CN104569129B - The assay method of single rare earth oxide content in steel - Google Patents
The assay method of single rare earth oxide content in steel Download PDFInfo
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Abstract
The invention discloses a kind of assay method of single rare earth oxide content in steel, will clean, dries, steel sample quality m after steel sample water and salt acid soak1；Using steel sample as anode, as negative electrode, the ethanol solution of anhydrous Lithium chloride and acetylacetone,2,4-pentanedione is electrolysed stainless steel as electrolyte；Steel sample after electrolysis is rinsed to obtain the first washing lotion with the mixed solution of iodine and absolute ethyl alcohol, steel sample quality m after electrolysis2；First washing lotion is heated, is filtrated to get the first precipitation；The precipitation of nitric acid washing first simultaneously heats the first precipitation, and filter paper is filtrated to get the second precipitation, the precipitation of nitric acid washing second；Nitric acid carbonization filter paper is added, after adding perchloric acid decomposition, adds hydrochloric acid, constant volume obtains 100mL test solutions；Single rare earth oxide mass m and m in test solution and blank test solution are determined using icp mses0；Single rare earth oxide content in steel is calculated.
Description
Technical field
The present invention relates to technical field of analytical chemistry, specifically, is related to a kind of survey of single rare earth oxide content in steel
Determine method.
Background technology
The research of the application of rare earth in steel, distribution etc. is a lot, due to complexity existing for rare earth in steel, chemical analysis
The research report of method is seldom.Rare earth and field trash are dissolved in the steel mainly recommended in the prior art using metallurgical analysis information network
Assay method.The defects of certain be present using electrolytic separation-photometry measure in the recommendation method.This method is numerous and diverse first, examines
Survey lower limit for height (0.001%), the content of single rare earth, the content of the various rare earth states of low content particularly in steel can not be provided
It can not be measured；Meanwhile recommend method dilute using the ethanol solution extraction of the ethylene glycol of+5% triethanolamine of 1% lithium chloride+5%
Soil is mingled with sulfide, and the electrolyte internal resistance is big, and with the increase of electrolysis time, electrolysis temperature constantly rises, it is difficult to control -10
It is electrolysed below DEG C, has considerable amount of field trash to be decomposed in electrolytic process, therefore Extraction of rare earth field trash can not be quantified.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of assay method of single rare earth oxide content in steel, can
Quickly, single rare earth oxide content in Accurate Determining steel.
Technical scheme is as follows：
The assay method of single rare earth oxide content in a kind of steel, including：To be cleaned after steel sample water and salt acid soak,
Dry, the steel sample quality of weighing is m1；Using the steel sample as anode, using stainless steel as negative electrode, by anhydrous Lithium chloride and
The ethanol solution of acetylacetone,2,4-pentanedione is electrolysed as electrolyte；By the electrolysis residue iodine of the steel sample after electrolysis and anhydrous second
The mixed solution of alcohol rinses to obtain the first washing lotion, and the quality of the steel sample after electrolysis of weighing is m2；First washing lotion is added
Heat, it is filtrated to get the first precipitation；First precipitation is washed with nitric acid and heats the described first precipitation, and use is quantitatively filtered at a slow speed
Paper is filtrated to get the second precipitation, and washs second precipitation with nitric acid；Added into the described second precipitation described in nitric acid carbonization
Filter paper, after adding perchloric acid decomposition, hydrochloric acid is added, constant volume obtains 100mL test solutions；Using caesium as internal standard element, using electricity
Feel the quality m that couple plasma mass spectrometer determines the single rare earth oxide in the test solution, and in blank solution
Single rare earth oxide quality m0；Using formulaObtain single rare earth oxygen in steel
Compound content.
Further：The weight/mass percentage composition of anhydrous Lithium chloride is 1%~1.2% in the electrolyte, the body of acetylacetone,2,4-pentanedione
Product percentage is 5%~7%, and the volume of the electrolyte is 200~250mL.
Further：The electric current of the electrolysis is 0.3A~0.6A, and temperature is less than -10 DEG C, and the time is 10min~30min.
Further：In described the step of heating first washing lotion, the temperature of heating is 48~52 DEG C, the time 1.8
~2.2h.
Further, described the step of washing first precipitation with nitric acid, includes：Washed with the nitric acid that mass concentration is 2%
After first precipitation, then wash described first with the nitric acid that 48~52mL mass concentrations are 2% and precipitate.
Further：In described the step of heating the described first precipitation, the temperature of heating is 48~52 DEG C, the time is 28~
32min。
Further：In described the step of washing second precipitation with nitric acid, the mass concentration of nitric acid is 2%.
Further：It is described that the nitric acid carbonization filter paper is added into the described second precipitation, after adding perchloric acid decomposition, add
In the step of entering hydrochloric acid, the volume of nitric acid is 8~12mL, and the volume of perchloric acid is 2~4mL, and the volume of hydrochloric acid is 2~4mL.
Further：The shape of the steel sample is that basal diameter is 8mm~10mm, a height of 80mm~100mm column；It is described
By in the step of steel sample water and salt acid soak, the volume of water is 20~30mL；The volume of hydrochloric acid is 20~30mL, and density is
1.19g/mL；Soak time is 10~20min.
Further：The single rare earth determined using icp mses in the test solution is aoxidized
The quality m of thing, and the quality m of the single rare earth oxide in blank solution0Process include：It is 1.0 μ to pipette concentration respectively
G/mL lanthanum, cerium, praseodymium, neodymium, samarium standard liquid 0mL, 0.50mL, 1.00mL, 2.50mL, 5.00mL, 10.00mL, add density p
1.42g/mL nitric acid 2mL, density p 1.19g/mL hydrochloric acid 2mL, are diluted with water to 100mL, using caesium as internal standard element, use
The icp mses measure, using the weight/mass percentage composition of single rare earth oxide as abscissa, mass spectrum is strong
Spend for ordinate, drawing curve；The list in the test solution is determined using the icp mses
The mass spectral intensities of one rare earth oxide, and the intensity of the single rare earth oxide in blank solution；According to the test solution
In the mass spectral intensities of single rare earth oxide, the mass spectral intensities of single rare earth oxide in the blank solution are in the work
Make the quality m of the single rare earth oxide in the test solution corresponding to being obtained on curve, and in the blank solution
The quality m of single rare earth oxide0。
The technique effect of the present invention is as follows：
The electrolyte internal resistance of the inventive method is small, can ensure that electrolysis temperature is maintained at less than -10 DEG C in electrolytic process,
The rare earth oxide of less stable is avoided to decompose；Meanwhile determined using ICP-MS, single rare earth oxide can be determined
Amount, substantially increases the degree of accuracy and precision.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is described in further detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit
The fixed present invention.
The assay method of single rare earth oxide content comprises the following steps that in the steel of the present invention：
Step S1：It is that basal diameter is 8~10mm that steel sample is made into shape, a height of 80~100mm column.
Step S2：It will clean, dry after 10~20min of immersion in above-mentioned steel sample water and hydrochloric acid, quality of weighing is m1。
Wherein, the volume of water is 20~30mL, preferably 25mL；The volume of hydrochloric acid is 20~30mL, preferably 25mL, close
Spend for 1.19g/mL；Soak time is 10~20min.Alcohol flushing can also be used after cleaning.Drying can use the side dried
Formula.
Step S3：Using above-mentioned steel sample as anode, using stainless steel as negative electrode, by the nothing of anhydrous Lithium chloride and acetylacetone,2,4-pentanedione
Hydrous ethanol solution is electrolysed as electrolyte.
The purpose of electrolysis is to extract the rare earth oxide in steel sample.
Wherein, stainless steel can make tubular.The electric current of electrolysis is 0.3A~0.6A, and temperature is less than -10 DEG C, and the time is
10min~30min.The weight/mass percentage composition of anhydrous Lithium chloride is 1%~1.2% in electrolyte, the volume basis of acetylacetone,2,4-pentanedione
Than for 5%~7%.The volume of electrolyte is 250mL.The internal resistance of the electrolyte is small, is positively retained under low temperature and is electrolysed.The electrolysis
Process is carried out in electrolytic cell, and electrolyte can be held with glass beaker, then glass beaker is placed in electrolytic cell.
Preferably, steel sample can be put into 150mL glass beakers after the process of step S3 electrolysis residual with rod power taking solution is wiped
Slag.
Step S4：The electrolysis residue of steel sample after electrolysis is rinsed to obtain first with the mixed solution of iodine and absolute ethyl alcohol and washed
Liquid, the quality of the steel sample after electrolysis of weighing is m2。
Purpose in the step is to rinse caused residue after the electrolysis of steel sample, and iodine and absolute ethyl alcohol can be decomposed in steel sample
Rare-earth sulfide.Iodine used and the fixing fabric structure of the mixed solution of absolute ethyl alcohol are in 40mL.Steel sample after rinsing can be adopted
It is re-weighed with alcohol flushing and after drying.
Step S5：First washing lotion is heated, is filtrated to get the first precipitation.
Wherein, the temperature of heating is 48~52 DEG C, and preferably 50 DEG C, the time is 1.8~2.2h, preferably 2h, can be adopted
Use heating water bath.Filtering can use the bottle,suction for being covered with filter membrane to filter.
Step S6：The first precipitation is washed with nitric acid.
The purpose of the step is to decompose rare-earth oxide sulfate with nitric acid.
Wherein, the process that the first precipitation is washed with nitric acid specifically includes：It is heavy that first is washed with the nitric acid that mass concentration is 2%
Behind shallow lake, then the nitric acid for being 2% with 48~52mL (being preferably 50mL) mass concentration washs the first precipitation.The washing of first nitroxylic acid
Number can be 3~5 times.
Step S7：First precipitation is heated, the second precipitation is filtrated to get using quantitative filter paper at a slow speed, and the is washed with nitric acid
Two precipitations.
The purpose of the step is that further decomposition is mingled with oxysulfide with nitric acid decomposition rare earth.
Wherein, the temperature of heating is 48~52 DEG C, and preferably 50 DEG C, the time is 28~32min, preferably 30min.Use nitre
In the step of acid elution second precipitates, the mass concentration of nitric acid is 2%, and the number of washing is preferably 8~10 times.
Preferably,, will not when can also second be deposited in immigration 150mL glass beakers after step S7 is carried out
Filter paper part containing precipitation is torn off, then precipitation is moved into 150mL glass beakers together with filter paper.The filter paper of precipitation will not contained
It is to reduce carbonization time that part, which is torn off,.
Step S8：Nitric acid carbonization filter paper is added into the second precipitation, after adding perchloric acid decomposition, adds hydrochloric acid, constant volume
Obtain 100mL test solutions.
The purpose of the step is to decompose rare earth oxide with nitric acid carbonization filter paper, perchloric acid, and hydrochloric acid is used to dissolve possible production
Raw solid controls solution acidity simultaneously.
Wherein, the volume of nitric acid is 8~12mL, preferably 10mL, and the volume of perchloric acid is 2~4mL, preferably 3mL, salt
The volume of acid is 2~4mL, preferably 3mL.Nitric acid density is about 1.42g/mL, and perchloric acid density is about 1.68g/mL, and hydrochloric acid is close
Spend for 1.19g/mL.
Step S9：Using caesium as internal standard element, determined using icp mses single in test solution
The quality m of rare earth oxide, and the quality m of the single rare earth oxide in blank solution0。
Specifically, step S9 includes following process：
Step S91：Pipette respectively concentration be 1.0 μ g/mL lanthanum, cerium, praseodymium, neodymium, samarium standard liquid 0mL, 0.50mL,
1.00mL, 2.50mL, 5.00mL, 10.00mL, add density p 1.42g/mL nitric acid 2mL, density p 1.19g/mL hydrochloric acid
2mL, 100mL is diluted with water to, using caesium as internal standard element, is determined using icp mses, with single rare earth
The weight/mass percentage composition of oxide is abscissa, and mass spectral intensities are ordinate, drawing curve；
Step S92：The matter of the single rare earth oxide in test solution is determined using icp mses
The intensity of single rare earth oxide in spectral intensity, and blank solution；
Step S93：Single rare earth in the mass spectral intensities of single rare earth oxide in test solution, blank solution
The mass spectral intensities of oxide obtained on working curve corresponding to single rare earth oxide in test solution quality m, and
The quality m of single rare earth oxide in blank solution0。
Above-mentioned steps use icp mses, be because it has, temperature is high, atomization efficiency is high, by
The features such as chemistry disruption is small, make its Monitoring lower-cut low, precision is high, the range of linearity of concentration is wide, is disturbed between sample composition small etc. excellent
Point, turn into the incomparable analysis means of other analytical technologies in multielement simultaneous determination.
Step S10：Using formulaObtain single rare earth oxide content in steel.
The parameter of the method for the present invention is described further below.
1st, the selection of electrolyte
It is 0.4A in Faradaic current, electrolyte temperature is -10 DEG C by Wuhan Iron and Steel Plant rare earth steel standard sample and self-control rare earth steel sample
Hereinafter, self-control 1 is respectively adopted#Electrolyte：1% (weight/mass percentage composition) anhydrous Lithium chloride+5% (percent by volume) acetylacetone,2,4-pentanedione
Ethanol solution 250mL and 2#Recommendation method electrolyte：The ethanol solution of the ethylene glycol of+5% triethanolamine of 1% lithium chloride+5%
250mL, 20min Extraction of rare earth field trash total amounts are electrolysed, steel sample is removed, is respectively put into supersonic oscillations in 250mL glass beakers
Sampling, is separately added into 5mL ρ 1.19g/mL hydrochloric acid and 5mL ρ 1.42g/mL nitric acid, dissolves by heating, is surveyed using ICP-MS
It is fixed, it the results are shown in Table 1.
The result of the different electrolytes of table 1 electrolysis
| Electrolyte | Asserting value (%) | ICP-MS measured values (%) |
| 1# | 0.018~0.023 (steel Rare Earth Inclusions total amount) | 0.0225 |
| 2# | 0.018~0.023 (steel Rare Earth Inclusions total amount) | 0.0196 |
| 1# | 0.012 (steel middle rare earth total amount) | 0.0114 |
| 2# | 0.012 (steel middle rare earth total amount) | 0.0096 |
From table 1 it follows that 1 using the inventive method#Electrolyte extraction, ICP-MS measure re inclusion total amounts
Value is higher than recommendation method 2#Electrolyte extraction, ICP-MS measure re inclusion total amounts.Using 1#It is electrolysed in electrolyte electrolytic process
Temperature control is below -10 DEG C, but 2#Temperature gradually rises in electrolyte electrolytic process, and temperature can reach 5 after about 20 minutes
~10 DEG C, it is impossible to meet the requirement of electrolysis temperature.
2nd, the determination of steel middle rare earth separation condition
By the rare earth steel sample containing 0.012% oxide, using the 1 of the inventive method#Electrolyte, it is in Faradaic current
0.5A, electrolysis temperature are less than -10 DEG C, electrolysis time is 30min, are electrolysed, removed, are put into 150mL glass beakers
Sampled with rod is wiped, the electrolysis residue rinsed with the iodo- absolute ethyl alcohols of the inventive method 40mL on steel sample, fixing fabric structure is in 40mL, steel
Sample is cleaned with absolute ethyl alcohol, dried, and is weighed.
By above-mentioned sample in 50 DEG C of stirred in water bath 2h, filtered in the bottle,suction for be covered with filter membrane, with mass concentration 2%
Nitric acid washing precipitation 3~5 times, then washed the precipitation on filter membrane in 150mL glass beakers with the nitric acid that mass concentration is 2%,
The fixing fabric structure of nitric acid is in 50mL, in 50 DEG C of stirred in water bath 30min.Filter (filter membrane or fine and close filter paper), be with mass concentration
2% salpeter solution washing precipitation.
Precipitation obtained above is washed in 150mL glass beakers (membrane filtration), adds 5mL nitric acid, the heating of 2mL hydrochloric acid
Dissolving, move into 100mL volumetric flasks, ICP-MS measure, the results are shown in Table 2.
Precipitation obtained above is filtered with quantitative filter paper at a slow speed, when moving into 150mL glass beakers, precipitation will not contained
Filter paper part tear off, then precipitation is moved into 150mL glass beakers together with filter paper, adds different amounts of nitric acid and be fully carbonized filter
Paper, add different amounts of perchloric acid and decompose, move into 100mL volumetric flasks, ICP-MS measure, the results are shown in Table 3.
The steel middle rare earth of table 2 separates and the result (%) of measure
| Decompose acid | La | Ce | Pr | Nd | Sm |
| HNO3、HCl | 0.0036 | 0.0045 | 0.00052 | 0.00078 | ＜ 0.00001 |
The steel middle rare earth separation of the decomposition condition containing filter paper of table 3 and the result (%) of measure
It can be seen from the results above that nitric acid and college entrance examination chloric acid can decompose precipitation well, and because of nitric acid and high chlorine
Acid can decompose filter paper, so using nitric acid and perchloric acid.
3rd, the interference of coexistence elements
Because other constituent contents are seldom in measure system, therefore the measure of lanthanum, cerium, praseodymium, neodymium, samarium is not disturbed.But when molten
In liquid containing the facile hydrolysis element such as niobium, tungsten in the presence of, it is necessary to determined after dry filtering because have the fine particles such as niobium, tungsten easily block up into
Sample system and measured value is unstable.
Technical scheme is described further with specific embodiment below.
In following embodiments, the inductively-coupled plasma spectrometer that uses for PE companies of the U.S. model ELAN
DRC-e inductively-coupled plasma spectrometer, the running parameter of the spectrometer are as shown in table 4.Conductor refrigeration power supply is day
Jin Zhilengqichang productions.
The Instrument working parameter of table 4
Note：Determine isotope139La、140Ce、141Pr、146Nd、147Sm。
Each embodiment agents useful for same：Anhydrous Lithium chloride, analysis are pure；Acetylacetone,2,4-pentanedione, analysis are pure；Absolute ethyl alcohol, top pure grade；
Iodine, top pure grade；Nitric acid density is about 1.42g/mL, top pure grade；Hydrochloric acid density is 1.19g/mL, top pure grade；Perchloric acid density is about
For 1.68g/mL, top pure grade；Standard Stock solutions：Lanthanum, cerium, praseodymium, neodymium, samarium are 1000 μ g/mL, in the research of national standard material
The heart；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.
The acquisition methods of the working curve of the icp mses of each embodiment are as follows：
In 6 100mL volumetric flasks, pipette respectively concentration be 1.0 μ g/mL lanthanum, cerium, praseodymium, neodymium, samarium standard liquid 0mL,
0.50mL, 1.00mL, 2.50mL, 5.00mL, 10.00mL, add ρ 1.42g/mL nitric acid 2mL, ρ 1.19g/mL hydrochloric acid
2mL, it is diluted with water to scale and shakes up, using caesium as internal standard element, is determined using icp mses, instrument is automatic
Drawing curve, its coefficient correlation is more than 0.999.
Each embodiment use inductive constitution spectrometer measure process for：
ICP-MS is opened, after instrument lights a fire complete stability, the condition of work according to ICP-MS establishes the analysis side of sample
Method.Initially enter matched somebody with somebody standard liquid, select the measure isotope of each Rare Earth Elements Determination for139La、140Ce、141Pr、146Nd、147Sm, it is measured under this isotope, it is noiseless.Then using caesium as internal standard element, successively carry out sample blank,
The test of testing sample.
Embodiment 1
By be 0.012% containing total amount of rare earth rare earth steel standard sample be made basal diameter be 8mm, a height of 80mm post
Shape, show non-porous, flawless away from the groove that a depth is 2mm, observation is dug at the 4mm of top at it.
By sample fill 25mL water, 25mL ρ 1.19g/mL hydrochloric acid measuring cup in soak 10min take out, clean, ethanol
Rinse, dry, accurately weigh steel sample weight m1=88.6385g.
The acetyl of the anhydrous Lithium chloride including weight/mass percentage composition 1.2% prepared and percent by volume 5% will be filled
The electrolyte 250mL of the ethanol solution of acetone glass beaker is put into electrolytic cell, conductor refrigeration power supply is opened, by temperature
Degree is adjusted to less than -20 DEG C, and liquid temperature degree to be electrolysed reaches less than -10 DEG C, and using steel sample as anode, stainless steel cylinder is negative electrode, electrolysis electricity
0.4A is flowed, less than -10 DEG C are electrolysed, and are electrolysed 20min, are removed steel sample, are put into 150mL glass beakers residual with rod power taking solution is wiped
Slag, rinse electrolysis residue with iodo- absolute ethyl alcohol and obtain the first washing lotion, the fixing fabric structure of iodo- absolute ethyl alcohol is in 40mL, alcohol flushing
Dry, weigh steel sample m2=88.4836g, in company with band reagent blank.The 150mL glass beakers for filling the first washing lotion are placed in 50
In DEG C water-bath, 2h is stirred, is filtered in the bottle,suction for be covered with filter membrane and obtains the first precipitation.It is with mass concentration by the first precipitation
2% nitric acid is washed 3 times, then the first precipitation on filter membrane is washed into 150mL glass beakers with the nitric acid that mass concentration is 2%
In, the fixing fabric structure of secondary nitric acid is in 50mL.50 DEG C of stirred in water bath 30min are deposited in by first, use is fine and close at a slow speed
Filter paper is filtrated to get the second precipitation.The second precipitation is washed with the salpeter solution that mass concentration is 2% 8 times, will not contain precipitation
Filter paper part is torn off, then the second precipitation is moved into 150mL glass beakers together with filter paper, and the nitric acid for adding 10mL is fully carbonized filter
Paper, the perchloric acid for adding 3mL decompose, and add ρ 1.19g/mL hydrochloric acid 3mL, constant volume obtains to be measured in 100mL volumetric flask
Test solution, in company with band blank.
Using caesium as internal standard element, test solution and blank solution are measured using ICP-MS single in test solution
The quality m of rare earth oxide, and the quality m of the single rare earth oxide in blank solution0, m and m0(or m-m0) by instrument
Automatically provide, formula is calculated as follows and is calculated, the results are shown in Table 4.
Embodiment 2
By be 0.019% containing total amount of rare earth Biobium rare-earth steel sample be made basal diameter be 8.3mm, a height of 82mm column,
Show non-porous, flawless away from the groove that a depth is 2mm, observation is dug at the 3mm of top at it.
By sample fill 20mL water, 20mL ρ 1.19g/mL hydrochloric acid measuring cup in soak 20min take out, clean, ethanol
Rinse, dry, accurately weigh steel sample weight m1=89.3781g.
The levulinic of the anhydrous Lithium chloride including weight/mass percentage composition 1% prepared and percent by volume 6% will be filled
The electrolyte 250mL of the ethanol solution of ketone glass beaker is put into electrolytic cell, conductor refrigeration power supply is opened, by temperature
Less than -20 DEG C are adjusted to, liquid temperature degree to be electrolysed reaches less than -10 DEG C, and using steel sample as anode, stainless steel cylinder is negative electrode, Faradaic current
0.5A, less than -10 DEG C are electrolysed, and are electrolysed 15min, are removed steel sample, are put into 150mL glass beakers residual with rod power taking solution is wiped
Slag, the electrolysis residue rinsed with iodo- absolute ethyl alcohol on steel sample obtain the first washing lotion, the fixing fabric structure of iodo- absolute ethyl alcohol in 40mL,
Alcohol flushing dries, and weigh steel sample m2=89.2654g, in company with band reagent blank.The 150mL glass for filling the first washing lotion is burnt
Cup is placed in 48 DEG C of water-baths, stirs 2.2h, is filtered in the bottle,suction for be covered with filter membrane and is obtained the first precipitation.By the first precipitation matter
Measure the nitric acid that concentration is 2% to wash 5 times, then the first precipitation on filter membrane is washed into 150mL glass with the nitric acid that mass concentration is 2%
In glass beaker, the fixing fabric structure of secondary nitric acid is in 48mL.48 DEG C of stirred in water bath 32min are deposited in by first, using slow
The fine and close filter paper of speed is filtrated to get the second precipitation.The second precipitation is washed with the salpeter solution that mass concentration is 2% 10 times, will not contained
The filter paper part of precipitation is torn off, then the second precipitation is moved into 150mL glass beakers together with filter paper, and the nitric acid for adding 8mL is abundant
Be carbonized filter paper, and the perchloric acid smoke for adding 2mL is decomposed, and adds ρ 1.19g/mL hydrochloric acid 2mL, constant volume is in 100mL volumetric flask
In obtain test solution, in company with band blank.
Using caesium as internal standard element, test solution and blank solution are measured using ICP-MS single in test solution
The quality m of rare earth oxide, and the quality m of the single rare earth oxide in blank solution0, m and m0Provided automatically by instrument,
Calculated by the calculation formula of embodiment 1, the results are shown in Table 4.
Embodiment 3
By be 0.0009% containing cerium rare earth steel sample be made basal diameter be 8.2mm, a height of 82mm column, at it away from top
The groove that a depth is 2mm is dug at portion 4mm, observation shows non-porous, flawless.
By sample fill 30mL water, 30mL ρ 1.19g/mL hydrochloric acid measuring cup in soak 10min take out, clean, ethanol
Rinse, dry, accurately weigh steel sample weight m1=90.5968g.
The acetyl of the anhydrous Lithium chloride including weight/mass percentage composition 1.2% prepared and percent by volume 5% will be filled
The electrolyte 200mL of the ethanol solution of acetone glass beaker is put into electrolytic cell, conductor refrigeration power supply is opened, by temperature
Degree is adjusted to less than -20 DEG C, and liquid temperature degree to be electrolysed reaches less than -10 DEG C, and using steel sample as anode, stainless steel cylinder is negative electrode, electrolysis electricity
0.5A is flowed, less than -10 DEG C are electrolysed, and are electrolysed 30min, are removed steel sample, are put into 150mL glass beakers residual with rod power taking solution is wiped
Slag, the electrolysis residue rinsed with iodo- absolute ethyl alcohol on steel sample obtain the first washing lotion, the fixing fabric structure of iodo- absolute ethyl alcohol in 40mL,
Alcohol flushing dries, and weigh steel sample m2=89.2564g, in company with band reagent blank.The 150mL glass for filling the first washing lotion is burnt
Cup is placed in 52 DEG C of water-baths, stirs 1.8h, is filtered in the bottle,suction for be covered with filter membrane and is obtained the first precipitation.By the first precipitation matter
Measure the nitric acid that concentration is 2% to wash 5 times, then the first precipitation on filter membrane is washed into 150mL glass with the nitric acid that mass concentration is 2%
In glass beaker, the fixing fabric structure of secondary nitric acid is in 52mL.52 DEG C of stirred in water bath 28min are deposited in by first, using slow
The fine and close filter paper of speed is filtrated to get the second precipitation.The second precipitation is washed with the salpeter solution that mass concentration is 2% 10 times, will not contained
The filter paper part of precipitation is torn off, then the second precipitation is moved into 150mL glass beakers together with filter paper, and the nitric acid for adding 12mL is abundant
Be carbonized filter paper, and the perchloric acid smoke for adding 4mL is decomposed, and adds ρ 1.19g/mL hydrochloric acid 4mL, constant volume is in 100mL volumetric flask
In obtain test solution, in company with band blank.
Using caesium as internal standard element, test solution and blank solution are measured using ICP-MS single in test solution
The quality m of rare earth oxide, and the quality m of the single rare earth oxide in blank solution0, m and m0Provided automatically by instrument,
Calculated by the calculation formula of embodiment 1, the results are shown in Table 5.
Each embodiment measurement result of table 5
As can be seen from Table 4, the results contrast tested using the method for the present invention is accurate.
In summary, method of the invention optimizes electrolyte of the prior art, the electrolyte internal resistance of the inventive method
It is small, it can ensure that electrolysis temperature is maintained at less than -10 DEG C in electrolytic process, avoid the rare earth oxide point of less stable
Solution；Meanwhile determined using ICP-MS, the amount of single rare earth oxide can be determined, substantially increases the degree of accuracy and precision.This hair
Bright method provides accurate data for the exploitation of the steel grade containing rare earth and the research of the mechanism of action of rare earth in steel, has certain
Economic benefit and significant social benefit.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (7)
- A kind of 1. assay method of single rare earth oxide content in steel, it is characterised in that including：It will clean, dry after steel sample water and salt acid soak, the steel sample quality of weighing is m1；Using the steel sample as anode, using stainless steel as negative electrode, by anhydrous Lithium chloride and the ethanol solution of acetylacetone,2,4-pentanedione It is electrolysed as electrolyte, the electric current of the electrolysis is 0.3A~0.6A, and temperature is less than -10 DEG C, and the time is 10min~30min； The weight/mass percentage composition of anhydrous Lithium chloride is 1%~1.2% in the electrolyte, the percent by volume of acetylacetone,2,4-pentanedione for 5%~ 7%, the volume of the electrolyte is 200mL~250mL；The electrolysis residue of the steel sample after electrolysis is rinsed with the mixed solution of iodine and absolute ethyl alcohol to obtain the first washing lotion, weighed The quality of the steel sample after electrolysis is m2；First washing lotion is heated, is filtrated to get the first precipitation, the temperature of heating is 48~52 DEG C, and the time is 1.8~2.2h；First precipitation is washed with nitric acid and heats the described first precipitation, and it is heavy to be filtrated to get second using quantitative filter paper at a slow speed Form sediment, and second precipitation is washed with nitric acid；The nitric acid carbonization filter paper is added into the described second precipitation, after adding perchloric acid decomposition, adds hydrochloric acid, constant volume obtains 100mL test solutions；Using caesium as internal standard element, the single rare earth determined using icp mses in the test solution is aoxidized The quality m of thing, and the quality m of the single rare earth oxide in blank solution0；Using formulaObtain single rare earth oxide content in steel.
- 2. the assay method of single rare earth oxide content in steel as claimed in claim 1, it is characterised in that described to use nitric acid The step of washing first precipitation includes：With the nitric acid that mass concentration is 2% wash described first precipitate after, then with 48~ Nitric acid washing first precipitation that 52mL mass concentrations are 2% is formed sediment.
- 3. the assay method of single rare earth oxide content in steel as claimed in claim 1, it is characterised in that：Described in the general In the step of first precipitation heating, the temperature of heating is 48~52 DEG C, and the time is 28~32min.
- 4. the assay method of single rare earth oxide content in steel as claimed in claim 1, it is characterised in that：It is described to use nitric acid In the step of washing second precipitation, the mass concentration of nitric acid is 2%.
- 5. the assay method of single rare earth oxide content in steel as claimed in claim 1, it is characterised in that：It is described to described Nitric acid is added in second precipitation to be carbonized the filter paper, is added after perchloric acid decomposes, in the step of adding hydrochloric acid, the volume of nitric acid For 8~12mL, the volume of perchloric acid is 2~4mL, and the volume of hydrochloric acid is 2~4mL.
- 6. the assay method of single rare earth oxide content in steel as claimed in claim 1, it is characterised in that：The steel sample Shape is that basal diameter is 8mm~10mm, a height of 80mm~100mm column；It is described by steel sample water and the step of salt acid soak In rapid, the volume of water is 20~30mL；The volume of hydrochloric acid is 20~30mL, density 1.19g/mL；Soak time be 10~ 20min。
- 7. the assay method of single rare earth oxide content in steel as claimed in claim 1, it is characterised in that：It is described to use electricity Feel the quality m that couple plasma mass spectrometer determines the single rare earth oxide in the test solution, and in blank solution Single rare earth oxide quality m0Process include：Pipette respectively concentration be 1.0 μ g/mL lanthanum, cerium, praseodymium, neodymium, samarium standard liquid 0mL, 0.50mL, 1.00mL, 2.50mL, 5.00mL, 10.00mL, density p 1.42g/mL nitric acid 2mL, density p 1.19g/mL hydrochloric acid 2mL are added, is diluted with water to 100mL, using caesium as internal standard element, determined using the icp mses, with the matter of single rare earth oxide Amount percentage composition is abscissa, and mass spectral intensities are ordinate, drawing curve；The mass spectrum that the single rare earth oxide in the test solution is determined using the icp mses is strong Degree, and the intensity of the single rare earth oxide in blank solution；Single rare earth oxidation in the mass spectral intensities of single rare earth oxide in the test solution, the blank solution The mass spectral intensities of thing obtained on the working curve corresponding to single rare earth oxide in the test solution quality m, And the quality m of the single rare earth oxide in the blank solution0。
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| CN111855644A (en) * | 2020-07-07 | 2020-10-30 | 中国科学院金属研究所 | Method for enriching and quantifying rare earth elements in solubility product driven electrolyte |
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| US3885020A (en) * | 1971-10-28 | 1975-05-20 | Univ Southern California | Method of oxidizing hydrocarbons and oxygenated hydrocarbons to carbon dioxide and water |
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