CN105842021A - Method for determining contents of impurity elements in alloy, and preparation method for sample solution - Google Patents
Method for determining contents of impurity elements in alloy, and preparation method for sample solution Download PDFInfo
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Abstract
The invention relates to a method for determining the contents of impurity elements in alloy and a preparation method for a sample solution, belonging to the technical field of element detection. According to the invention, the sample solution is prepared by digesting a sample with nitric acid, hydrogen peroxide, hydrochloric acid and hydrofluoric acid according to specific steps; then ICP-OES is used for direct and simultaneous determination of the contents of impurity elements including boron, cobalt, chromium, copper, molybdenum, nickel, lead, titanium, phosphorus, etc. in the sample solution. The preparation method for the sample solution has the characteristics that sample digestion is complete and lossless; operation is rapid; an examination period is short; the prepared sample solution is simple in composition; the usage amount of reagents is small; blank is low; the number of interference factors is small; etc. The determination method has the advantages of few interference factors, high efficiency, rapidness and high precision, and meets demands for both product quality examination and control on the impurity elements in an alloy material.
Description
Technical field
The present invention relates to measure method and the preparation method of sample solution of impurity content in alloy, belong to Element detection technology
Field.
Background technology
Silicomangan, manganeisen and Antaciron etc. are necessary auxiliary materials in steel smelting procedure, are most commonly used as alloy
Additive, double deoxidizer or desulfurizing agent etc., the past Focus On Quality point of this type of alloy product is mainly silicon, manganese, phosphorus, aluminum,
The alloy such as carbon, sulfur or impurity composition, control and improving constantly that steel quality requires now with smelting, be gradually increased silicon
The examination and test of products of the impurity content such as boron, cobalt, chromium, copper, molybdenum, nickel, lead, titanium in the alloy materials such as manganese, ferromanganese, ferrosilicon
Require and limit index is the strictest.Its reason be practice find boron in alloy adjuvant, cobalt, chromium, copper, molybdenum, nickel, lead,
Steel product quality is produced and has a strong impact on by the impurity such as titanium, and such as trace B can be greatly enhanced the quenching degree of steel, but if steel
In mass fraction containing boron more than 0.01%, then cause steel toughness relatively low because organizational structure occurs the most crisp boride.
For this reason, it may be necessary to boron, cobalt, chromium, copper, molybdenum, nickel, lead, titanium etc. are miscellaneous in grasping alloy materials such as measuring silicomanganese, ferromanganese, ferrosilicon
The sample preparation methods of prime element content and detection method.
At present, measure alloying element in the alloy material such as silicomanganese, ferromanganese, ferrosilicon mainly use the chemical analysis methods such as volumetric method or
The instrument analytical methods such as X fluorescence spectrum (XRF), measure trace impurity be then mainly use the chemical analysis method such as light splitting degree or
The instrument analytical methods such as inductively coupled plasma atomic emission spectrum (ICP-OES).
ICP-OES measure impurity content in the alloy material such as silicomanganese, ferromanganese, ferrosilicon mainly use with hydrochloric acid, nitric acid,
Fluohydric acid. and perchloric acid clear up sample as composite reagent heating, and high temperature evaporation emits that perchloric acid cigarette is the most dry to solution or wet salt shape,
The most again with the sample preparation methods of dissolving with hydrochloric acid salt.This type of method all employs a large amount of Fluohydric acid., anti-with silicon by Fluohydric acid.
Effumability Silicon fluoride. should be generated thus promote to clear up the alloy samples such as silicon content the highest silicomanganese, ferromanganese and ferrosilicon completely,
But its clear up agent combination, heating for dissolving sample and evaporation smolder catch up with acid etc. sample preparation condition, do not only exist sample digestion
Preparation time length, clear up the shortcomings such as the impact of reagent dosage background big, blank is serious, it is important to cause hydrogen fluorine at this point in the reaction
Acid and boron react and generate the boron trifluoride of effumability and volatilize from solution and escape, thus this sample preparation methods cannot be fitted completely
Content for Accurate Determining boron.Although, it is followed by improving this type of Wet technology, also has employing in clearing up agent combination
Increase and employ phosphoric acid, improve stability to boron by the effect of phosphoric acid, but be introduced into there is high boiling point, high density, height
The phosphoric acid of the characteristics such as viscosity not only further increases the complexity that prepared sample detection solution matrix is constituted, and adds matrix effect
Should, background influence ICP-OES is measured the interference of boron content, and phosphoric acid stablizes boron under this Specimen eliminating preparation condition
Actual effect the most undesirable, even control slightly deviation due to heating-up temperature and reaction condition, be easily generated pyrophosphate precipitation,
Have a strong impact on testing result accuracy.Use and clear up using hydrochloric acid, nitric acid and Fluohydric acid. as composite reagent, sealed microwave heating be
A kind of technical method of the above-mentioned difficult problem of preferable solution, but the analysis special microwave that laboratory is necessary for this configuration expensive clears up instrument,
Method is difficult to penetration and promotion.
Measure boron content in the alloy samples such as silicomanganese, ferromanganese, ferrosilicon at present and be mainly Beryllium ReagentⅢ spectrophotography, its sample
The reagent such as product preparation method is by the alkaline reagents such as sodium hydroxide fusion and decomposition sample in high temperature Muffle furnace, dilute hydrochloric acid leaching is molten
Melting thing, then with in brium carbonate and produce red precipitate separating, boron forms solubility barium metaborate and remaines in solution；
Detection method is then that in acid medium, boron and Beryllium ReagentⅢ react generation violet complex, by measuring it at wavelength 567nm
Absorbance thus be calculated the content of boron element.This type of chemical analysis method existence operation complexity is loaded down with trivial details, interference effect factor is many,
The technical disadvantages such as round of visits length, single element determination efficiency are low, it is impossible to meet quick, Accurate Determining silicomanganese, ferromanganese, ferrosilicon etc.
In alloy material, the needs of the impurity content such as boron, its know-why and operating procedure and this programme do not have relatedness.And,
The sample preparation method of alkaline reagent high-temperature fusion used by chemical method is not suitable for ICP-OES mensuration Specimen eliminating and prepares solution
The content of the impurity elements such as middle boron, cobalt, chromium, copper, molybdenum, nickel, lead, titanium, because the method introduces the alkali gold such as substantial amounts of sodium
Belong to ion, considerably increase the interference factor such as matrix effect, background influence, result in testing result accuracy and elaboration declines.
Summary of the invention
The present invention is directed to drawbacks described above, it is provided that a kind of measure the preparation method of the sample solution of impurity content in alloy, through pre-
Processing the sample solution after preparation can use ICP-OES to measure impurity content in the alloy materials such as silicomanganese, ferromanganese, ferrosilicon.
First technical problem that the present invention solves is to provide and measures the preparation method of the sample solution of impurity content in alloy.
The present invention measures the preparation method of the sample solution of impurity content in alloy, and its step is followed successively by:
A, take alloy sample to be measured, be placed in container, and it is mixed with nitric acid and hydrogen peroxide, be heated to boiling, carry out anti-
Should, obtain reactant liquor A；
B, under fluidized state, reactant liquor A is mixed with hydrogen peroxide, carry out high temperature Strong oxdiative reaction；
C, addition hydrochloric acid continuation reaction under fluidized state；
D, with water eluant container wall, continue to react under fluidized state；Or after water eluant container wall, evaporation and concentration is molten
Liquid is to solution small size；
E, with water eluant container wall, and solution is cooled to 55 DEG C～60 DEG C, holds at addition Fluohydric acid., quiet
Putting reaction complete to Specimen eliminating, solution is clarified；
F, cooling, constant volume, the detection sample solution of impurity content in alloy must be measured；
Wherein, described alloy is silicomangan, manganeisen or Antaciron.
Preferably, by volume, nitric acid: hydrogen peroxide: hydrochloric acid=1:0.8～1.2:0.8～1.2, wherein, hydrogen peroxide is a
The total amount of the hydrogen peroxide used by step and b step, is preferably by volume, nitric acid: hydrogen peroxide: hydrochloric acid=1:1:1.
Further, preferably sample quality: nitric acid volume=0.2～0.5g:4～10mL, more preferably sample quality: nitric acid volume
=0.2g:4mL.
Further, the most every 0.1 gram of sample adds 0.5～1.5mL Fluohydric acid..
Preferably, a step reaction time is 4～8min, and b step oxidation time is 3～5min, and step c is anti-
Should produce without nitrogen dioxide Brown gas to solution, now, solution colour shoals；The Step d response time is 5～10min, d
Step evaporation and concentration to liquor capacity is 5ml.
Further, in step e, adding Fluohydric acid. and standing and reacting the most at twice to Specimen eliminating completely, solution is clarified.
Preferably, described nitric acid mass percent concentration is 65%～68%, the mass percent concentration of hydrogen peroxide >=
30%, hydrochloric acid mass percent concentration is 36%～38%.
The present invention, by controlling the reaction conditions such as the ratio of reagents of Specimen eliminating, addition sequence, time and temperature, promotes that sample disappears
The volatilization loss of boron is it also avoid while solution.That is, first with nitric acid, hydrogen peroxide and hydrochloric acid under high temperature heating conditions
Most elements in addition to silicon in sample are cleared up and are reacted into solution by composite reagent, clear up the element to be measured entered in solution
Boron stably remaines in the form such as ion or boric acid and avoids its volatilization loss in solution；Then reaction temperature is reduced to trifluoro
Change 55 DEG C～the tepid state of 60 DEG C that boron water solublity is fair, then add Fluohydric acid. for mainly clearing up high level in sample
The element silicon of slightly solubility and alloy crystal, and it is wrapped and fails other materials effectively cleared up, it is ensured that sample
Clear up completely and without any residue, avoid that reaction in hydrofluoric medium generates has low boiling, low melting point etc. property simultaneously
The boron trifluoride volatilization loss of matter, therefore scheme is simultaneously achieved and avoids because Specimen eliminating not exclusively causes element boron to be measured to wrap up
Among insoluble residue, or escape because element boron to be measured decomposes volatilization with boron trifluoride form from solution, thus effective guarantee
The reliability of sample preparation methods, solves and causes the residual of element to be measured or volatilization in Sample Preparation Procedure and lose, serious shadow
Ring the technical problem of measurement result accuracy.
It addition, hydrogen peroxide decomposes carbide with nitric acid the efficient oxidation, and hydrogen peroxide decomposes simply by boiling solution mode
Remove；Add hydrogen peroxide Strong oxdiative or add concentrated hydrochloric acid reaction time, a large amount of nitric acid reactions generate nitrogen dioxide brown flue gas from
Solution escapes, reduce further the impact that acidity crosses effect, follow-up ICP-AES is measured by matrix effect；Do not use high boiling
The reagent such as point, high density, full-bodied phosphoric acid, perchloric acid, prepared sample solution constitutes simple, reagent blank background is little,
Reduce the factor such as matrix effect, background influence interference ICP-AES and measure the content of micro impurity element.
Second technical problem that the present invention solves is to provide the method for impurity content in alloy that measures.
The present invention measures the method for impurity content in alloy, uses preparation method of the present invention to prepare sample solution, adopts
With ICP-AES (ICP-OES), boron in Simultaneous Direct Determination sample solution, cobalt, chromium, copper,
The content of the impurity elements such as molybdenum, nickel, lead, titanium, phosphorus.
Preferably detection parameter includes: HF acid resistant device, RF power 1350W, and secondary air speed 1.5L/min is compacted
Dynamic pump pump speed 85r/min, height of observation 11.2mm, nebulizer pressure 0.32MPa, measure the time of integration 15～20s.
Preferably analysis spectral line is: B 208.959nm, Co 231.160nm, Cr 206.157nm, Cu 327.396nm, Mo
204.598nm, Ni 231.604nm, Pb 220.353nm, Ti 336.121nm, P 178.284nm.
The preparation method of inventive samples solution, simply effectively prevent the volatilization loss of element boron to be measured, and does not uses high boiling
The reagent such as point, high density, full-bodied phosphoric acid, perchloric acid, more efficiently promote carbide oxidation Decomposition in sample complete simultaneously
Entirely.Have that Specimen eliminating round of visits completely lossless, swift to operate is short, sample preparation solutions constitutes simple, the few sky of reagent dosage
The features such as the lowest, interference effect factor is few, it is achieved that ICP-OES measures boron cobalt chromium-copper in silicomanganese, ferromanganese, Antaciron simultaneously
The target of the constituent contents such as molybdenum nickel lead titanium phosphorus.
The detection method of the present invention has that interference effect factor is few, multielement simultaneous determination, the most quickly, precision high accuracy
The feature such as good, meet simultaneously to boron in the alloy materials such as silicomanganese, ferromanganese, ferrosilicon, cobalt, chromium, copper, molybdenum, nickel, lead, titanium,
The impurity elements such as phosphorus carry out the needs of product quality inspection and control.
Detailed description of the invention
The present invention measures the preparation method of the sample solution of impurity content in alloy, and its step is followed successively by:
A, take alloy sample to be measured, be placed in container, and it is mixed with nitric acid and hydrogen peroxide, be heated to boiling, carry out anti-
Should, obtain reactant liquor A；
B, under fluidized state, reactant liquor A is mixed with hydrogen peroxide, carry out high temperature Strong oxdiative reaction；
C, addition hydrochloric acid continuation reaction under fluidized state；
D, with water eluant container wall, continue to react under fluidized state；Or after water eluant container wall, evaporation and concentration is molten
Liquid is to solution small size；
E, with water eluant container wall, and solution is cooled to 55 DEG C～60 DEG C, holds at addition Fluohydric acid., quiet
Putting reaction complete to Specimen eliminating, solution is clarified；
F, cooling, constant volume, the detection sample solution of impurity content in alloy must be measured；
Wherein, described alloy is silicomangan, manganeisen or Antaciron.
Wherein, by volume, nitric acid: hydrogen peroxide: hydrochloric acid=1:0.8～1.2:0.8～1.2, wherein, hydrogen peroxide is a step
The total amount of the hydrogen peroxide suddenly and used by b step, is preferably the most by volume, nitric acid: hydrogen peroxide: hydrochloric acid=1:1:1.The most whole
The volume ratio of whole consumptions of nitric acid, hydrogen peroxide and hydrochloric acid used in Specimen eliminating preparation process is 1:0.8～1.2:
0.8～1.2, preferably 1:1:1；Further, hydrogen peroxide is divided into twice in two differential responses stages (a step and b step)
It is separately added into.B step is again supplemented in reactant liquor A under fluidized state and is added hydrogen peroxide, mainly by high temperature shape
The nascent oxygen with Strong oxdiative ability that under state, peroxide decomposition is formed, is conducive to fully decomposing sample by the reaction of its Strong oxdiative
Indissoluble carbide in product；Easily decompose owing to hydrogen peroxide is heated, if a step the most all adds, can be in solution thermal histories
The just major part that not yet plays a role decomposes volatilization loss；And second step supplements when adding hydrogen peroxide, major part sample is
Being resolved entrance solution, the hydrogen peroxide now added more can the direct indissoluble carbide effect with residual effectively.
Further, preferably sample quality: nitric acid volume=0.2～0.5g:4～10mL, more preferably sample quality: nitric acid volume
=0.2g:4mL.
Further, every 0.1 gram of sample adds 0.5～1.5mL Fluohydric acid..Silicomangan and manganeisen often 0.1 gram of sample
Being preferably added to 0.5ml Fluohydric acid., Antaciron can increase by 0.5～1mL Fluohydric acid. with silicone content height on this basis more.
Further, a step reaction time is 4～8min, and b step oxidation time is 3～5min, and step c is reacted extremely
Producing without nitrogen dioxide Brown gas in solution, now, solution colour shoals；The Step d response time is 5～10min, and d walks
Flash evaporation is sent out and is concentrated into liquor capacity is 5ml.
Further, in step e, with water eluant container wall after solution evaporation concentration, and solution is cooled to 55 DEG C～60
DEG C, it is maintained in low temp. electric hot plate or water-bath in this temperature range, adds Fluohydric acid. and standing and reacting at twice to sample
Clearing up completely, solution is clarified；After cooling, test solution is diluted to scale with water, mixing.
Nitric acid used in the present invention, hydrogen peroxide and hydrochloric acid are both preferably the denseest reagent of the market sale of not diluted, as
Preferred version, described nitric acid mass percent concentration is 65%～68%, mass percent concentration >=30% of hydrogen peroxide, salt
Acid mass percent concentration is 36%～38%.
Concrete, the present invention can use following steps: weighs sample 0.2～0.5g sample, is placed in the containers such as polytetrafluoroethylene beaker
In, in the way of rinsing wall of cup, wall of cup adds concentrated nitric acid and the 2～5mL hydrogen peroxide of 4～10mL not diluted, carries out high temperature
Reacting by heating and holding reaction 4～8min under boil condition；2～5mL peroxidating are again added under solution fluidized state
Hydrogen carries out Strong oxdiative reaction, and keeps solution boiling 3～5min；It is subsequently added into 4～10mL concentrated hydrochloric acid to seethe with excitement at high-temperature heating
Reaction is continued, until the generation amount of nitrogen dioxide brown flue gas significantly reduces color and gradually becomes shallower as in solution under state；Then with about
3～5mL water eluant container walls, continue to react under solution fluidized state 5～10min, or heating evaporation concentrates solution
Volume is to about 5mL；With about 3～5mL water eluant container walls and solution is cooled to 55 DEG C～60 DEG C, at Low-temp. electrothermal
Plate or water-bath are maintained under this state of temperature, add 1～2.5mL Fluohydric acid. and standing and reacting altogether at twice and disappear to sample
Solving completely, solution is clarified；After cooling, test solution is transferred in 100mL plastics volumetric flask, is diluted to scale with water, mixing.
The present invention, by controlling the reaction conditions such as the ratio of reagents of Specimen eliminating, addition sequence, time and temperature, promotes that sample disappears
The volatilization loss of boron is it also avoid while solution.That is, first with nitric acid, hydrogen peroxide and hydrochloric acid under high temperature heating conditions
Most elements in addition to silicon in sample are cleared up and are reacted into solution by composite reagent, clear up the element to be measured entered in solution
Boron stably remaines in the form such as ion or boric acid and avoids its volatilization loss in solution；Then reaction temperature is reduced to trifluoro
Change 55 DEG C～the tepid state of 60 DEG C that boron water solublity is fair, then add Fluohydric acid. for mainly clearing up high level in sample
The element silicon of slightly solubility and alloy crystal, and it is wrapped and fails other materials effectively cleared up, it is ensured that sample
Clear up completely and without any residue, avoid that reaction in hydrofluoric medium generates has low boiling, low melting point etc. property simultaneously
The boron trifluoride volatilization loss of matter, therefore scheme is simultaneously achieved and avoids because Specimen eliminating not exclusively causes element boron to be measured to wrap up
Among insoluble residue, or escape because element boron to be measured decomposes volatilization with boron trifluoride form from solution, thus effective guarantee
The reliability of sample preparation methods, solves and causes the residual of element to be measured or volatilization in Sample Preparation Procedure and lose, serious shadow
Ring the technical problem of measurement result accuracy.
It addition, hydrogen peroxide decomposes carbide with nitric acid the efficient oxidation, and hydrogen peroxide decomposes simply by boiling solution mode
Remove；Add hydrogen peroxide Strong oxdiative or add concentrated hydrochloric acid reaction time, a large amount of nitric acid reactions generate nitrogen dioxide brown flue gas from
Solution escapes, reduce further the impact that acidity crosses effect, follow-up ICP-AES is measured by matrix effect；Do not use high boiling
The reagent such as point, high density, full-bodied phosphoric acid, perchloric acid, prepared sample solution constitutes simple, reagent blank background is little,
Reduce the factor such as matrix effect, background influence interference ICP-AES and measure the content of micro impurity element.
The present invention measures the method for impurity content in alloy, uses preparation method of the present invention to prepare sample solution, adopts
With ICP-AES (ICP-OES), boron in Simultaneous Direct Determination sample solution, cobalt, chromium, copper,
The content of the impurity elements such as molybdenum, nickel, lead, titanium, phosphorus.
Preferably detection parameter includes: HF acid resistant device, RF power 1350W, and secondary air speed 1.5L/min is compacted
Dynamic pump pump speed 85r/min, height of observation 11.2mm, nebulizer pressure 0.32MPa, measure the time of integration 15～20s.
Preferably analysis spectral line is: B 208.959nm, Co 231.160nm, Cr 206.157nm, Cu 327.396nm, Mo
204.598nm, Ni 231.604nm, Pb 220.353nm, Ti 336.121nm, P 178.284nm.
Below in conjunction with embodiment, the detailed description of the invention of the present invention is further described, the most therefore limits the present invention to institute
Among the scope of embodiments stated.
Embodiment 1
Clearing up of silicomangan sample
Weighing silicomangan sample 0.2g (hereinafter referred to as No. 1 sample), in the way of rinsing wall of cup, wall of cup adds 4mL without dilute
The concentrated nitric acid released and 2mL hydrogen peroxide, high-temperature heating reaction and holding 4min under boil condition；At solution fluidized state
Under again add 2mL hydrogen peroxide and carry out Strong oxdiative reaction, and keep solution to seethe with excitement 3min；Add 4mL concentrated hydrochloric acid at height
Continue reaction under temperature ebuillition of heated state to gradually become shallower as to generation color without nitrogen dioxide brown flue gas in solution；With about 3mL water
Eluant container wall, continues to react 5min under solution fluidized state；With about 3mL water eluant container wall and solution is cold
But to 55 DEG C, and on low temp. electric hot plate, it is maintained at solution in 55 DEG C of temperature ranges, adds at twice and amount to 1mL Fluohydric acid.
And standing and reacting is complete to Specimen eliminating, solution is clarified；After cooling, test solution is transferred in 100mL plastics volumetric flask, with water
It is diluted to scale, mixing.
The content of impurity element in ICP-OES detection silicomangan sample solution
Emission spectrometry (ICP-OES) is cleared up as detection means, Simultaneous Direct Determination to have used inductively coupled plasma former
The content of the impurity element such as boron, cobalt, chromium, copper, molybdenum, nickel, lead, titanium, phosphorus in the sample solution of preparation.The instrument of ICP-OES
Device detection parameter specifically includes that HF acid resistant device, RF power 1350W, secondary air speed 1.5L/min, peristaltic pump
Pump speed 85r/min, height of observation 11.2mm, nebulizer pressure 0.32MPa, measure the time of integration 15～20s.Impurity element
Analysis spectral line is preferably: B 208.959nm, Co 231.160nm, Cr 206.157nm, Cu 327.396nm, Mo 204.598nm,
Ni 231.604nm, Pb 220.353nm, Ti 336.121nm, P 178.284nm.
Embodiment 2
Sample to be cleared up is 0.5000g silicomanganese sample (hereinafter referred to as No. 2 sample), adds 10mL concentrated nitric acid and 5mL mistake
Hydrogen oxide, pyroreaction also keeps 8min under boil condition；Again add 5mL hydrogen peroxide Strong oxdiative and keep boiling
5min；Add the reaction of 10mL concentrated hydrochloric acid high-boiling to produce to without nitrogen dioxide brown flue gas；With about 5mL water eluant container also
Evaporation and concentration liquor capacity is to about 5mL；With 5mL water eluant container and solution to be cooled to 57 DEG C, solution is placed in 57 DEG C of water
Bath is incubated, and addition 2.5mL Fluohydric acid. altogether reacts at twice.
In addition, clear up this silicomangan sample according to the method identical with the method for embodiment 1 and measure miscellaneous with ICP-OES
Prime element content.
Embodiment 3
Sample to be cleared up is 0.3000g manganeisen sample (hereinafter referred to as No. 3 sample), adds 6mL concentrated nitric acid and 3mL
Hydrogen peroxide, pyroreaction also keeps boil condition 5min；Again add 3mL hydrogen peroxide Strong oxdiative and keep the 4min that seethes with excitement；
Add the reaction of 6mL concentrated hydrochloric acid high-boiling to produce to without nitrogen dioxide brown flue gas；With about 4mL water eluant container and evaporate dense
Contracting liquor capacity is to about 5mL；With 5mL water eluant container and solution to be cooled to 58 DEG C, solution is placed in 58 DEG C of water-baths
Insulation, and addition 1.5mL Fluohydric acid. altogether reacts at twice.
In addition, clear up this ferromanganese sample according to the method identical with the method for embodiment 1 and measure impurity unit with ICP-OES
Cellulose content.
Embodiment 4
Sample to be cleared up is 0.4000g manganeisen sample (hereinafter referred to as No. 4 sample), adds 8mL concentrated nitric acid and 4mL
Hydrogen peroxide, pyroreaction also keeps boil condition 7min；Again add 4mL hydrogen peroxide Strong oxdiative and keep the 5min that seethes with excitement；
Add the reaction of 8mL concentrated hydrochloric acid high-boiling to produce to without nitrogen dioxide brown flue gas；With about 5mL water eluant container and at solution
10min is kept under fluidized state；With 5mL water eluant container and solution to be cooled to 60 DEG C, solution is placed in 60 DEG C of water-baths
Middle insulation, and addition 2.0mL Fluohydric acid. altogether reacts at twice.
In addition, clear up this ferromanganese sample according to the method identical with the method for embodiment 1 and measure impurity unit with ICP-OES
Cellulose content.
Embodiment 5
Sample to be cleared up is 0.2500g Antaciron sample (hereinafter referred to as No. 5 sample), adds 5mL concentrated nitric acid and 2.5mL
Hydrogen peroxide, pyroreaction also keeps boil condition 6min；Again add 2.5mL hydrogen peroxide Strong oxdiative and keep boiling
5min；Add the reaction of 5mL concentrated hydrochloric acid high-boiling to produce to without nitrogen dioxide brown flue gas；With about 5mL water eluant container also
Evaporation and concentration liquor capacity is to about 5mL；With 5mL water eluant container and solution to be cooled to 60 DEG C, solution is placed in 60 DEG C of water
Bath is incubated, and addition 2mL Fluohydric acid. altogether reacts at twice.
In addition, clear up this ferrosilicon sample according to the method identical with the method for embodiment 1 and measure impurity unit with ICP-OES
Cellulose content.
Embodiment 6 response rate is assessed
The present invention has carried out recovery test to No. 2 samples and No. 4 samples.First pass through embodiment 2 and embodiment 4 is surveyed respectively
Obtained the content of the impurity element such as institute's boracic, cobalt, chromium, copper, molybdenum, nickel, lead, titanium, phosphorus in sample 2 and sample 4；Then
The most additionally weigh sample 2 and sample 4, and be separately added into the standard solution of the impurity element to be measured of respective concentration, whole process
Repeat sample preparation and the detection operation of embodiment 2 and embodiment 4.
By the assessment of the response rate in order to verify sample solution preparation method and the detection method of the present invention, disappear completely solving sample
The effectiveness of the aspects such as the volatilization loss of the impurity to be measured such as solution and effumability element boron, and ICP-OES detection method mensuration is miscellaneous
The accuracy of prime element.Result of the test is shown in Table 1.
Table 1 recovery test
Table 1 is visible, and method measures the response rate of impurity element in the alloy such as silicomanganese, ferromanganese and, between 90%～110%, shows
Element determination result has higher accuracy and reliability.
Embodiment 7 precision is assessed
The present invention clears up preparation to embodiment 1, embodiment 3 and embodiment 5 carry out 8 independent sample solutions respectively and divides
Analysis measures, and the result measured 8 times carries out statistical disposition, the detection precision water represented according to relative standard deviation (RSD)
Flat, in order to assess the concordance of the duplicate test of the present invention.Measurement result is shown in Table 2.
Method precision (n=8) (%) analyzed by table 2
Table 2 is visible, method be used for measuring boron in the alloy samples such as silicomanganese, ferromanganese, ferrosilicon, cobalt, chromium, copper, molybdenum, nickel, lead,
The content of the impurity element such as titanium, phosphorus, its RSD is less than 10%, shows that repeatedly measurement result is consistent, the repeatability of method, reproduction
Property good, method has higher precision level.
Claims (10)
1. measure the preparation method of the sample solution of impurity content in alloy, it is characterised in that its step is followed successively by:
A, take alloy sample to be measured, be placed in container, and it is mixed with nitric acid and hydrogen peroxide, be heated to boiling, carry out anti-
Should, obtain reactant liquor A；
B, under fluidized state, reactant liquor A is mixed with hydrogen peroxide, carry out oxidation reaction；
C, addition hydrochloric acid continuation reaction under fluidized state；
D, with water eluant container wall, continue to react under fluidized state；Or with water eluant container wall, evaporation and concentration solution；
E, with water eluant container wall, and solution is cooled to 55 DEG C～60 DEG C, holds at addition Fluohydric acid., quiet
Putting reaction complete to Specimen eliminating, solution is clarified；
F, cooling, constant volume, the detection sample solution of impurity content in alloy must be measured；
Wherein, described alloy is silicomangan, manganeisen or Antaciron.
The preparation method of the sample solution of impurity content in mensuration alloy the most according to claim 1, it is characterised in that:
By volume, nitric acid: hydrogen peroxide: hydrochloric acid=1:0.8～1.2:0.8～1.2, wherein, hydrogen peroxide is a step and b step
The total amount of hydrogen peroxide used；It is preferably by volume, nitric acid: hydrogen peroxide: hydrochloric acid=1:1:1.
The preparation method of the sample solution of impurity content in mensuration alloy the most according to claim 1, it is characterised in that:
Sample quality: nitric acid volume=0.2～0.5g:4～10mL, preferably sample quality: nitric acid volume=0.2g:4mL.
The preparation method of the sample solution of impurity content in mensuration alloy the most according to claim 1, it is characterised in that:
Every 0.1 gram of sample adds 0.5～1.5mL Fluohydric acid..
The preparation method of the sample solution of impurity content in mensuration alloy the most according to claim 1, it is characterised in that:
The a step reaction time is 4～8min, and b step oxidation time is 3～5min, without titanium dioxide in step c reaction to solution
Nitrogen Brown gas produces；The Step d response time is 5～10min, and Step d evaporation and concentration to liquor capacity is 5mL.
The preparation method of the sample solution of impurity content in mensuration alloy the most according to claim 1, it is characterised in that:
In step e, adding Fluohydric acid. and standing and reacting at twice to Specimen eliminating completely, solution is clarified.
The preparation method of the sample solution of impurity content in mensuration alloy the most according to claim 1, it is characterised in that:
Described nitric acid mass percent concentration is 65%～68%, mass percent concentration >=30% of hydrogen peroxide, hydrochloric acid percent mass
Specific concentration is 36%～38%.
8. measure the method for impurity content in alloy, it is characterised in that: use the system described in any one of claim 1～7
Preparation Method prepares sample solution, uses ICP-AES, in Simultaneous Direct Determination sample solution
Constituent content, described element is boron, cobalt, chromium, copper, molybdenum, nickel, lead, titanium and phosphorus.
9. want the method for impurity content in the mensuration alloy described in 8 according to right, it is characterised in that: detection parameter includes:
HF acid resistant device, RF power 1350W, secondary air speed 1.5L/min, peristaltic pump pump speed 85r/min, height of observation
11.2mm, nebulizer pressure 0.32MPa, measure the time of integration 15～20s.
10. want the method for impurity content in the mensuration alloy described in 8 according to right, it is characterised in that: analysis spectral line is:
B 208.959nm, Co 231.160nm, Cr 206.157nm, Cu 327.396nm, Mo 204.598nm, Ni 231.604nm,
Pb 220.353nm, Ti 336.121nm, P 178.284nm.
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