horizontal ordinate, intensity is ordinate, drawing curve, and the related coefficient of this working curve is 0.999.
Step S42: adopt icp ms to measure the intensity of the solid solution niobium in the solution of steel sample, and the intensity of solid solution niobium in blank solution.
Wherein, when mass percentage≤0.010% of solid solution niobium in steel sample, the solution of the steel sample after electrolysis 20 ~ 30min is directly loaded into the test solution as solid solution niobium in icp ms; As the mass percentage > 0.010% of solid solution niobium in steel sample, the solution of the steel sample after electrolysis 5 ~ 10min is directly loaded into the test solution as solid solution niobium in icp ms, this is because content of niobium is high, easy enrichment, so electrolysis time is short.
Step S43: the quality m obtaining the solid solution niobium in the solution of corresponding steel sample according to the intensity of the solid solution niobium in the intensity of the solid solution niobium in the solution of steel sample, blank solution on working curve, and the quality m of solid solution niobium in blank solution
0.
Step S5: adopt following formula to obtain solid solution content of niobium in steel
Method of the present invention at room temperature adopts constant current electrolysis to extract solid solution niobium, electrolytic solution directly adopts icp ms to measure solid solution niobium, eliminate bath composition by matching method to affect Instrument measuring, analysis time is short, measuring accuracy is high and environmental protection.
Below the parameter of method of the present invention is described further.
1, the selection of electrolytic solution
By the rare earth steel sample of 1# containing niobium 0.016%, be 0.8A at Faradaic current, electrolysis temperature is under room temperature, adopt a electrolytic solution respectively: 1% (mass percentage) potassium chloride and 1% (mass percentage) aqueous citric acid solution and b electrolytic solution: 7.5% (mass percentage) potassium chloride and 1% (mass percentage) aqueous citric acid solution carry out electrolysis, electrolysis 10min takes off, electrolysis residue is washed in 150mL glass beaker, add the hydrochloric acid that 5mL density is 1.19g/mL more respectively, 5mL density is that the nitric acid of 1.42g/mL and 5mL density are about the hydrofluorite of 1.13g/mL in electrolysis residue, heating for dissolving, take off, constant volume is in 100mL volumetric flask, ICP-OES is adopted to measure, the results are shown in Table 1.
The measurement result of table 1 different electrolytes
| Electrolytic solution | Chemical combination niobium (%) | Total niobium amount (%) |
| a | 0.0154 | 0.016 |
| b | 0.0156 | 0.016 |
As can be seen from Table 2, two kinds of electrolytic solution all can quantitatively extract chemical combination niobium, namely all can extract niobium carbonitrides, niobium oxide.Show two kinds of electrolytic solution all energy Quantitative Separation solid solution niobium and chemical combination niobiums, therefore, in electrolytic solution, the mass percentage of potassium chloride is preferably 0.9% ~ 1.1%, and the mass percentage of citric acid is preferably 1% ~ 1.5%.
2, the impact of bath composition
Adopt the niobium standard solution containing electrolytic solution and the niobium standard solution containing isodose to carry out the strength detection of niobium respectively, the results are shown in Table 2.
The impact of table 2 bath composition
| Mensuration system | Not containing electrolytic solution measured value | Containing electrolytic solution measured value |
| Intensity | 338.51 | 5118.44 |
As can be seen from Table 2, the mensuration intensity of the niobium containing bath composition is far away higher than the mensuration intensity of the niobium not containing bath composition, namely the mensuration of bath composition on niobium has impact, therefore, iron and the bath composition (potassium chloride and citric acid) of close content must be mated in the standard serial solution of drawing curve, eliminate electrolytic solution to the impact of measurement result.
3, co-existing element interference test
Iron-based body and electrolytic solution there is situation under, inductively coupled plasma atomic emission spectrometry instrument ICP-OES and icp ms ICP-MS is adopted to measure respectively, the standard solution of the niobium of different content is carried out to the interference measurement of the element such as Mn, V, Ni, Mo, Cr, Ti, Cu, RE (rare metal), W, Nb, result is as shown in table 3.
Table 3 co-existing element interference test findings
| Mark liquid/% | 0.0005 | 0.0010 | 0.002 | 0.01 |
| Measured value/% | 0.00054 | 0.00097 | 0.0205 | 0.0097 |
From the results shown in Table 3, the disturbed condition of each coexistence elements is: Mn≤4.00%, Cr, Ni, V, Ti, Mo≤2.00%, Cu, RE≤1.00% not interference measurement.
With specific embodiment, technical scheme of the present invention is described further below.
In following embodiment, the inductively-coupled plasma spectrometer of the inductively-coupled plasma spectrometer of employing to be the model of PE company of the U.S. be ELAN DRC-e, the running parameter of this spectrometer is as shown in table 4.Silicon rectifier is silicon rectifier prepared by Beijing Ailanthus altissima.
Table 4 Instrument working parameter
| Project | Parameter | Project | Parameter |
| Power | 1100w | Lens voltage | 7.5V |
| Plasma gas flow rate | 15L/min | Sampling spiroid | φ1.1 |
| Assisted gas flow | 1.2L/min | Intercept cone | φ0.9 |
| Carrier gas flux | 0.80L/min | Scan mode | Jump peak |
| Sample introduction speed | 1.5L/min | Multiplicity | 2 |
Note: measure isotope
93nb.
Each embodiment agents useful for same: potassium chloride is pure for analyzing, citric acid is pure for analyzing, and ethanol is pure for analyzing, and nitric acid density is about 1.42g/mL, and top grade is pure; Hydrochloric acid density is 1.19g/mL, and top grade is pure; Hydrofluorite density is 1.13g/mL, and top grade is pure; Perchloric acid density is 1.68g/mL, and top grade is pure; Standard Stock solutions: the concentration of niobium is 1000 μ g/mL, State Standard Matter Research Centre; Caesium Standard Stock solutions: the concentration of caesium is 1000 μ g/mL, caesium inner mark solution: the concentration of caesium is 1.0 μ g/mL; Deionized water is self-control.
The acquisition methods of the working curve of the icp ms of each embodiment is as follows:
Take 8 parts of 0.1000g pure iron respectively in 250mL beaker, add 10mL water respectively, nitric acid dissolution in low temperature that 10mL density is 1.42g/mL, solution after dissolving is moved in 8 100mL volumetric flasks respectively, respectively add the solution of 1g potassium chloride and 1.3g citric acid water, pipette niobium standard solution 0.00mL, 0.50mL, 2.00mL, 5.00mL, 10.00mL of 0.1 μ g/mL respectively, niobium standard solution 10.00mL, 20.00mL, 50.00mL of 1.0 μ g/mL are in each volumetric flask, use water constant volume, take caesium as internal standard element, adopt plasma mass spectrometry to measure.With the massfraction of niobium for horizontal ordinate, intensity is ordinate, drawing curve.
Embodiment 1
The rare earth steel sample containing niobium total amount being 0.016% being made diameter is 8.5mm, the long column for 80mm, digs the groove that a degree of depth is 2mm, observe and show this steel sample atresia, flawless at it apart from 4mm place, top.
Being placed in by steel sample and filling 25mL water and 25mL density is that the measuring cup of the hydrochloric acid of 1.19g/mL soaks 10min and takes out, clean, and after drying, accurately takes the quality m of steel sample with alcohol flushing steel sample
1for 87.6248g.
The glass beaker filling the 250mL electrolytic solution prepared is put into electrolytic cell.In this electrolytic solution containing mass percentage be 1% potassium chloride and mass percentage be the aqueous citric acid solution of 1.2%.Using the steel sample of having weighed as anode, stainless steel cylinder is as negative electrode, and open silicon rectifier, setting Faradaic current is 0.7A, carries out electrolysis under room temperature, after electrolysis 30min, takes off steel sample, puts into 150mL glass beaker and wipes excellent sampling.Rinse the electrolysis residue on steel sample with water, then dry with this steel sample of alcohol flushing, the quality m of the steel sample after electrolysis of weighing
2for 87.3106g.
The glass beaker that electrolytic solution is housed is taken out from electrolytic cell, make it even with the electrolytic solution after glass bar stirs electrolysis steel sample, take caesium as internal standard element, icp ms is adopted to measure electrolytic solution, and measure blank sample in company with band reagent blank, by comparison work curve, obtain the quality m of the solid solution niobium in the quality m of the solid solution niobium in the solution of steel sample and blank solution
0.M and m
0automatically provided by instrument.
Wherein, the specific operation process adopting inductively-coupled plasma spectrometer to measure is: open ICP-MS, after instrument igniting complete stability, sets up the analytical approach of steel sample according to the condition of work of ICP-MS in table 4.First load institute and join niobium standard serial solution, the mensuration isotope of selection niobium is
93nb, measures under this isotope, all noiseless.Then be internal standard element with caesium, carry out the mensuration of sample blank, steel sample to be measured successively.
Calculate by following computing formula, measurement result is as shown in table 5.
Solid solution content of niobium in steel sample
m-m
0automatically provided by instrument.
Embodiment 2
The niobium steel sample containing niobium being 0.016% is made diameter 8.5mm, the long column for 81mm, dig apart from 3mm place, top the groove that a degree of depth is 2mm at it, observation shows this steel sample atresia, flawless, and in 1350 DEG C of Quenching Treatment, niobium in steel is all existed with solid solution niobium form.
Being placed in by steel sample and filling 30mL water and 30mL density is that the measuring cup of the hydrochloric acid of 1.19g/mL soaks 15min and takes out, and clean, alcohol flushing steel sample also, after drying, accurately takes steel sample weight m
1for 96.6396g.
The glass beaker filling the 250mL electrolytic solution prepared is put into electrolytic cell.In this electrolytic solution containing mass percentage be 0.9% potassium chloride and mass percentage be the aqueous citric acid solution of 1.5%.Using the steel sample of having weighed as anode, stainless steel cylinder is as negative electrode, and open silicon rectifier, setting Faradaic current is 0.5A, carries out electrolysis under room temperature, after electrolysis 10min, takes off steel sample, puts into 150mL glass beaker and wipes excellent sampling.Rinse the electrolysis residue on steel sample with water, then dry with this steel sample of alcohol flushing, the quality m of the steel sample after electrolysis of weighing
2for 96.5278g.
The glass beaker that electrolytic solution is housed is taken out from electrolytic cell, make it even with the electrolytic solution after glass bar stirs electrolysis steel sample, take caesium as internal standard element, icp ms is adopted to measure electrolytic solution, and measure blank sample in company with band reagent blank, by comparison work curve, obtain the quality m of the solid solution niobium in the quality m of the solid solution niobium in the solution of steel sample and blank solution
0.M and m
0automatically provided by instrument.
In steel sample, the computing formula of solid solution content of niobium is with embodiment 1, and measurement result is in table 5.
Embodiment 3
The niobium steel sample containing niobium being 0.030% being made diameter is 8.0mm, the long column for 85mm, digs the groove that a degree of depth is 2mm, observe and show this steel sample atresia, flawless at it apart from 3mm place, top.
Being placed at by sample and filling 30mL water and 30mL density is soak 15min in the measuring cup of the hydrochloric acid of 1.19g/mL to take out, and clean, alcohol flushing steel sample also, after drying, accurately takes steel sample weight m
1for 81.3842g.
The glass beaker filling the 250mL electrolytic solution prepared is put into electrolytic cell.In this electrolytic solution containing mass percentage be 0.9% potassium chloride and mass percentage be the aqueous citric acid solution of 1.5%.Using the steel sample of having weighed as anode, stainless steel cylinder is as negative electrode, and open silicon rectifier, setting Faradaic current is 0.5A, carries out electrolysis under room temperature, and electrolysis 26min takes off steel sample, puts into 150mL glass beaker and wipes excellent sampling.Rinse the electrolysis residue on steel sample with water, then dry with this steel sample of alcohol flushing, the quality m of the steel sample after electrolysis of weighing
2for 81.0842g.
The glass beaker that electrolytic solution is housed is taken out from electrolytic cell, make it even with the electrolytic solution after glass bar stirs electrolysis steel sample, take caesium as internal standard element, icp ms is adopted to measure electrolytic solution, and measure blank sample in company with band reagent blank, by comparison work curve, obtain the quality m of the solid solution niobium in the quality m of the solid solution niobium in the solution of steel sample and blank solution
0.M and m
0automatically provided by instrument.
In steel sample, the computing formula of solid solution content of niobium is with embodiment 1, and measurement result is in table 5.
Embodiment 4
The niobium steel sample containing niobium being 0.030% being made diameter is 8.0mm, the long column for 85mm, dig apart from 3mm place, top the groove that a degree of depth is 2mm at it, observation shows this steel sample atresia, flawless in 1350 DEG C of Quenching Treatment, niobium in steel is all existed with solid solution niobium form.
Being placed at by sample and filling 25mL water and 25mL density is soak 15min in the measuring cup of the hydrochloric acid of 1.19g/mL to take out, and clean, alcohol flushing steel sample also, after drying, accurately takes steel sample weight m
1for 81.3842g.
The glass beaker filling the 250mL electrolytic solution prepared is put into electrolytic cell.In this electrolytic solution containing mass percentage be 0.9% potassium chloride and mass percentage be the aqueous citric acid solution of 1.5%.Using the steel sample of having weighed as anode, stainless steel cylinder is as negative electrode, and open silicon rectifier, setting Faradaic current is 0.5A, carries out electrolysis under room temperature, and electrolysis 5min takes off steel sample, puts into 150mL glass beaker and wipes excellent sampling.Rinse the electrolysis residue on steel sample with water, then dry with this steel sample of alcohol flushing, the quality m of the steel sample after electrolysis of weighing
2for 81.3468g.
The glass beaker that electrolytic solution is housed is taken out from electrolytic cell, make it even with the electrolytic solution after glass bar stirs electrolysis steel sample, take caesium as internal standard element, icp ms is adopted to measure electrolytic solution, and measure blank sample in company with band reagent blank, by comparison work curve, obtain the quality m of the solid solution niobium in the quality m of the solid solution niobium in the solution of steel sample and blank solution
0.M and m
0automatically provided by instrument.
In steel sample, the computing formula of solid solution content of niobium is with embodiment 1, and measurement result is in table 5.
The measurement result (%) of the solid solution niobium of each embodiment of table 5
| Sample | Composition | Measured value | Total niobium | Chemical combination niobium |
| Containing niobium steel sample | Solid solution niobium | 0.000076 | 0.016 | 0.0155 |
| Containing niobium steel 1350 DEG C quenching | Solid solution niobium | 0.015 | 0.016 | / |
| Containing Biobium rare-earth steel sample | Solid solution niobium | 0.000084 | 0.030 | 0.029 |
| Containing Biobium rare-earth steel 1350 DEG C quenching | Solid solution niobium | 0.028 | 0.030 | / |
As can be seen from Table 5, the results contrast adopting method of the present invention to test is accurate.
In sum, method of the present invention only needs electrolysis 5 ~ 30min steel sample, without any process, directly adopts ICP-MS to measure.This method environmental protection, safety, analysis time are short, only need 1 ~ 2 hour.In addition, because the content of solid solution niobium in steel is general very low, adopt ICP-MS to measure and be better than ICP-OES mensuration, the Monitoring lower-cut of ICP-MS is 0.00005%, and ICP-OES is 0.001%.Method of the present invention is applied in production and scientific research, plays a part positive, have certain economic benefit and significant social benefit to production technology and exploitation containing niobium steel grade.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the assay method of solid solution content of niobium in steel, is characterized in that, comprising:
Steel sample is soaked afterwash in water and hydrochloric acid, alcohol flushing, the quality m of the described steel sample before obtaining electrolysis of weighing after drying
1;
Using described steel sample as anode, using stainless steel as negative electrode, using the mixed solution of potassium chloride and citric acid as electrolytic solution, electrolysis makes described electrolytic solution extract solid solution niobium in described steel sample, obtains the solution of described steel sample;
Wash away the electrolysis residue on described steel sample, alcohol flushing, dry, the quality m of the described steel sample after obtaining electrolysis of weighing
2;
Take caesium as internal standard element, adopt icp ms to measure the quality m of the solid solution niobium in the solution of described steel sample, and the quality m of solid solution niobium in blank solution
0;
Following formula is adopted to obtain solid solution content of niobium in steel
2. the assay method of solid solution content of niobium in steel as claimed in claim 1, it is characterized in that: in described electrolytic solution, the mass percentage of potassium chloride is 0.9% ~ 1.1%, in described electrolytic solution, the mass percentage of citric acid is 1% ~ 1.5%.
3. the assay method of solid solution content of niobium in steel as claimed in claim 1, is characterized in that: the volume of described electrolytic solution is 250mL.
4. the assay method of solid solution content of niobium in steel as claimed in claim 1, it is characterized in that: the electric current of described electrolysis is 0.5A ~ 1A, the time of described electrolysis is 10min ~ 30min, and the temperature of described electrolysis is room temperature.
5. the assay method of solid solution content of niobium in steel as claimed in claim 4, it is characterized in that: when mass percentage≤0.010% of solid solution niobium in described steel sample, described electrolysis time is 20 ~ 30min; As the mass percentage > 0.010% of solid solution niobium in described steel sample, described electrolysis time is 5 ~ 10min.
6. the assay method of solid solution content of niobium in steel as claimed in claim 1, is characterized in that:
When mass percentage≤0.010% of solid solution niobium in described steel sample, the solution of the described steel sample after electrolysis 20 ~ 30min is directly loaded into the test solution as solid solution niobium in described icp ms;
As the mass percentage > 0.010% of solid solution niobium in described steel sample, the solution of the described steel sample after electrolysis 5 ~ 10min is directly loaded into the test solution as solid solution niobium in described icp ms.
7. the assay method of solid solution content of niobium in steel as claimed in claim 1, is characterized in that: described employing icp ms measures the quality m of the solid solution niobium in the solution of described steel sample, and the quality m of solid solution niobium in blank solution
0process comprise the steps:
Take 8 parts of 0.1000g pure iron respectively in 250mL beaker, add 10mL water respectively, nitric acid dissolution in low temperature that 10mL density is 1.42g/mL, solution after dissolving is moved in 8 100mL volumetric flasks respectively, respectively add the solution of 1g potassium chloride and 1.3g citric acid water, pipette niobium standard solution 0.00mL, 0.50mL, 2.00mL, 5.00mL, 10.00mL of 0.1 μ g/mL respectively, niobium standard solution 10.00mL, 20.00mL, 50.00mL of 1.0 μ g/mL are in each volumetric flask, use water constant volume, take caesium as internal standard element, adopt plasma mass spectrometry to measure.With the massfraction of niobium for horizontal ordinate, intensity is ordinate, drawing curve;
Icp ms is adopted to measure the intensity of the solid solution niobium in the solution of described steel sample, and the intensity of solid solution niobium in blank solution;
On described working curve, the quality m of the solid solution niobium in the solution of corresponding described steel sample is obtained according to the intensity of the solid solution niobium in the intensity of the solid solution niobium in the solution of described steel sample, described blank solution, and the quality m of solid solution niobium in described blank solution
0.
8. the assay method of solid solution content of niobium in steel as claimed in claim 1, is characterized in that: described steel sample is the columnar samples of diameter 8mm ~ 10mm, long 80mm ~ 100mm.
9. the assay method of solid solution content of niobium in steel as claimed in claim 1, it is characterized in that: in described process of being soaked in water and hydrochloric acid by steel sample, the time of described immersion is 10min ~ 20min.
10. the assay method of solid solution content of niobium in steel as claimed in claim 9, it is characterized in that: in the described process that steel sample is soaked in water and hydrochloric acid, the volume of described water is 20mL ~ 30mL, and the density of described hydrochloric acid is 1.19g/mL, and the volume of described hydrochloric acid is 20mL ~ 30mL.
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| CN117110128A (en) * | 2023-10-24 | 2023-11-24 | 中国航发北京航空材料研究院 | Quantitative test method for gamma' -phase mass fraction in nickel-based powder superalloy |
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| CN117110128B (en) * | 2023-10-24 | 2024-01-30 | 中国航发北京航空材料研究院 | Quantitative test method for gamma' -phase mass fraction in nickel-based powder superalloy |
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