CN106596700A - Method for determination of content of trace impurity elements in high-purity chromium by acylating chlorination separation/ICP-MS method - Google Patents
Method for determination of content of trace impurity elements in high-purity chromium by acylating chlorination separation/ICP-MS method Download PDFInfo
- Publication number
- CN106596700A CN106596700A CN201611134164.9A CN201611134164A CN106596700A CN 106596700 A CN106596700 A CN 106596700A CN 201611134164 A CN201611134164 A CN 201611134164A CN 106596700 A CN106596700 A CN 106596700A
- Authority
- CN
- China
- Prior art keywords
- high pure
- pure chromium
- sample
- chromium sample
- icp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
Abstract
The invention discloses a method for determination of the content of trace impurity elements in high-purity chromium by an acylating chlorination separation/ICP-MS method; the method comprises the steps: firstly, dissolving a high-purity chromium sample by hydrochloric acid, followed by using a characteristic of low boiling point of chromium acyl chloride generated from a reaction of the high-purity chromium sample with perchloric acid and hydrochloric acid, separating a matrix, and then determining the content of the impurity elements in the high-purity chromium sample by an inductively coupled plasma mass spectrometer, wherein the impurity elements comprise Al, Cu, Mn, Ni, Zn, Rb, Bi, Sn, Sb, V and Ti. The method for determination of the content of the trace impurity elements in high-purity chromium is simple, applies acylating chlorination separation of the matrix and the ICP-MS method to be combined, and can effectively eliminate the interference of the matrix and matrix residue; the measurement method is rapid and accurate, has good precision and labelling recovery rate, and can fully meet the requirements of determination of the trace impurities in high-purity chromium.
Description
Technical field
The invention belongs to trace impurity content measurement technical field in High Pure Chromium, and in particular to a kind of chloride point
From the method that-ICP-MS determines trace impurity content in High Pure Chromium.
Background technology
High Pure Chromium (purity >=99.99%) is high due to molten, boiling point, and hardness is big, and corrosion resistance is strong, quilt the advantages of glossiness is good
It is widely used in modern high technology industry, national defence and sophisticated technology.It is added as alloying element generally in the form of chromium or ferrochrome
To in alloy, to change the performance of alloy, therefore the content of trace impurity is not only the weight for determining its trade mark in High Pure Chromium
Will foundation, while playing vital impact to the performance and quality of prepared alloy.Due to the impurity element in High Pure Chromium
Content is very low, and the method for setting up trace impurity content in a kind of chloride separation-ICP-MS measure High Pure Chromiums is simple, real
With the analysis method for being adapted to multielement simultaneous determination has important practical significance.At present for impurity determination in High Pure Chromium
Method has chemical method, atomic absorption method (AAS), X fluorescence spectrum method (XRF), high-resolution inductively coupled plasma atomic emissions
Spectroscopic methodology (ICP-OES) etc..Chemical method operation is tediously long miscellaneous；The impurity that AAS methods, XRF methods, ICP-OES methods are surveyed in High Pure Chromium is all
Presence needs Matrix Match to eliminate Matrix effects, and the Matrix Match of High Pure Chromium is more difficult in real work.Inductive etc. from
Daughter mass spectrography (ICP-MS) has been widely used in the measure of trace impurity content in other high purity materials, but it is deposited
Matrix effects and matrix to remain the pollution that causes to follow-up other species sample analysis be the method difficulty anxious to be resolved
Topic.
The content of the invention
The technical problem to be solved is for above-mentioned the deficiencies in the prior art, there is provided a kind of chloride point
From the method that/ICP-MS methods determine trace impurity content in High Pure Chromium.The method letter of trace impurity in the measurement High Pure Chromium
Single, chloride to separate and can effectively eliminate matrix to the interference of measurement with reference to ICP-MS methods and eliminate matrix residual, and the method is fast
Speed, accurately, preferably, the measure that can fully meet trace impurity in High Pure Chromium is required for precision and recovery of standard addition.
To solve above-mentioned technical problem, the technical solution used in the present invention is：A kind of chloride separation/ICP-MS determines high
The method of trace impurity content in pure chromium, it is characterised in that the method is：Initially with dissolving with hydrochloric acid High Pure Chromium sample,
Secondly the acyl chlorides chromium for being generated using High Pure Chromium sample and perchloric acid, hydrochloric acid reaction has lower boiling characteristic matrix separation, then
The content of impurity element in High Pure Chromium sample is determined using icp mses.
The method that above-mentioned chloride separation/ICP-MS methods determine trace impurity content in High Pure Chromium, its feature exists
In the method is comprised the following steps：
Step one, weigh High Pure Chromium sample：
0.1000g High Pure Chromium samples are weighed, weighing is accurate to 0.0001g；
Step 2, prepare High Pure Chromium sample dissolving with hydrochloric acid liquid and High Pure Chromium sample blank dissolving with hydrochloric acid liquid：
Two identical beakers are taken, the High Pure Chromium sample weighed in step one is put in one of beaker, another burning
Do not stride in cup the High Pure Chromium sample weighed in rapid, the hydrochloric acid of same volume is then separately added into in two beakers, cover
The temperature to 50 DEG C of the hydrochloric acid after surface plate in two beakers of reheating～60 DEG C, High Pure Chromium sample starts dissolving, and dissolving is complete
Afterwards, High Pure Chromium sample lysate and High Pure Chromium sample blank lysate are obtained；
High Pure Chromium sample solution and High Pure Chromium sample blank solution are prepared after step 3, chloride matrix separation：
Same volume is separately added into in the lysate of High Pure Chromium sample described in step 2 and High Pure Chromium sample blank lysate
Long-pending perchloric acid, is then heated to 120 DEG C～150 DEG C perchloric acid and emits white cigarette, when there is blood in the High Pure Chromium sample lysate
When red, the hydrochloric acid of same volume is added dropwise respectively in the High Pure Chromium sample lysate and High Pure Chromium sample blank lysate,
It is heated to 120 DEG C～150 DEG C High Pure Chromium sample lysates to start to emit tobacco, after tobacco disappears, continues to be heated to 120 DEG C
When occurring blood red again in～150 DEG C of High Pure Chromium sample lysates, again to the High Pure Chromium sample lysate and height
The hydrochloric acid of same volume is added dropwise in pure chromium sample blank lysate respectively, is repeated several times, until the High Pure Chromium sample lysate
After middle addition hydrochloric acid, till no longer there is tobacco, the High Pure Chromium sample lysate and High Pure Chromium sample blank lysate are cooled down
To 25 DEG C of room temperature, rinsed after beaker outer wall with water, moved in two identical volumetric flasks respectively, finally diluted with salpeter solution
To groove, and it is well mixed, High Pure Chromium sample solution and High Pure Chromium sample blank solution is obtained；Nitric acid in the salpeter solution
Percentage by volume is 5%；
Step 4, preparation work curve solution：
The standard reserving solution that 0 μ L, 10 μ L, 50 μ L, 100 μ L mass concentrations are 10mg/L impurity elements is accurately pipetted, respectively
In being added to 4 volumetric flasks, it is settled to groove, is shaken up with salpeter solution；The working curve standard for obtaining four parts of impurity elements is molten
Liquid；The percentage by volume of nitric acid is 5% in the salpeter solution；
Step 5, setting apparatus measures condition of work：
The measurement parameter of icp mses is set；
Step 6, drawing curve：
With set in step 5 measurement condition of work icp mses with Sc, Rh, Tm as internal standard
Element, is obtained respectively the intensity of the working curve standard liquid of four parts of impurity elements in determination step four, measured intensity is made
For ordinate, the concentration using impurity element standard liquid draws out working curve as abscissa；
Step 7, the content of the impurity element determined in High Pure Chromium sample solution
Carrier gas is made with argon gas, Sc, Rh, Tm are internal standard element, with the inductance coupling that measurement condition of work is set in step 5
Close the intensity I that High Pure Chromium sample solution is obtained in plasma mass spectrograph determination step three1, then it is obtained in determination step three again
The intensity I of High Pure Chromium sample blank solution2, then the working curve by drawing from step 6 check in I1And I2Correspond to respectively miscellaneous
Concentration ρ of prime element1And ρ2, ρ1And ρ2Unit be mg/L；
Step 8, the content of the impurity element calculated in High Pure Chromium sample：
The content of the impurity element in High Pure Chromium sample is with the mass fraction w of impurity elementwRepresent, numerical value is represented with %,
And calculate according to equation below：
Wherein V is the volume of High Pure Chromium sample solution, and unit is mL；M is the quality that High Pure Chromium sample is weighed in step one,
Unit is g.
The method that above-mentioned chloride separation/ICP-MS methods determine trace impurity content in High Pure Chromium, its feature exists
In the addition volume of hydrochloric acid described in step 2 is 4mL.
The method that above-mentioned chloride separation/ICP-MS methods determine trace impurity content in High Pure Chromium, its feature exists
In beaker described in step 2 is the polytetrafluoroethylene beaker of 100mL.
The method that above-mentioned chloride separation/ICP-MS methods determine trace impurity content in High Pure Chromium, its feature exists
In hydrochloric acid described in step 2 and step 3 is that MOS levels reagent is obtained through secondary sub- boiling purification；Perchloric acid described in step 3
It is obtained through secondary sub- boiling purification for MOS levels reagent；Nitric acid is MOS level reagents in salpeter solution described in step 3 and step 4
It is obtained through secondary sub- boiling purification.
The method that above-mentioned chloride separation/ICP-MS methods determine trace impurity content in High Pure Chromium, its feature exists
In the volume of volumetric flask is 100mL described in step 3 and step 4.
The method that above-mentioned chloride separation/ICP-MS methods determine trace impurity content in High Pure Chromium, its feature exists
In 130 DEG C of perchloric acid being heated in step 3 and emit white cigarette；It is heated to 130 DEG C of High Pure Chromium sample lysates to start to emit tobacco.
The method that above-mentioned chloride separation/ICP-MS methods determine trace impurity content in High Pure Chromium, its feature exists
In the addition volume of perchloric acid described in step 3 is 20mL；The volume that hydrochloric acid is added dropwise every time is 3mL, and hydrochloric acid is added dropwise repeatedly
Four times.
The method that above-mentioned measure chloride separation/ICP-MS methods determine trace impurity content in High Pure Chromium, it is special
Levy and be, the measurement parameter that icp mses are arranged in step 4 is specially：RF power is 1200W, is cooled down
Throughput is 15L/min, and secondary air amount is 1.2L/min, and carrier gas flux 0.8L/min, scan mode is jump peak, sampling depth
For 7mm, number of repetition is 7 times, and detector voltage is -12V.
The method that above-mentioned chloride separation/ICP-MS methods determine trace impurity content in High Pure Chromium, its feature exists
In the impurity element is Al, Cu, Mn, Ni, Zn, Rb, Bi, Sn, Sb, V and Ti.
The present invention has compared with prior art advantages below：
1st, the boiling point of High Pure Chromium of the invention is 2672.0 DEG C, and the chromyl chloride boiling point Jing after chloride is 115.7 DEG C, then should
The content of trace impurity in High Pure Chromium is determined with ICP-MS, the method can effectively eliminate Matrix effects and matrix residual；
Method is quick, accurate, and preferably, the measure that can fully meet trace impurity in High Pure Chromium is required for precision and recovery of standard addition.
2nd, the present invention measures the method for Determination of trace element contents in High Pure Chromium under selected experiment condition, method detection limit (3
σ) between 0.00001%-0.00006%, relative standard deviation (RSD) 1.7%-5.8%, recovery of standard addition be 90%～
104%.
3rd, this method of the present invention is simple and practical, disclosure satisfy that 11 kinds of impurity in High Pure Chromium of the quality purity more than 99.99%
The Accurate Determining of element.
Technical scheme is described in further detail below by embodiment.
Specific embodiment
The icp mses of the embodiment of the present invention 1～3 are produced by Perkin Elmer companies of the U.S.,
Model NexION 300X types；The inductively-coupled plasma spectrometer that comparative example of the present invention 1 is adopted is public by U.S. Thermo
Department's production, model iCAP 7000；The DC-Arc Atomic Emission Spectrometer AESs that comparative example of the present invention 2 is adopted are by U.S. Leeman
Company produces, model Prodigy.
The MOS that hydrochloric acid, nitric acid and perchloric acid used of the invention are produced by Tianjin Kermel Chemical Reagent Co., Ltd.
Level reagent；The sub-boiling distillation of MOS grade hydrochloric acids, nitric acid and perchloric acid/acid purification system is that had by Beijing LabTech instrument share
Limit company produces, model SD 3A.
The standard reserving solution of Al, Cu, Mn, Ni, Zn, Rb, Bi, Sn, Sb, V and Ti used by the present invention is by U.S. Perkin
Elmer companies and national ferrous materials test center production.High Pure Chromium sample used by the present invention is ground by northwest non-ferrous metal
Jiu Yuan titanium alloys research institute provides, and quality purity is 99.99%.
Embodiment 1
The present embodiment is included using the method that chloride separation/ICP-MS methods determine trace impurity content in High Pure Chromium
Following steps：
Step one, weigh High Pure Chromium sample (quality purity more than 99.99% High Pure Chromium sample)：
0.1000g High Pure Chromium samples are weighed, weighing is accurate to 0.0001g；
Step 2, prepare High Pure Chromium sample dissolving with hydrochloric acid liquid and High Pure Chromium sample blank dissolving with hydrochloric acid liquid：
The polytetrafluoroethylene beaker of two 100mL is taken, is put in step one in one of polytetrafluoroethylene beaker and is weighed
High Pure Chromium sample, the High Pure Chromium sample weighed in rapid of not strideing in another polytetrafluoroethylene beaker is then poly- to two
The hydrochloric acid of 4mL is separately added in tetrafluoroethene beaker, the hydrochloric acid in two polytetrafluoroethylene beakers is reheated after cap upper surface ware
Temperature to 55 DEG C, High Pure Chromium sample starts dissolving, after dissolving completely, obtains High Pure Chromium sample lysate and High Pure Chromium sample is empty
White lysate；
High Pure Chromium sample solution and High Pure Chromium sample blank solution are prepared after step 3, chloride matrix separation：
It is separately added into 20mL's in the lysate of High Pure Chromium sample described in step 2 and High Pure Chromium sample blank lysate
Perchloric acid, is then heated to 130 DEG C of perchloric acid and emits white cigarette, when occurring blood red in the High Pure Chromium sample lysate, to institute
The hydrochloric acid that 3mL is added dropwise in High Pure Chromium sample lysate and High Pure Chromium sample blank lysate respectively is stated, 130 DEG C of height are heated to
Pure chromium sample lysate starts to emit tobacco, after tobacco disappears, continues to be heated in 130 DEG C of High Pure Chromium sample lysates again
It is secondary occur it is blood red when, again 3mL is added dropwise respectively in the High Pure Chromium sample lysate and High Pure Chromium sample blank lysate
Hydrochloric acid, quadruplication, altogether be added dropwise 12mL hydrochloric acid, until in the High Pure Chromium sample lysate add hydrochloric acid after, no longer
Till there is tobacco, the High Pure Chromium sample lysate and High Pure Chromium sample blank lysate are cooled down to 25 DEG C of room temperature, use water
After rinsing beaker outer wall, during the volumetric flask of two 100mL is moved into respectively, finally groove is diluted to salpeter solution, and mixes equal
It is even, High Pure Chromium sample solution and High Pure Chromium sample blank solution is obtained；The percentage by volume of nitric acid is in the salpeter solution
5%；
Step 4, preparation work curve solution：
The standard reserving solution that 0 μ L, 10 μ L, 50 μ L, 100 μ L mass concentrations are 10mg/L impurity elements is accurately pipetted, respectively
In being added to the volumetric flask of 4 100mL, it is settled to groove, is shaken up with salpeter solution；Obtain the working curve of four parts of impurity elements
Standard liquid；The percentage by volume of nitric acid is 5% in the salpeter solution；
Step 5, setting apparatus measures condition of work：
The measurement parameter for arranging icp mses is specially：RF power is 1200W, and cooling gas flow is
15L/min, secondary air amount is 1.2L/min, carrier gas flux 0.8L/min, and to jump peak, sampling depth is 7mm to scan mode, weight
Again number is 7 times, and detector voltage is -12V.
Step 6, drawing curve：
With set in step 5 measurement condition of work icp mses with Sc, Rh, Tm as internal standard
Element, is obtained respectively the intensity of the working curve standard liquid of four parts of impurity elements in determination step four, measured intensity is made
For ordinate, the concentration using impurity element standard liquid draws out working curve as abscissa；
Step 7, the content of the trace element determined in High Pure Chromium sample solution
Carrier gas is made with argon gas, Sc, Rh, Tm are internal standard element, with the inductance coupling that measurement condition of work is set in step 5
Close the intensity I that High Pure Chromium sample solution is obtained in plasma mass spectrograph determination step three1, then it is obtained in determination step three again
The intensity I of High Pure Chromium sample blank solution2, then the working curve by drawing from step 6 check in I1And I2Correspond to respectively miscellaneous
Concentration ρ of prime element1And ρ2, ρ1And ρ2Unit be mg/L；
Step 8, the content of the impurity element calculated in High Pure Chromium sample：
The content of the impurity element in High Pure Chromium sample is with the mass fraction w of impurity elementwRepresent, numerical value is represented with %,
And calculate according to equation below：
Wherein V is the volume of High Pure Chromium sample solution, and unit is mL；M is the quality that High Pure Chromium sample is weighed in step one,
Unit is g.
In the present embodiment, the hydrochloric acid is that MOS levels reagent is obtained through secondary sub- boiling purification；The perchloric acid is MOS levels
Reagent is obtained through secondary sub- boiling purification；Nitric acid is that MOS levels reagent is obtained through secondary sub- boiling purification in the salpeter solution.
In the present embodiment, the impurity element is Al, Cu, Mn, Ni, Zn, Rb, Bi, Sn, Sb, V and Ti, and each impurity is first
Element prepares four parts of working curve standard liquids by step 4, and draws the work song of each impurity element by step 6
Line, calculates the content of each impurity element in High Pure Chromium sample, as shown in table 1 finally by step 8.
Table 1 measures content, the relative standard deviation of each impurity element in High Pure Chromium sample using the method for embodiment 1
And recovery of standard addition
Embodiment 2
The present embodiment is included using the method that chloride separation/ICP-MS methods determine trace impurity content in High Pure Chromium
Following steps：
Step one, weigh High Pure Chromium sample (quality purity more than 99.99% High Pure Chromium sample)：
0.1000g High Pure Chromium samples are weighed, weighing is accurate to 0.0001g；
Step 2, prepare High Pure Chromium sample dissolving with hydrochloric acid liquid and High Pure Chromium sample blank dissolving with hydrochloric acid liquid：
The polytetrafluoroethylene beaker of two 100mL is taken, is put in step one in one of polytetrafluoroethylene beaker and is weighed
High Pure Chromium sample, the High Pure Chromium sample weighed in rapid of not strideing in another polytetrafluoroethylene beaker is then poly- to two
The hydrochloric acid of 4mL is separately added in tetrafluoroethene beaker, the hydrochloric acid in two polytetrafluoroethylene beakers is reheated after cap upper surface ware
Temperature to 50 DEG C, High Pure Chromium sample starts dissolving, after dissolving completely, obtains High Pure Chromium sample lysate and High Pure Chromium sample is empty
White lysate；
High Pure Chromium sample solution and High Pure Chromium sample blank solution are prepared after step 3, chloride matrix separation：
It is separately added into 20mL's in the lysate of High Pure Chromium sample described in step 2 and High Pure Chromium sample blank lysate
Perchloric acid, is then heated to 120 DEG C of perchloric acid and emits white cigarette, when occurring blood red in the High Pure Chromium sample lysate, to institute
The hydrochloric acid that 3mL is added dropwise in High Pure Chromium sample lysate and High Pure Chromium sample blank lysate respectively is stated, 120 DEG C of height are heated to
Pure chromium sample lysate starts to emit tobacco, after tobacco disappears, continues to be heated in 120 DEG C of High Pure Chromium sample lysates again
It is secondary occur it is blood red when, again 3mL is added dropwise respectively in the High Pure Chromium sample lysate and High Pure Chromium sample blank lysate
Hydrochloric acid, quadruplication, altogether be added dropwise 12mL hydrochloric acid, until in the High Pure Chromium sample lysate add hydrochloric acid after, no longer
Till there is tobacco, the High Pure Chromium sample lysate and High Pure Chromium sample blank lysate are cooled down to 25 DEG C of room temperature, use water
After rinsing beaker outer wall, during the volumetric flask of two 100mL is moved into respectively, finally groove is diluted to salpeter solution, and mixes equal
It is even, High Pure Chromium sample solution and High Pure Chromium sample blank solution is obtained；The percentage by volume of nitric acid is in the salpeter solution
5%；
Step 4, preparation work curve solution：
The standard reserving solution that 0 μ L, 10 μ L, 50 μ L, 100 μ L mass concentrations are 10mg/L impurity elements is accurately pipetted, respectively
In being added to the volumetric flask of 4 100mL, it is settled to groove, is shaken up with salpeter solution；Obtain the working curve of four parts of impurity elements
Standard liquid；The percentage by volume of nitric acid is 5% in the salpeter solution；
Step 5, setting apparatus measures condition of work：
The measurement parameter for arranging icp mses is specially：RF power is 1200W, and cooling gas flow is
15L/min, secondary air amount is 1.2L/min, carrier gas flux 0.8L/min, and to jump peak, sampling depth is 7mm to scan mode, weight
Again number is 7 times, and detector voltage is -12V.
Step 6, drawing curve：
With set in step 5 measurement condition of work icp mses with Sc, Rh, Tm as internal standard
Element, is obtained respectively the intensity of the working curve standard liquid of four parts of impurity elements in determination step four, measured intensity is made
For ordinate, the concentration using impurity element standard liquid draws out working curve as abscissa；
Step 7, the content of the trace element determined in High Pure Chromium sample solution
Carrier gas is made with argon gas, Sc, Rh, Tm are internal standard element, with the inductance coupling that measurement condition of work is set in step 5
Close the intensity I that High Pure Chromium sample solution is obtained in plasma mass spectrograph determination step three1, then it is obtained in determination step three again
The intensity I of High Pure Chromium sample blank solution2, then the working curve by drawing from step 6 check in I1And I2Correspond to respectively miscellaneous
Concentration ρ of prime element1And ρ2, ρ1And ρ2Unit be mg/L；
Step 8, the content of the impurity element calculated in High Pure Chromium sample：
The content of the impurity element in High Pure Chromium sample is with the mass fraction w of impurity elementwRepresent, numerical value is represented with %,
And calculate according to equation below：
Wherein V is the volume of High Pure Chromium sample solution, and unit is mL；M is the quality that High Pure Chromium sample is weighed in step one,
Unit is g.
In the present embodiment, the hydrochloric acid is that MOS levels reagent is obtained through secondary sub- boiling purification；The perchloric acid is MOS levels
Reagent is obtained through secondary sub- boiling purification；Nitric acid is that MOS levels reagent is obtained through secondary sub- boiling purification in the salpeter solution.
In the present embodiment, the impurity element is Al, Cu, Mn, Ni, Zn, Rb, Bi, Sn, Sb, V and Ti, and each impurity is first
Element prepares four parts of working curve standard liquids by step 4, and draws the work song of each impurity element by step 6
Line, calculates the content of each impurity element in High Pure Chromium sample, as shown in table 2 finally by step 8.
Table 2 measures content, the relative standard deviation of each impurity element in High Pure Chromium sample using the method for embodiment 2
And recovery of standard addition
Embodiment 3
The present embodiment is included using the method that chloride separation/ICP-MS methods determine trace impurity content in High Pure Chromium
Following steps：
Step one, weigh High Pure Chromium sample (quality purity more than 99.99% High Pure Chromium sample)：
0.1000g High Pure Chromium samples are weighed, weighing is accurate to 0.0001g；
Step 2, prepare High Pure Chromium sample dissolving with hydrochloric acid liquid and High Pure Chromium sample blank dissolving with hydrochloric acid liquid：
The polytetrafluoroethylene beaker of two 100mL is taken, is put in step one in one of polytetrafluoroethylene beaker and is weighed
High Pure Chromium sample, the High Pure Chromium sample weighed in rapid of not strideing in another polytetrafluoroethylene beaker is then poly- to two
The hydrochloric acid of 4mL is separately added in tetrafluoroethene beaker, the hydrochloric acid in two polytetrafluoroethylene beakers is reheated after cap upper surface ware
Temperature to 60 DEG C, High Pure Chromium sample starts dissolving, after dissolving completely, obtains High Pure Chromium sample lysate and High Pure Chromium sample is empty
White lysate；
High Pure Chromium sample solution and High Pure Chromium sample blank solution are prepared after step 3, chloride matrix separation：
It is separately added into 20mL's in the lysate of High Pure Chromium sample described in step 2 and High Pure Chromium sample blank lysate
Perchloric acid, is then heated to 150 DEG C of perchloric acid and emits white cigarette, when occurring blood red in the High Pure Chromium sample lysate, to institute
The hydrochloric acid that 3mL is added dropwise in High Pure Chromium sample lysate and High Pure Chromium sample blank lysate respectively is stated, 150 DEG C of height are heated to
Pure chromium sample lysate starts to emit tobacco, after tobacco disappears, continues to be heated in 150 DEG C of High Pure Chromium sample lysates again
It is secondary occur it is blood red when, again 3mL is added dropwise respectively in the High Pure Chromium sample lysate and High Pure Chromium sample blank lysate
Hydrochloric acid, quadruplication, altogether be added dropwise 12mL hydrochloric acid, until in the High Pure Chromium sample lysate add hydrochloric acid after, no longer
Till there is tobacco, the High Pure Chromium sample lysate and High Pure Chromium sample blank lysate are cooled down to 25 DEG C of room temperature, use water
After rinsing beaker outer wall, during the volumetric flask of two 100mL is moved into respectively, finally groove is diluted to salpeter solution, and mixes equal
It is even, High Pure Chromium sample solution and High Pure Chromium sample blank solution is obtained；The percentage by volume of nitric acid is in the salpeter solution
5%；
Step 4, preparation work curve solution：
The standard reserving solution that 0 μ L, 10 μ L, 50 μ L, 100 μ L mass concentrations are 10mg/L impurity elements is accurately pipetted, respectively
In being added to the volumetric flask of 4 100mL, it is settled to groove, is shaken up with salpeter solution；Obtain the working curve of four parts of impurity elements
Standard liquid；The percentage by volume of nitric acid is 5% in the salpeter solution；
Step 5, setting apparatus measures condition of work：
The measurement parameter for arranging icp mses is specially：RF power is 1200W, and cooling gas flow is
15L/min, secondary air amount is 1.2L/min, carrier gas flux 0.8L/min, and to jump peak, sampling depth is 7mm to scan mode, weight
Again number is 7 times, and detector voltage is -12V.
Step 6, drawing curve：
With set in step 5 measurement condition of work icp mses with Sc, Rh, Tm as internal standard
Element, is obtained respectively the intensity of the working curve standard liquid of four parts of impurity elements in determination step four, measured intensity is made
For ordinate, the concentration using impurity element standard liquid draws out working curve as abscissa；
Step 7, the content of the trace element determined in High Pure Chromium sample solution
Carrier gas is made with argon gas, Sc, Rh, Tm are internal standard element, with the inductance coupling that measurement condition of work is set in step 5
Close the intensity I that High Pure Chromium sample solution is obtained in plasma mass spectrograph determination step three1, then it is obtained in determination step three again
The intensity I of High Pure Chromium sample blank solution2, then the working curve by drawing from step 6 check in I1And I2Correspond to respectively miscellaneous
Concentration ρ of prime element1And ρ2, ρ1And ρ2Unit be mg/L；
Step 8, the content of the impurity element calculated in High Pure Chromium sample：
The content of the impurity element in High Pure Chromium sample is with the mass fraction w of impurity elementwRepresent, numerical value is represented with %,
And calculate according to equation below：
Wherein V is the volume of High Pure Chromium sample solution, and unit is mL；M is the quality that High Pure Chromium sample is weighed in step one,
Unit is g.
In the present embodiment, the hydrochloric acid is that MOS levels reagent is obtained through secondary sub- boiling purification；The perchloric acid is MOS levels
Reagent is obtained through secondary sub- boiling purification；Nitric acid is that MOS levels reagent is obtained through secondary sub- boiling purification in the salpeter solution.
In the present embodiment, the impurity element is Al, Cu, Mn, Ni, Zn, Rb, Bi, Sn, Sb, V and Ti, and each impurity is first
Element prepares four parts of working curve standard liquids by step 4, and draws the work song of each impurity element by step 6
Line, calculates the content of each impurity element in High Pure Chromium sample, as shown in table 3 finally by step 8.
Table 3 measures content, the relative standard deviation of each impurity element in High Pure Chromium sample using the method for embodiment 3
And recovery of standard addition
Comparative example 1
The High Pure Chromium sample that this comparative example is determined is identical with the High Pure Chromium sample used by embodiment 1, direct by ICP-OES
Molten sample method determines impurity elements Al, the content of Cu, Mn, Ni, Zn, Rb, Bi, Sn, Sb, V and Ti, test result such as table 4.
The ICP-OES equipment that directly molten sample method is adopted is the inductively coupled plasma spectrometry of Thermo companies of U.S. production
Instrument, model is iCAP 7000, the parameter of inductively-coupled plasma spectrometer is arranged during test and is：RF power 1150kw, cooling
Throughput 14L/min, nebulizer pressure 50PSI, secondary air amount 0.5L/min, solution elevating amount 1.0L/min, the time of integration
10s。
Comparative example 2
The High Pure Chromium sample that this comparative example is determined is identical with the High Pure Chromium sample used by embodiment 1, by DC-Arc-AES
Method determines impurity elements Al, the content of Cu, Mn, Ni, Zn, Rb, Bi, Sn, Sb, V and Ti, test result such as table 4.
DC-Arc-AES methods adopt equipment be Leeman companies of the U.S. production DC-Arc Atomic Emission Spectrometer AESs, model
It is Prodigy, the parameter of DC-Arc Atomic Emission Spectrometer AESs is arranged during test is：Excitation current is 10A, and current duration is
50s, with the mixture of silver chlorate and carbon dust buffer is made, and anode is carried out as working electrode using the thin neck cup-shaped electrode of shallow bore hole thin-walled
Excite, by single exposure, be capable of achieving to be detected while 11 kinds of elements.
Each impurity element contains in the High Pure Chromium sample that table 4 is determined by the method for embodiment 1, comparative example 1 and comparative example 2
Amount
| Impurity element | Embodiment 1 (%) | Comparative example 1 (%) | Comparative example 2 (%) |
| Al | 0.00032 | 0.0004 | 0.0003 |
| Cu | 0.00016 | 0.0002 | 0.0002 |
| Mn | 0.00081 | 0.0006 | 0.0009 |
| Ni | 0.00064 | 0.0004 | 0.0004 |
| Zn | 0.00055 | 0.0006 | 0.0005 |
| Rb | 0.00016 | 0.0001 | 0.0002 |
| Bi | 0.00011 | 0.0001 | 0.0001 |
| Sn | 0.00034 | 0.0005 | 0.0003 |
| Sb | 0.00042 | 0.0006 | 0.0005 |
| V | 0.00029 | 0.0002 | 0.0003 |
| Ti | 0.00013 | 0.0001 | 0.0002 |
The content data of each impurity element in by observing table 4, as a result shows that chloride is separated and combines inductive
ICP-MS is determined while can meeting Simultaneous Determination of Trace Elements in High Pure Chromium, and matrix can be effectively eliminated again to unit to be measured
The interference of element, while will not pollute to the measure of Determination of Trace Chromium in follow-up other high purity materials；ICP-OES needs Matrix Match
To eliminate interference, and the more difficult matching of the matrix of High Pure Chromium in real work, and matrix residual can make instrument produce memory effect, make
Into the pollution of instrument sampling system, normal measure is affected；DC-Arc-AES method complex pretreatments, the measure cycle is longer, while needing
Substantial amounts of high-purity standard substance is consumed, it is relatively costly.
The above, is only presently preferred embodiments of the present invention, and not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence changes that art is substantially made to above example, still fall within technical solution of the present invention
Protection domain in.
Claims (10)
1. a kind of method that chloride separation/ICP-MS determines trace impurity content in High Pure Chromium, it is characterised in that the party
Method is：Initially with dissolving with hydrochloric acid High Pure Chromium sample, the acyl chlorides for secondly being generated with perchloric acid, hydrochloric acid reaction using High Pure Chromium sample
Chromium has lower boiling characteristic matrix separation, then determines impurity in High Pure Chromium sample using icp mses
The content of element.
2. chloride separation/ICP-MS methods according to claim 1 determine the side of trace impurity content in High Pure Chromium
Method, it is characterised in that the method is comprised the following steps：
Step one, weigh High Pure Chromium sample：
0.1000g High Pure Chromium samples are weighed, weighing is accurate to 0.0001g；
Step 2, prepare High Pure Chromium sample dissolving with hydrochloric acid liquid and High Pure Chromium sample blank dissolving with hydrochloric acid liquid：
Two identical beakers are taken, the High Pure Chromium sample weighed in step one is put in one of beaker, in another beaker
Do not stride the High Pure Chromium sample weighed in rapid, the hydrochloric acid of same volume, cap upper surface are then separately added into in two beakers
The temperature to 50 DEG C of the hydrochloric acid after ware in two beakers of reheating～60 DEG C, High Pure Chromium sample starts dissolving, after dissolving completely, obtains
To High Pure Chromium sample lysate and High Pure Chromium sample blank lysate；
High Pure Chromium sample solution and High Pure Chromium sample blank solution are prepared after step 3, chloride matrix separation：
Same volume is separately added into in the lysate of High Pure Chromium sample described in step 2 and High Pure Chromium sample blank lysate
Perchloric acid, is then heated to 120 DEG C～150 DEG C perchloric acid and emits white cigarette, blood red when occurring in the High Pure Chromium sample lysate
When, the hydrochloric acid of same volume is added dropwise respectively in the High Pure Chromium sample lysate and High Pure Chromium sample blank lysate, heat
Start to emit tobacco to 120 DEG C～150 DEG C High Pure Chromium sample lysates, after tobacco disappears, continue to be heated to 120 DEG C～
When occurring blood red again in 150 DEG C of High Pure Chromium sample lysates, again to the High Pure Chromium sample lysate and high-purity
The hydrochloric acid of same volume is added dropwise in chromium sample blank lysate respectively, is repeated several times, until in the High Pure Chromium sample lysate
After adding hydrochloric acid, till no longer there is tobacco, the cooling High Pure Chromium sample lysate and High Pure Chromium sample blank lysate are extremely
25 DEG C of room temperature, is rinsed after beaker outer wall with water, is moved in two identical volumetric flasks respectively, is finally diluted to salpeter solution
Groove, and be well mixed, High Pure Chromium sample solution and High Pure Chromium sample blank solution is obtained；The body of nitric acid in the salpeter solution
Product percentage is 5%；
Step 4, preparation work curve solution：
The standard reserving solution that 0 μ L, 10 μ L, 50 μ L, 100 μ L mass concentrations are 10mg/L impurity elements is accurately pipetted, is separately added into
To in 4 volumetric flasks, it is settled to groove, is shaken up with salpeter solution；Obtain the working curve standard liquid of four parts of impurity elements；Institute
The percentage by volume for stating nitric acid in salpeter solution is 5%；
Step 5, setting apparatus measures condition of work：
The measurement parameter of icp mses is set；
Step 6, drawing curve：
With set in step 5 measurement condition of work icp mses with Sc, Rh, Tm as internal standard element,
The intensity of the working curve standard liquid of four parts of impurity elements is obtained in determination step four respectively, measured intensity is used as vertical seat
Mark, the concentration using impurity element standard liquid draws out working curve as abscissa；
Step 7, the content of the impurity element determined in High Pure Chromium sample solution
Carrier gas is made with argon gas, Sc, Rh, Tm are internal standard element, with inductive that measurement condition of work is set in step 5 etc.
The intensity I of High Pure Chromium sample solution is obtained in gas ions mass spectrograph determination step three1, then it is obtained in determination step three again high-purity
The intensity I of chromium sample blank solution2, then the working curve by drawing from step 6 check in I1And I2Impurity unit is corresponded to respectively
Concentration ρ of element1And ρ2, ρ1And ρ2Unit be mg/L；
Step 8, the content of the impurity element calculated in High Pure Chromium sample：
The content of the impurity element in High Pure Chromium sample is with the mass fraction w of impurity elementwRepresent, numerical value is represented with %, and according to
Equation below is calculated：
Wherein V is the volume of High Pure Chromium sample solution, and unit is mL；M is that the quality of High Pure Chromium sample, unit are weighed in step one
For g.
3. chloride separation/ICP-MS methods according to claim 2 determine the side of trace impurity content in High Pure Chromium
Method, it is characterised in that the addition volume of hydrochloric acid described in step 2 is 4mL.
4. chloride separation/ICP-MS methods according to claim 2 determine the side of trace impurity content in High Pure Chromium
Method, it is characterised in that beaker described in step 2 is the polytetrafluoroethylene beaker of 100mL.
5. chloride separation/ICP-MS methods according to claim 2 determine the side of trace impurity content in High Pure Chromium
Method, it is characterised in that hydrochloric acid described in step 2 and step 3 is that MOS levels reagent is obtained through secondary sub- boiling purification；Step 3
Described in perchloric acid be that MOS levels reagent is obtained through secondary sub- boiling purification；Nitre in salpeter solution described in step 3 and step 4
Acid is obtained for MOS levels reagent through secondary sub- boiling purification.
6. chloride separation/ICP-MS methods according to claim 2 determine the side of trace impurity content in High Pure Chromium
Method, it is characterised in that the volume of volumetric flask is 100mL described in step 3 and step 4.
7. chloride separation/ICP-MS methods according to claim 2 determine the side of trace impurity content in High Pure Chromium
Method, it is characterised in that 130 DEG C of perchloric acid are heated in step 3 and emit white cigarette；It is heated to 130 DEG C of High Pure Chromium sample lysates
Start to emit tobacco.
8. chloride separation/ICP-MS methods according to claim 2 determine the side of trace impurity content in High Pure Chromium
Method, it is characterised in that the addition volume of perchloric acid described in step 3 is 20mL；The volume that hydrochloric acid is added dropwise every time is 3mL, instead
Hydrochloric acid four times is added dropwise again.
9. measure chloride separation/ICP-MS methods according to claim 2 determine trace impurity content in High Pure Chromium
Method, it is characterised in that in step 4 arrange icp mses measurement parameter be specially：RF power is
1200W, cooling gas flow is 15L/min, and secondary air amount is 1.2L/min, and carrier gas flux 0.8L/min, scan mode is jump
Peak, sampling depth is 7mm, and number of repetition is 7 times, and detector voltage is -12V.
10. chloride separation/ICP-MS methods according to claim 1 and 2 determine trace impurity content in High Pure Chromium
Method, it is characterised in that the impurity element be Al, Cu, Mn, Ni, Zn, Rb, Bi, Sn, Sb, V and Ti.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611134164.9A CN106596700A (en) | 2016-12-10 | 2016-12-10 | Method for determination of content of trace impurity elements in high-purity chromium by acylating chlorination separation/ICP-MS method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611134164.9A CN106596700A (en) | 2016-12-10 | 2016-12-10 | Method for determination of content of trace impurity elements in high-purity chromium by acylating chlorination separation/ICP-MS method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106596700A true CN106596700A (en) | 2017-04-26 |
Family
ID=58598787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611134164.9A Pending CN106596700A (en) | 2016-12-10 | 2016-12-10 | Method for determination of content of trace impurity elements in high-purity chromium by acylating chlorination separation/ICP-MS method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106596700A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108572213A (en) * | 2018-04-24 | 2018-09-25 | 株洲科能新材料有限责任公司 | A kind of high purity tellurium impurity enriched device and its method for 5N grades of tellurium analysis detections |
| CN112834486A (en) * | 2020-12-29 | 2021-05-25 | 河钢股份有限公司 | Method for measuring chromium content in nickel-based alloy |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103412027A (en) * | 2013-08-01 | 2013-11-27 | 中国航空工业集团公司北京航空材料研究院 | Analysis method for testing cobalt in high-chrome and high-temperature alloy |
| CN103604800A (en) * | 2013-10-25 | 2014-02-26 | 中国航空工业集团公司北京航空材料研究院 | Analysis method for determining titanium, vanadium, tungsten, manganese and silicon in K25 chromium-base high temperature alloy |
| CN104458730A (en) * | 2014-12-10 | 2015-03-25 | 内蒙古包钢钢联股份有限公司 | Method for measuring aluminum content of high carbon ferro-chrome by using compleximetry |
| CN104597110A (en) * | 2015-01-23 | 2015-05-06 | 河北钢铁股份有限公司 | ICP-MS measuring method of microelement impurities in high-purity chromium |
| JP2015134799A (en) * | 2015-03-06 | 2015-07-27 | 宇部興産株式会社 | High-purity zirconium alkoxide raw material and production method of the same, and analytical method of raw material |
-
2016
- 2016-12-10 CN CN201611134164.9A patent/CN106596700A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103412027A (en) * | 2013-08-01 | 2013-11-27 | 中国航空工业集团公司北京航空材料研究院 | Analysis method for testing cobalt in high-chrome and high-temperature alloy |
| CN103604800A (en) * | 2013-10-25 | 2014-02-26 | 中国航空工业集团公司北京航空材料研究院 | Analysis method for determining titanium, vanadium, tungsten, manganese and silicon in K25 chromium-base high temperature alloy |
| CN104458730A (en) * | 2014-12-10 | 2015-03-25 | 内蒙古包钢钢联股份有限公司 | Method for measuring aluminum content of high carbon ferro-chrome by using compleximetry |
| CN104597110A (en) * | 2015-01-23 | 2015-05-06 | 河北钢铁股份有限公司 | ICP-MS measuring method of microelement impurities in high-purity chromium |
| JP2015134799A (en) * | 2015-03-06 | 2015-07-27 | 宇部興産株式会社 | High-purity zirconium alkoxide raw material and production method of the same, and analytical method of raw material |
Non-Patent Citations (2)
| Title |
|---|
| 李中禄: "原子吸收法测定纯铬中铜、铁和铅", 《冶金分析》 * |
| 黄慧萍 等: "电感耦合等离子体质谱法测定铬铁矿单矿物中痕量稀土元素", 《冶金分析》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108572213A (en) * | 2018-04-24 | 2018-09-25 | 株洲科能新材料有限责任公司 | A kind of high purity tellurium impurity enriched device and its method for 5N grades of tellurium analysis detections |
| CN112834486A (en) * | 2020-12-29 | 2021-05-25 | 河钢股份有限公司 | Method for measuring chromium content in nickel-based alloy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105823772B (en) | The detection method of impurity element in a kind of measurement tungsten carbide | |
| CN107121426B (en) | Clear up the method for vanadium chromium titanium alloy and the detection method of digestion solution | |
| CN106596518A (en) | Method for determining zirconium and impurity contents in uranium-zirconium alloy | |
| CN110031535A (en) | The method that sodium peroxide inductivity coupled plasma mass spectrometry measures tin amount in tin ore | |
| CN108375568A (en) | Micro-wave digestion-inductive coupling plasma emission spectrograph method measures impurity element in rafifinal | |
| CN107290333A (en) | A kind of method that ICP AES methods determine impurity element in the special low titanium ferrophosphorus of high grade silicon steel | |
| CN107561061A (en) | The assay method of potassium sodium Pb, Zn content in a kind of iron ore | |
| Bourgarit et al. | The elemental analysis of ancient copper-based artefacts by inductively-coupled-plasma atomic-emission spectrometry: an optimized methodology reveals some secrets of the Vix crater | |
| CN101408506A (en) | Method for measuring iron and nickel contents in cobalt-base alloy welding wire by flame atomic absorption method | |
| CN106979945A (en) | A kind of method of Zn content in measure zincizing agent | |
| CN106596700A (en) | Method for determination of content of trace impurity elements in high-purity chromium by acylating chlorination separation/ICP-MS method | |
| CN107219200A (en) | The method that inductively coupled plasma atomic emission spectrometry determines W content in molybdenum-iron | |
| CN110455783B (en) | Method for rapidly analyzing tungsten, manganese, copper, silicon and phosphorus in ferrotungsten | |
| CN106153711A (en) | The assay method of rare earth aluminium alloy Rare Earth Element Contents | |
| CN103149196A (en) | Method for determining content of silicon, phosphor and aluminium in ferrocolumbium through inductive coupling plasma emission spectroscopy | |
| CN106770199A (en) | A kind of method that application ICP AES determine W content in molybdenum-iron | |
| CN109557079A (en) | The ICP-OES measuring method of constituent content in sintering dust separation ash | |
| CN105738347B (en) | A kind of method of elemental lithium in measurement magnesium lithium alloy | |
| CN107727643A (en) | A kind of method of Ti content in inductively coupled plasma atomic emission spectrometry measure manganese metal | |
| CN102928271A (en) | Sample treatment method for measuring niobium, tungsten and zirconium in steel | |
| CN107860762A (en) | A kind of method of iron content in measure zincizing agent | |
| CN108872201A (en) | A kind of method of chromium, manganese content in measurement ferronickel | |
| CN108362684A (en) | The analysis method of gallium element in a kind of measurement rafifinal | |
| CN110161016A (en) | A kind of method of phosphorus content in measurement Fe Ni matrix high temperature alloy | |
| CN111595835A (en) | Method for measuring cerium content in high-silicon stainless steel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170426 |