CN105842021B - Measure the method for impurity content and the preparation method of sample solution in alloy - Google Patents
Measure the method for impurity content and the preparation method of sample solution in alloy Download PDFInfo
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Abstract
The present invention relates to the method for impurity content and the preparation method of sample solution in alloy is measured, belong to Element detection technical field.The technical problem to be solved by the present invention is to provide measure the method for impurity content and the preparation method of sample solution in alloy.The present invention carries out resolution sample by nitric acid, hydrogen peroxide, hydrochloric acid and hydrofluoric acid with specific step, sample solution is prepared, recycles the content of the impurity elements such as boron, cobalt, chromium, copper, molybdenum, nickel, lead, titanium, phosphorus in ICP OES Simultaneous Direct Determination product solution.The preparation method of inventive samples solution, have the characteristics that Specimen eliminating is completely lossless, round of visits swift to operate is short, sample preparation solutions constitute simple, reagent dosage and lack that blank is low, interference effect factor is lacked, its detection method interference effect factor is few, efficiently quick, precision is high, meets while being carried out to the impurity element in alloy material the needs of product quality inspection and control.
Description
Technical field
The present invention relates to the method for impurity content and the preparation method of sample solution in alloy is measured, belong to element inspection
Survey technology field.
Background technology
Silicomangan, manganeisen and Antaciron etc. are necessary auxiliary materials in steel smelting procedure, the most frequently used
Make alloy addition, double deoxidizer or desulfurizing agent etc., the past to the Focus On Quality point of such alloy product be mainly silicon, manganese,
The alloys such as phosphorus, aluminium, carbon, sulphur or impurity composition are gradually increased now with the continuous improvement for smelting control and steel quality requirement
The examination and test of products to impurity contents such as boron, cobalt, chromium, copper, molybdenum, nickel, lead, titaniums in the alloy materials such as silicomanganese, ferromanganese, ferrosilicon
It is required that and limit index it is more stringent.Its reason, which is to put into practice, finds boron, cobalt, chromium, copper, molybdenum, nickel, lead, titanium etc. in alloy auxiliary material
Impurity seriously affects steel product quality generation, such as trace B can greatly improve the quenching degree of steel, if but in steel
Mass fraction containing boron is more than 0.01%, then causes steel toughness relatively low because there is firmly crisp boride in institutional framework.
The impurity elements such as boron, cobalt, chromium, copper, molybdenum, nickel, lead, titanium in the alloy materials such as silicomanganese, ferromanganese, ferrosilicon are measured for this reason, it may be necessary to grasp
The sample preparation methods and detection method of content.
Currently, measuring alloying element in the alloy materials such as silicomanganese, ferromanganese, ferrosilicon mainly uses the chemical analyses sides such as volumetric method
The instrument analytical methods such as method or X fluorescence spectrum (XRF), it is then mainly using chemical analysis methods such as light splitting degree to measure trace impurity
Or the instrument analytical methods such as inductively coupled plasma atomic emission spectrum (ICP-OES).
ICP-OES measures impurity content in the alloy materials such as silicomanganese, ferromanganese, ferrosilicon and mainly uses with hydrochloric acid, nitre
Acid, hydrofluoric acid and perchloric acid clear up sample as composite reagent heating, and high temperature evaporation emit perchloric acid cigarette to solution it is closely dry or
Wet salt shape, then again with the sample preparation methods of dissolving with hydrochloric acid salt.Such method has used a large amount of hydrofluoric acid, passes through hydrogen fluorine
Acid generates effumability ocratation to promote to clear up the usually higher silicomanganese of silicon content, ferromanganese and ferrosilicon completely with pasc reaction
Equal alloy samples, but the combination of its digestive reagent, heating for dissolving sample and evaporation smolder and catch up with the sample preparations condition such as acid, not only
The shortcomings of long, digestive reagent dosage that there are sample digestion preparation times is greatly, the influence of blank background is serious, it is important to react item herein
Hydrofluoric acid is caused to react the boron trifluoride for generating effumability with boron under part and effusion of volatilizing from solution, thus the sample preparation
Method can not be suitable for the content of Accurate Determining boron completely.Such wet digestion technology is improved although being followed by, also has and uses
Increase in digestive reagent combination and used phosphoric acid, the stability to boron is improved by the effect of phosphoric acid, but what is introduced has height
The phosphoric acid of the characteristics such as boiling point, high density, high viscosity not only further increases answering for prepared sample detection solution matrix composition
Polygamy increases the interference of matrix effect, background influence to ICP-OES measurement boron contents, and in the Specimen eliminating system
The actual effect of phosphoric acid stabilization boron is very undesirable under the conditions of standby, or even since heating temperature and reaction condition control slightly deviation,
It is also easy to produce pyrophosphate precipitation, seriously affects testing result accuracy.It uses and is tried using hydrochloric acid, nitric acid and hydrofluoric acid as combination
Agent, sealed microwave heating resolution is a kind of technical method preferably solving above-mentioned problem, but laboratory must configure thus
Expensive analysis special microwave clears up instrument, and method is difficult to popularize.
It is mainly Beryllium ReagentⅢ spectrophotometry to measure boron content in the alloy samples such as silicomanganese, ferromanganese, ferrosilicon at present,
Its sample preparation methods be by alkaline reagents such as sodium hydroxides in high temperature Muffle furnace fusion and decomposition sample, the reagents such as dilute hydrochloric acid
Fusant is leached, then in barium carbonate and to generate and red precipitate and detached, boron forms soluble barium metaborate and remaines in
In solution；Detection method is then that boron reacts generation violet complex with Beryllium ReagentⅢ in acid medium, by wavelength 567nm
Place measures its absorbance to which the content of boron element be calculated.There are cumbersome, interference complicated for operation for such chemical analysis method
The technical disadvantages such as influence factor is more, round of visits is long, single element determination efficiency is low cannot be satisfied quick, Accurate Determining silicomanganese, manganese
The needs of the impurity contents such as boron in the alloy materials such as iron, ferrosilicon, technical principle and operating procedure do not have pass with this programme
Connection property.Moreover, the sample preparation mode of alkaline reagent high-temperature fusion used in chemical method is not suitable for ICP-OES determination samples
Resolution prepares the content of the impurity elements such as boron in solution, cobalt, chromium, copper, molybdenum, nickel, lead, titanium, because this method introduces largely
The alkali metal ions such as sodium considerably increase the disturbing factors such as matrix effect, background influence, result in testing result accuracy and essence
Close property declines.
Invention content
The present invention in view of the foregoing drawbacks, provides a kind of preparation side measuring the sample solution of impurity content in alloy
Method, the sample solution after preprocessed preparation can be used ICP-OES and measure impurity member in the alloy materials such as silicomanganese, ferromanganese, ferrosilicon
Cellulose content.
First technical problem that the present invention solves is to provide the system for measuring the sample solution of impurity content in alloy
Preparation Method.
The present invention measures the preparation method of the sample solution of impurity content in alloy, and step is followed successively by：
A, alloy sample to be measured is taken, is placed in container, and it is mixed with nitric acid and hydrogen peroxide, is heated to boiling, into
Row reaction, obtains reaction solution A；
B, reaction solution A is mixed under fluidized state with hydrogen peroxide, carries out high temperature Strong oxdiative reaction；
C, the reaction was continued for addition hydrochloric acid under fluidized state；
D, with water eluant container wall, continuation is reacted under fluidized state；Or with water eluant container wall after, evaporation it is dense
Contracting solution is to solution small size；
E, with water eluant container wall, and solution is cooled to 55 DEG C~60 DEG C, is kept at this temperature addition hydrofluoric acid,
It is complete to Specimen eliminating to stand reaction, solution clarification；
F, cooling, constant volume to get measure alloy in impurity content detection sample solution；
Wherein, the 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
For the total amount of the hydrogen peroxide used in a steps and b step, preferably by volume, nitric acid:Hydrogen peroxide:Hydrochloric acid=1:1:1.
Further, preferred sample quality:Nitric acid volume=0.2~0.5g:4~10mL, more preferably sample quality:Nitre
Sour volume=0.2g:4mL.
Further, 0.5~1.5mL hydrofluoric acid is added in preferably every 0.1 gram of sample.
Preferably, a step reactions time is 4~8min, and b step oxidation time is 3~5min, step c
It is generated without nitrogen dioxide Brown gas in reaction to solution, at this point, solution colour shoals；The Step d reaction time is 5~10min,
It is 5ml that Step d, which is concentrated by evaporation to liquor capacity,.
Further, in step e, hydrofluoric acid is preferably added in two portions and stands and reacts, solution complete to Specimen eliminating
Clarification.
Preferably, the nitric acid mass percent concentration is 65%~68%, the mass percent of hydrogen peroxide
Concentration >=30%, hydrochloric acid mass percent concentration are 36%~38%.
The present invention promotes sample by reaction conditions such as ratio of reagents, addition sequence, time and the temperature of control Specimen eliminating
Product also avoid the volatilization loss of boron while resolution.That is, first with nitric acid, hydrogen peroxide and salt under high temperature heating conditions
Most elements resolution in sample in addition to silicon is reacted into solution by the composite reagent of acid, and resolution, which enters in solution, to be waited for
Element boron is surveyed steadily to remain in solution in the form of ion or boric acid etc. and avoid its volatilization loss；Then reaction temperature is reduced
It spends to water-soluble 55 DEG C~60 DEG C fair of the tepid state of boron trifluoride, then adds hydrofluoric acid for mainly clearing up sample
The element silicon and its alloy crystal of the slightly solubility of middle high level and its be wrapped and fail other objects effectively cleared up
Matter, it is ensured that the complete resolution of sample and without any residue, while having of avoiding in hydrofluoric medium that reaction generates is low
The boron trifluoride volatilization loss of the properties such as boiling point, low melting point, therefore scheme realizes avoid due to Specimen eliminating is incomplete simultaneously
Element boron to be measured is caused to be wrapped among insoluble residue, or because element boron to be measured decomposes volatilization in the form of boron trifluoride from solution
Effusion, to the effective guarantee reliability of sample preparation methods, solving leads to the residual of element to be measured in sample preparation procedure
The technical issues of staying or volatilize and lose, seriously affecting measurement result accuracy.
In addition, hydrogen peroxide decomposes carbide with nitric acid the efficient oxidation, and hydrogen peroxide is simple by boiling solution mode
Ground, which decomposes, to be removed；When hydrogen peroxide Strong oxdiative is added or concentrated hydrochloric acid reaction is added, a large amount of nitric acid reactions generate nitrogen dioxide palm fibre
Color flue gas is escaped from solution, further reduced the influence that acidity crosses effect, matrix effect measures follow-up ICP-AES；Not
Using reagents such as higher boiling, high density, highly viscous phosphoric acid, perchloric acid, prepared sample solution constitutes simple, reagent blank
The factors such as background is small, reduce matrix effect, background influence interference ICP-AES measures the content of micro impurity element.
Second technical problem that the present invention solves is to provide the method for measuring impurity content in alloy.
The method that the present invention measures impurity content in alloy, it is molten to prepare sample using preparation method of the present invention
Liquid, using inductively coupled plasma atomic emission spectrometry (ICP-OES), boron in Simultaneous Direct Determination sample solution, cobalt,
The content of the impurity elements such as chromium, copper, molybdenum, nickel, lead, titanium, phosphorus.
Preferably detection parameters include：HF acid resistant device, RF power 1350W, secondary air speed 1.5L/min are compacted
Dynamic pump pump speed 85r/min, height of observation 11.2mm, nebulizer pressure 0.32MPa, measure 15~20s of the time of integration.
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, it is simple and effective to avoid the volatilization loss of element boron to be measured, and do not make
With reagents such as higher boiling, high density, highly viscous phosphoric acid, perchloric acid, while carbide in sample more efficiently being promoted to aoxidize
It decomposes complete.Round of visits completely lossless with Specimen eliminating, swift to operate is short, sample preparation solutions constitute simple, reagent and use
The features such as few blank of amount is low, interference effect factor is few, realizes ICP-OES while measuring boron cobalt in silicomanganese, ferromanganese, Antaciron
The target of the constituent contents such as chromium-copper molybdenum nickel lead titanium phosphorus.
The detection method of the present invention has few interference effect factor, multielement simultaneous determination, efficiently quick, precision Gao Zhun
The features such as exactness is good meets while to boron, cobalt, chromium, copper, molybdenum, nickel, lead, titanium, phosphorus in the alloy materials such as silicomanganese, ferromanganese, ferrosilicon
Equal impurity elements carry out the needs of product quality inspection and control.
Specific implementation mode
The present invention measures the preparation method of the sample solution of impurity content in alloy, and step is followed successively by：
A, alloy sample to be measured is taken, is placed in container, and it is mixed with nitric acid and hydrogen peroxide, is heated to boiling, into
Row reaction, obtains reaction solution A；
B, reaction solution A is mixed under fluidized state with hydrogen peroxide, carries out high temperature Strong oxdiative reaction；
C, the reaction was continued for addition hydrochloric acid under fluidized state；
D, with water eluant container wall, continuation is reacted under fluidized state；Or with water eluant container wall after, evaporation it is dense
Contracting solution is to solution small size；
E, with water eluant container wall, and solution is cooled to 55 DEG C~60 DEG C, is kept at this temperature addition hydrofluoric acid,
It is complete to Specimen eliminating to stand reaction, solution clarification；
F, cooling, constant volume to get measure alloy in impurity content detection sample solution；
Wherein, the 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
The total amount of hydrogen peroxide used in a steps and b step, preferably by volume, nitric acid:Hydrogen peroxide:Hydrochloric acid=1:1:1.I.e.
The volume ratio of whole dosages of nitric acid, hydrogen peroxide and hydrochloric acid used in entire Specimen eliminating preparation process is 1:0.8~
1.2:0.8~1.2, preferably 1:1:1；Also, hydrogen peroxide is divided into twice in two differential responses stages (a steps and b steps
Suddenly it is separately added into).Hydrogen peroxide is added in supplement to b step in reaction solution A again under fluidized state, mainly utilizes in high temperature
Peroxide decomposition is formed by the nascent oxygen with Strong oxdiative ability under state, is conducive to fully divide by the reaction of its Strong oxdiative
Solve indissoluble carbide in sample；It is easily decomposed since hydrogen peroxide is heated, it can be heated in solution if a step is directly all added
Not yet play a role just most of decomposition volatilization loss in the process；It is most of and when second step supplement addition hydrogen peroxide
Sample, which has been resolved the hydrogen peroxide being added at this time into solution, more can effectively directly make with remaining indissoluble carbide
With.
Further, preferred sample quality:Nitric acid volume=0.2~0.5g:4~10mL, more preferably sample quality:Nitre
Sour volume=0.2g:4mL.
Further, 0.5~1.5mL hydrofluoric acid is added in every 0.1 gram of sample.Often 0.1 gram of silicomangan and manganeisen
Sample is preferably added to 0.5ml hydrofluoric acid, and Antaciron can increase by 0.5~1mL hydrofluoric acid with silicone content height on this basis more.
Further, a step reactions time is 4~8min, and b step oxidation time is 3~5min, step c reaction
It is generated in solution without nitrogen dioxide Brown gas, at this point, solution colour shoals；The Step d reaction time is 5~10min, d steps
It is 5ml that flash evaporation hair, which is concentrated into liquor capacity,.
Further, in step e, with water eluant container wall after solution evaporation and concentration, and solution is cooled to 55 DEG C
It~60 DEG C, keeps within this temperature range, hydrofluoric acid being added in two portions and stands reaction in low temperature electric hot plate or water-bath
It is complete to Specimen eliminating, solution clarification；Test solution is diluted to scale, mixing with water after cooling.
Nitric acid, hydrogen peroxide and hydrochloric acid used in the present invention are both preferably the most dense examination of not diluted market sale
Agent, preferably, the nitric acid mass percent concentration are 65%~68%, the mass percent concentration of hydrogen peroxide >=
30%, hydrochloric acid mass percent concentration is 36%~38%.
Specifically, following steps can be used in the present invention：Sample 0.2~0.5g samples are weighed, polytetrafluoroethylene beaker is placed in
In equal containers, the not diluted concentrated nitric acids and 2~5mL hydrogen peroxide of 4~10mL is added in wall of cup in a manner of rinsing wall of cup, carries out
High-temperature heating reaction and 4~8min of holding reaction under boil condition；2~5mL mistakes are added again under solution fluidized state
Hydrogen oxide carries out Strong oxdiative reaction, and keeps 3~5min of solution boiling；4~10mL concentrated hydrochloric acids are subsequently added into be heated at high temperature
The reaction was continued under fluidized state, is gradually become shallower as up to the yield of nitrogen dioxide brown flue gas in solution significantly reduces color；So
Afterwards with about 3~5mL water eluant container walls, continue to react 5~10min or heating evaporation concentration under solution fluidized state
The volume of solution is to 5mL or so；55 DEG C~60 DEG C are cooled to about 3~5mL water eluant container walls and by solution, in low temperature
It is maintained in electric hot plate or water-bath under the state of temperature, total 1~2.5mL hydrofluoric acid is added in two portions and stands reaction extremely
Specimen eliminating is complete, solution clarification；Test solution is transferred in 100mL plastics volumetric flasks after cooling, scale is diluted to water, is mixed
It is even.
The present invention promotes sample by reaction conditions such as ratio of reagents, addition sequence, time and the temperature of control Specimen eliminating
Product also avoid the volatilization loss of boron while resolution.That is, first with nitric acid, hydrogen peroxide and salt under high temperature heating conditions
Most elements resolution in sample in addition to silicon is reacted into solution by the composite reagent of acid, and resolution, which enters in solution, to be waited for
Element boron is surveyed steadily to remain in solution in the form of ion or boric acid etc. and avoid its volatilization loss；Then reaction temperature is reduced
It spends to water-soluble 55 DEG C~60 DEG C fair of the tepid state of boron trifluoride, then adds hydrofluoric acid for mainly clearing up sample
The element silicon and its alloy crystal of the slightly solubility of middle high level and its be wrapped and fail other objects effectively cleared up
Matter, it is ensured that the complete resolution of sample and without any residue, while having of avoiding in hydrofluoric medium that reaction generates is low
The boron trifluoride volatilization loss of the properties such as boiling point, low melting point, therefore scheme realizes avoid due to Specimen eliminating is incomplete simultaneously
Element boron to be measured is caused to be wrapped among insoluble residue, or because element boron to be measured decomposes volatilization in the form of boron trifluoride from solution
Effusion, to the effective guarantee reliability of sample preparation methods, solving leads to the residual of element to be measured in sample preparation procedure
The technical issues of staying or volatilize and lose, seriously affecting measurement result accuracy.
In addition, hydrogen peroxide decomposes carbide with nitric acid the efficient oxidation, and hydrogen peroxide is simple by boiling solution mode
Ground, which decomposes, to be removed；When hydrogen peroxide Strong oxdiative is added or concentrated hydrochloric acid reaction is added, a large amount of nitric acid reactions generate nitrogen dioxide palm fibre
Color flue gas is escaped from solution, further reduced the influence that acidity crosses effect, matrix effect measures follow-up ICP-AES；Not
Using reagents such as higher boiling, high density, highly viscous phosphoric acid, perchloric acid, prepared sample solution constitutes simple, reagent blank
The factors such as background is small, reduce matrix effect, background influence interference ICP-AES measures the content of micro impurity element.
The method that the present invention measures impurity content in alloy, it is molten to prepare sample using preparation method of the present invention
Liquid, using inductively coupled plasma atomic emission spectrometry (ICP-OES), boron in Simultaneous Direct Determination sample solution, cobalt,
The content of the impurity elements such as chromium, copper, molybdenum, nickel, lead, titanium, phosphorus.
Preferably detection parameters include：HF acid resistant device, RF power 1350W, secondary air speed 1.5L/min are compacted
Dynamic pump pump speed 85r/min, height of observation 11.2mm, nebulizer pressure 0.32MPa, measure 15~20s of the time of integration.
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 specific implementation mode of the present invention is further described with reference to embodiment, is not therefore limited the present invention
System is among the embodiment described range.
Embodiment 1
The resolution of silicomangan sample
Weigh silicomangan sample 0.2g (hereinafter referred to as No. 1 sample), in a manner of rinsing wall of cup wall of cup be added 4mL without
Diluted concentrated nitric acid and 2mL hydrogen peroxide, high-temperature heating react and keep 4min under boil condition；In solution fluidized state
Under be added again 2mL hydrogen peroxide carry out Strong oxdiative reaction, and keep solution boil 3min；4mL concentrated hydrochloric acids are added in high temperature
The reaction was continued under ebuillition of heated state gradually becomes shallower as to the generation color without nitrogen dioxide brown flue gas in solution；With about 3mL water
Eluant container wall, continuation react 5min under solution fluidized state；It is cooled down with about 3mL water eluant container walls and by solution
To 55 DEG C, and solution is maintained in 55 DEG C of temperature ranges on low temperature electric hot plate, be added in two portions total 1mL hydrofluoric acid and
It is complete to Specimen eliminating to stand reaction, solution clarification；Test solution is transferred in 100mL plastics volumetric flasks after cooling, is diluted with water
To scale, mixing.
ICP-OES detects the content of impurity element in silicomangan sample solution
Detection means, Simultaneous Direct Determination are used as using inductively coupled plasma original emission spectrometry (ICP-OES)
Clear up the content of the impurity elements such as boron, cobalt, chromium, copper, molybdenum, nickel, lead, titanium, phosphorus in the sample solution prepared.The instrument of ICP-OES
Detection parameters include mainly：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 15~20s of the time of integration.Impurities analysis spectral line
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 samples), and 10mL concentrated nitric acids and 5mL mistakes is added
Hydrogen oxide, pyroreaction simultaneously keep 8min under boil condition；5mL hydrogen peroxide Strong oxdiative is added again and keeps boiling
5min；10mL concentrated hydrochloric acid high-boilings are added to react to the generation of no nitrogen dioxide brown flue gas；With about 5mL water eluant container and steam
Concentrate solution volume is sent out to about 5mL；It is cooled to 57 DEG C with 5mL water eluant container and by solution, solution is placed in 57 DEG C of water-baths
Middle heat preservation, and total 2.5mL hydrofluoric acid is added in two portions and is reacted.
In addition to this, it clears up the silicomangan sample according to method identical with the method for embodiment 1 and is surveyed with ICP-OES
Determine impurity content.
Embodiment 3
Sample to be cleared up is 0.3000g manganeisens sample (hereinafter referred to as No. 3 samples), and 6mL concentrated nitric acids and 3mL is added
Hydrogen peroxide, pyroreaction simultaneously keep boil condition 5min；3mL hydrogen peroxide Strong oxdiative is added again and keeps boiling
4min；6mL concentrated hydrochloric acid high-boilings are added to react to the generation of no nitrogen dioxide brown flue gas；With about 4mL water eluant container and steam
Concentrate solution volume is sent out to about 5mL；It is cooled to 58 DEG C with 5mL water eluant container and by solution, solution is placed in 58 DEG C of water-baths
Middle heat preservation, and total 1.5mL hydrofluoric acid is added in two portions and is reacted.
In addition to this, it clears up the ferromanganese sample according to method identical with the method for embodiment 1 and is measured with ICP-OES miscellaneous
Prime element content.
Embodiment 4
Sample to be cleared up is 0.4000g manganeisens sample (hereinafter referred to as No. 4 samples), and 8mL concentrated nitric acids and 4mL is added
Hydrogen peroxide, pyroreaction simultaneously keep boil condition 7min；4mL hydrogen peroxide Strong oxdiative is added again and keeps boiling
5min；8mL concentrated hydrochloric acid high-boilings are added to react to the generation of no nitrogen dioxide brown flue gas；With about 5mL water eluant container and
10min is kept under solution fluidized state；It is cooled to 60 DEG C with 5mL water eluant container and by solution, solution is placed in 60 DEG C of water-baths
It is kept the temperature in pot, and total 2.0mL hydrofluoric acid is added in two portions and is reacted.
In addition to this, it clears up the ferromanganese sample according to method identical with the method for embodiment 1 and is measured with ICP-OES miscellaneous
Prime element content.
Embodiment 5
Sample to be cleared up is 0.2500g Antacirons sample (hereinafter referred to as No. 5 samples), be added 5mL concentrated nitric acids and
2.5mL hydrogen peroxide, pyroreaction simultaneously keep boil condition 6min；2.5mL hydrogen peroxide Strong oxdiative is added again and keeps
Boil 5min；5mL concentrated hydrochloric acid high-boilings are added to react to the generation of no nitrogen dioxide brown flue gas；With about 5mL water eluant containers
And liquor capacity is concentrated by evaporation to about 5mL；It is cooled to 60 DEG C with 5mL water eluant container and by solution, solution is placed in 60 DEG C of water
It is kept the temperature in bath, and total 2mL hydrofluoric acid is added in two portions and is reacted.
In addition to this, it clears up the ferrosilicon sample according to method identical with the method for embodiment 1 and is measured with ICP-OES miscellaneous
Prime element content.
6 rate of recovery of embodiment is assessed
No. 2 samples of the present invention couple and No. 4 samples have carried out recovery test.Distinguished first by embodiment 2 and embodiment 4
The content of the impurity elements such as institute's boracic, cobalt, chromium, copper, molybdenum, nickel, lead, titanium, phosphorus in sample 2 and sample 4 is measured；Then another respectively
Sample 2 and sample 4 are weighed outside, and is separately added into the standard solution of the impurity element to be measured of respective concentration, whole process repeats real
The sample preparation and detection for applying example 2 and embodiment 4 operate.
By the assessment of the rate of recovery to verify the sample solution preparation method and detection method of the present invention, sample is being solved
The validity of volatilization loss of impurity to be measured such as resolution and effumability element boron etc. and the detection sides ICP-OES completely
Method measures the accuracy of impurity element.Test result is shown in Table 1.
1 recovery test of table
Table 1 is as it can be seen that method measures the rate of recovery of impurity element in silicomanganese, the alloys such as ferromanganese between 90%~110%, table
Bright element determination result has higher accuracy and reliability.
7 precision of embodiment is assessed
The present invention prepare to carrying out 8 independent sample solutions resolutions respectively to embodiment 1, embodiment 3 and embodiment 5 and
Analysis measures, and the result measured 8 times carries out statistical disposition, the detection precision water indicated according to relative standard deviation (RSD)
It is flat, to assess the consistency of duplicate test of the invention.Measurement result is shown in Table 2.
2 analysis method precision (n=8) (%) of table
Table 2 as it can be seen that method for measure boron in the alloy samples such as silicomanganese, ferromanganese, ferrosilicon, cobalt, chromium, copper, molybdenum, nickel, lead,
The content of the impurity elements such as titanium, phosphorus, RSD are less than 10%, show that multiple measurement result is consistent, repeatability, the reproducibility of method
Well, method has higher precision horizontal.
Claims (12)
1. measuring the preparation method of the sample solution of impurity content in alloy, which is characterized in that its step is followed successively by：
A, alloy sample to be measured is taken, is placed in container, and it is mixed with nitric acid and hydrogen peroxide, is heated to boiling, is carried out anti-
It answers, obtains reaction solution A；
B, reaction solution A is mixed under fluidized state with hydrogen peroxide, carries out oxidation reaction；
C, the reaction was continued for addition hydrochloric acid under fluidized state；
D, with water eluant container wall, continuation is reacted under fluidized state；Or it with water eluant container wall, is concentrated by evaporation molten
Liquid；
E, with water eluant container wall, and solution is cooled to 55 DEG C~60 DEG C, is kept at this temperature addition hydrofluoric acid, stood
Reaction is complete to Specimen eliminating, solution clarification；
F, cooling, constant volume to get measure alloy in impurity content detection sample solution；
Wherein, the alloy is silicomangan, manganeisen or Antaciron；The impurity element includes boron.
2. the preparation method according to claim 1 for measuring the sample solution of impurity content in alloy, feature exist
In：By volume, nitric acid:Hydrogen peroxide:Hydrochloric acid=1:0.8~1.2:0.8~1.2, wherein hydrogen peroxide is that a steps and b are walked
The total amount of rapid hydrogen peroxide used.
3. the preparation method according to claim 2 for measuring the sample solution of impurity content in alloy, feature exist
In：By volume, nitric acid:Hydrogen peroxide:Hydrochloric acid=1:1:1.
4. the preparation method according to claim 1 for measuring the sample solution of impurity content in alloy, feature exist
In：Sample quality:Nitric acid volume=0.2~0.5g:4~10mL.
5. the preparation method according to claim 4 for measuring the sample solution of impurity content in alloy, feature exist
In：Sample quality:Nitric acid volume=0.2g:4mL.
6. the preparation method according to claim 1 for measuring the sample solution of impurity content in alloy, feature exist
In：0.5~1.5mL hydrofluoric acid is added in every 0.1 gram of sample.
7. the preparation method according to claim 1 for measuring the sample solution of impurity content in alloy, feature exist
In：The a step reaction times are 4~8min, and b step oxidation time is 3~5min, and step c is reacted into solution without dioxy
Change nitrogen Brown gas to generate；The Step d reaction time is 5~10min, and it is 5mL that Step d, which is concentrated by evaporation to liquor capacity,.
8. the preparation method according to claim 1 for measuring the sample solution of impurity content in alloy, feature exist
In：In step e, hydrofluoric acid is added in two portions and stands and reacts complete to Specimen eliminating, solution clarification.
9. the preparation method according to claim 1 for measuring the sample solution of impurity content in alloy, feature exist
In：The nitric acid mass percent concentration is 65%~68%, mass percent concentration >=30% of hydrogen peroxide, hydrochloric acid quality
Percent concentration is 36%~38%.
10. the method for measuring impurity content in alloy, it is characterised in that：Using claim 1~9 any one of them system
Preparation Method prepares sample solution, using inductively coupled plasma atomic emission spectrometry, in Simultaneous Direct Determination sample solution
Constituent content, the element be boron, cobalt, chromium, copper, molybdenum, nickel, lead, titanium and phosphorus.
11. the method according to claim 10 for measuring impurity content in alloy, it is characterised in that：Detection parameters packet
It 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 15~20s of the time of integration.
12. the method according to claim 10 for measuring impurity content in alloy, it is characterised in that：Analysis spectral line
For：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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