CN104267092B - A kind of method utilizing mass spectrograph test hafnium isotope - Google Patents
A kind of method utilizing mass spectrograph test hafnium isotope Download PDFInfo
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- CN104267092B CN104267092B CN201410522711.5A CN201410522711A CN104267092B CN 104267092 B CN104267092 B CN 104267092B CN 201410522711 A CN201410522711 A CN 201410522711A CN 104267092 B CN104267092 B CN 104267092B
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Abstract
The present invention provides a kind of method utilizing mass spectrograph test hafnium isotope: when utilizing many reception icp mses to carry out hafnium isotope analysis, testing sample is carried out prescan, if there is fluctuation in signal, then dividing and adding volume fraction several times is the Fluohydric acid. of 50%, until signal is steady, after using the inventive method, without again separating the sample that can obtain signal smoothing, scavenging period is greatly shortened, test accurate to hafnium isotope provides effective support, hafnium content sample low for part, due to without being again evaporated and extracting, decrease secondary pollution and the loss of the secondary separation response rate.
Description
Technical field
The present invention relates to mass spectrograph and measure hafnium isotope, be specifically related to optimize mass spectrograph test hafnium isotope signal and put down
The chemical method of stability.
Background technology
Hafnium is a kind of chemical element, and its symbol of element is Hf.The atomic number of hafnium is 72, and atomic weight is
178.49, belong to Group IVB element.Simple substance hafnium is the glossiness silver gray transition metal of a kind of band.Its fusing point is
2233 DEG C, boiling point is 4602 DEG C, and density is 13.31g/cm3.Fine and close metal hafnium character torpescence, table
Face is easily formed oxide cap, the most stable.Hafnium not with dilute hydrochloric acid, dilute sulfuric acid and strong base solution effect,
But dissolve in Fluohydric acid. and chloroazotic acid.The oxidation state of hafnium is+2 ,+3 ,+4 valencys, and wherein the compound of+4 valencys is the most
Stable.Lutecium-hafnium isotope system is widely used in field of earth sciences, wherein hafnium isotope separation and point
Analysis method of testing have also been obtained further investigation.Geological sample is cleared up through mixed acid High Temperature High Pressure, amberlite
Fat separates, extract the step such as hafnium after form purer hafnium solution to be measured, finally utilize receive inductive etc. from
Daughter mass spectrograph (MC-ICPMS) carries out isotope test.
Existing extraction hafnium operating procedure is:
1. the purer hafnium solution through ion exchange resin separator well is positioned over electric hot plate to be evaporated completely；
2. in the sample being evaporated, add 50 μ L high-pure hydrofluoric acids；
3. the sample adding high-pure hydrofluoric acid it is positioned on electric hot plate and steams to a droplet (about 3 at 140 DEG C
Minute), add 20 μ L high pure nitric acids, and 1mL high purity water, cover bottle cap and obtain solution to be measured；
But, in test process, often occur that in part solution to be measured, hafnium constituent content is extremely low, or tested
The great phenomenon of hafnium elemental signals fluctuation in journey.Hafnium content is too low in testing, it is considered that be to extract hafnium unit
Element time, Fluohydric acid. is excessively evaporated, the hafnium element in sample in nitric acid cannot dissolution, cause can't detect.And
Hafnium signal fluctuation is excessive, it may be possible to owing to the existence of some matrix in separation process causes, so that again
Separate.If hafnium content is too low in Ce Shi, it is molten that solution to be measured is evaporated weight by the many employings of forefathers, again carries with Fluohydric acid.
Take, 2,3 steps must be repeated；If test signal fluctuation is excessive, even need to use the method again separated to carry out
Processing, but this method is the longest, is easily introduced pollution, particular for some rare samples and low hafnium content
Sample, it is impossible to use the method to process.
It addition, hafnium can well be dissolved in Fluohydric acid., and solute effect is the best in nitric acid.Therefore same at hafnium
In the element test process of position, solution to be measured the most all can contain Fluohydric acid..And quartz is had the strongest by Fluohydric acid.
Corrosivity, the nebulizer of MC-ICPMS and torch pipe be all quartz material, therefore, utilizing MC-ICPMS
When carrying out hafnium isotope analysis, PFA corrosion-resistant miniflow nebulizer and film need to be used to go molten equipment (to remove to be measured
Solvent in solution), to reduce Fluohydric acid. to nebulizer and the corrosion of torch pipe.But hafnium is easily adsorbed in film and goes molten
Internal duct, when utilizing MC-ICPMS to test hafnium isotope, sample collecting (i.e. test) time is about
10～12min, scavenging period is about 5～6min.But often occur that sample background value is higher, cannot in the short time
Clean to baseline values, need to significantly extend scavenging period.Wash even with 2% nitric acid+0.5% Fluohydric acid.
Liquid and 2% nitric acid washing liquid alternately cleaning are also required to more than 15min, make troubles to sample analysis.
Summary of the invention
It is an object of the invention to provide a kind of method utilizing mass spectrograph test hafnium isotope.
For reaching above-mentioned purpose, present invention employs techniques below scheme:
1) when utilizing many reception icp mses to carry out hafnium isotope analysis, according to sweeping in advance
Retouch result to process by one of following three kinds of situations:
Situation one, after sample to be analyzed is carried out prescan, if the hafnium isotope signal that obtains of prescan steadily and176Hf signal numerical value is more than 10 times of detection limits, then be directly entered step 2)；
Situation two, after sample to be analyzed is carried out prescan, if there is ripple in the hafnium isotope signal that prescan obtains
Dynamic, then in sample to be analyzed, add Fluohydric acid. by several times, after often adding a Fluohydric acid., again carry out prescan,
Until the hafnium isotope signal that prescan obtains is steady, subsequently into step 2)；
Situation three, after sample to be analyzed is carried out prescan, if although the hafnium isotope signal that prescan obtains is put down
Steady but176Hf signal numerical value is less than or equal to 10 times of detection limits, then add Fluohydric acid. in sample to be analyzed by several times,
Often add after a Fluohydric acid. supersound process 1～5 minutes, and the most again carry out prescan, until
Prescan obtains176Hf signal numerical value is more than 10 times of detection limits, subsequently into step 2)；
2) through step 1) after, according to analyzing the concentration of hafnium standard sample solution used in sample to be analyzed
The concentration of hafnium is adjusted coupling.
Described adjustment coupling specifically includes following steps:
Through step 1) after, if the concentration of hafnium is more than 300ppb in sample to be analyzed, then will with mixed acid solution
In sample to be analyzed, the concentration dilution of hafnium is to 100～300ppb, the volume fraction of nitric acid in described mixed acid solution
Being 2%, the volume fraction of Fluohydric acid. is 0.1%.
Described mixed acid solution uses high purity water, pure through the pure Fluohydric acid. of top grade and the top grade of sub-boiling distillation purification
Nitric acid is formulated.
In situation two and situation three, the single addition of Fluohydric acid. is 5 μ L, and the volume fraction of Fluohydric acid. is
50%, the Fluohydric acid. of volume fraction 50% uses high purity water and the pure Fluohydric acid. of top grade through sub-boiling distillation purification
Formulated.
Through step 2) after, in sample to be analyzed, the volume fraction of Fluohydric acid. controls less than or equal to 2%.
Beneficial effects of the present invention is embodied in:
After using the inventive method, it is not necessary to again separate and can obtain the stable sample of signal, accurate to hafnium isotope
Really test provides effective support, hafnium content sample low for part, due to without being again evaporated and extracting,
Decrease secondary pollution and the loss of the secondary separation response rate.
Further, by being suitably added Fluohydric acid., utilize the ability of Fluohydric acid. dissolution hafnium, solve hafnium and film
Go the problem that molten internal duct combines so that before detection fresh sample, the scavenging period to equipment is greatly shortened.
Accompanying drawing explanation
Fig. 1 is the hafnium isotope test of sample BHVO-2180Hf signal intensity figure.
Detailed description of the invention
With embodiment, the present invention is elaborated below in conjunction with the accompanying drawings.
A certain amount of Fluohydric acid. high-purity solutions is added in solution to be measured by the present invention, obtains smoothly, higher test
Signal, and guarantee that sample signal can be reduced to baseline values in the scavenging period of 6min, receive based on more
The hafnium isotope high precision measurement of icp ms (MC-ICPMS) provides strong propping up
Hold.
The mixed solution of Fluohydric acid. and nitric acid, has highly acid, strong oxidizing property and strong to the element of high quantivalence
Coordination ability, transition elements and non-metal simple-substance before solubilized.Wherein, Fluohydric acid. (HF) and silicon dioxide
(SiO2) the most easily react, its reactional equation is:
SiO2(s)+4 HF(aq)→SiF4(g)+2H2O(l)
In view of Fluohydric acid. to instrument and equipment (the mainly torch pipe part of plasma mass spectrograph, quartz material,
SiO2Content > 99%) severe corrosive, hafnium isotope separate after avoid a large amount of Fluohydric acid. to remain as far as possible.Often
In the Chemical Decomposition product of rule, fluohydric acid content is generally 0.05%～0.1%.Due to sample composition and hafnium element
Content is not quite similar, the hafnium content after separation and matrix composition the most difference, in test process, and part
There is the situation that signal fluctuation is big in sample.Suspect in nitric acid medium, produce moiety complex, in sample introduction mistake
Journey is easily attached to sample introduction pipeline or degree of ionization is weak, cause hafnium signal to fluctuate widely.
After adding a small amount of Fluohydric acid. in the sample of separator well, signal fluctuation is obviously improved.And containing Fluohydric acid.
Sample is readily cleaned, and effectively reduces ambient interferences, reduces and separates or extract the secondary pollution introduced.
Experiment shows, fluohydric acid content is less than the aqueous solution PFA corrosion-resistant miniflow mist of 4% (volume fraction)
Change device (100 μ L/min) and film removes molten (DSN) sample introduction 24 hours, torch pipe is not produced corrosiveness.
Experimental example 1
The operating procedure of this experimental example is:
1. geological sample (BHVO-2) through mixed acid High Temperature High Pressure clear up (Yuan Honglin etc., rock journal,
2007) purer hafnium solution to be measured is formed after the steps such as, ion exchange resin separation, extraction hafnium；
2. utilize high purity water, high-pure hydrofluoric acid and high pure nitric acid preparation containing 2% (volume fraction) nitric acid+0.1%
The mixed acid solution (being designated as reagent A) of (volume fraction) Fluohydric acid.；Utilize high purity water and high-pure hydrofluoric acid
The Fluohydric acid. (being designated as reagent B) of dose volume mark 50%；
3. by solution prescan to be measured, if signal steadily and176Hf signal numerical value is more than 10 times of detection limits, then use
Reagent A dilutes in solution to be measured the concentration of hafnium to 100～300ppb (if solution hafnium concentration to be measured is less than or equal to
300ppb, does not the most do and dilutes or other process)；
4. through prescan, if there is the solution to be measured that hafnium signal fluctuation is big, in this solution to be measured the most repeatedly
Adding reagent B, each addition is 5 μ L, until pre-scan signal is steady, (described steady finger any two is swept
Retouch the absolute value of difference of signal strength values corresponding to time point less than 100mV), then to be measured with reagent A dilution
In solution, the concentration of hafnium (if solution hafnium concentration to be measured is less than or equal to 300ppb, is not done to 100～300ppb
Dilution or other process).
Within the addition concentration of general Fluohydric acid. can be controlled in 1% (volume fraction), indivedual particular sample are slightly higher,
But hydrofluoric acid concentration is less than 2% (volume fraction).After above-mentioned steps 3 or 4, can carry out formal
Based on the hafnium isotope analysis receiving icp ms (MC-ICPMS) more.
Seeing Fig. 1, for the hafnium solution to be measured that the fluctuation of certain pre-scan signal is big, curve A represents and does not adds reagent
During B180Hf signal intensity, curve B represents after adding second time (for the last time) reagent B180Hf believes
Number variation trends.It is clearly visible by Fig. 1, adds the sample signal fluctuation before reagent B greatly,
Cannot accurately measure hafnium isotope ratio；And after adding the reagent B of a certain amount of (10 μ L), sample signal
Tend to be steady, isotopic ratio test can be carried out.
For the solution to be measured that pre-scan signal fluctuation is big, the total amount of most reagent B needing to add is
5～20 μ L, the total amount of indivedual reagent B needing to add is slightly higher.
Experimental example 2
The operating procedure of this experimental example is:
1. geological sample (AGV-1) is cleared up through mixed acid High Temperature High Pressure, ion exchange resin separates, carries
Purer hafnium solution to be measured is formed after taking the steps such as hafnium；
2. utilize high-pure hydrofluoric acid and high pure nitric acid preparation containing 2% (volume fraction) nitric acid+0.1% (volume
Mark) mixed acid solution (being designated as reagent A) of Fluohydric acid.；Utilize high-pure hydrofluoric acid dose volume mark 50%
Fluohydric acid. (is designated as reagent B)；
3. by solution prescan to be measured, if signal steadily and176Hf signal numerical value is more than 10 times of detection limits, then use
Reagent A dilutes in solution to be measured the concentration of hafnium to 100～300ppb (if solution hafnium concentration to be measured is less than or equal to
300ppb, does not the most do and dilutes or other process)；
4. through prescan, right176Hf signal intensity is less than or equal to the solution to be measured of 10 times of detection limits, permissible
Step 4 with reference to experimental example 1 is carried out, but in order to promote the dissolution of hafnium, needs after adding reagent B every time
Carrying out supersound process (time is 3 minutes, and power is 100%), the most again carrying out prescan, until sweeping in advance
Retouch and obtain176Hf signal numerical value is more than 10 times of detection limits；Then hafnium in solution to be measured is diluted by reagent A
Concentration (, is not the most done to 100～300ppb and is diluted or other if solution hafnium concentration to be measured is less than or equal to 300ppb
Process).
Within the addition concentration of general Fluohydric acid. can be controlled in 1% (volume fraction), indivedual particular sample are slightly higher,
But hydrofluoric acid concentration is less than 2% (volume fraction).After above-mentioned steps 3 or 4, can carry out formal
Based on the hafnium isotope analysis receiving icp ms (MC-ICPMS) more.
For experimental example 1, it is generally separated the hafnium obtained solution to be measured176Hf signal numerical value can be much larger than 10 times
Detection limit, therefore, adds after Fluohydric acid. makes the signal of solution to be measured steadily by a small amount of by several times, it is ensured that176Hf signal numerical value is more than 10 times of detection limits.For experimental example 2, a small amount of Fluohydric acid. that adds by several times is not result in
Pre-scan signal fluctuates.In experimental example 1～2, use the purpose that is diluted of reagent A be make to be measured molten
In liquid, hafnium concentration of element is close with standard sample solution concentration (usually 100～300ppb), reduces test
Systematic error.
In this experimental example 1～2, high-pure hydrofluoric acid used (about 23mol/L) uses the pure Fluohydric acid. of top grade through three
Secondary sub-boiling distillation obtains after purification, and its hafnium background is less than 200pg；Described high pure nitric acid (about 14mol/L) is adopted
Obtain after purification through twice sub-boiling distillation with the pure nitric acid of top grade；Milli-Q high purity water (high purity water), resistivity
Reach 18.2M Ω cm-1(25℃)。
Claims (4)
1. the method utilizing mass spectrograph test hafnium isotope, it is characterised in that: comprise the following steps:
1) when utilizing many reception icp mses to carry out hafnium isotope analysis, according to sweeping in advance
Retouch result to process by one of following three kinds of situations:
Situation one, after sample to be analyzed is carried out prescan, if the hafnium isotope signal that obtains of prescan steadily and176Hf signal numerical value is more than 10 times of detection limits, then be directly entered step 2)；
Situation two, after sample to be analyzed is carried out prescan, if there is ripple in the hafnium isotope signal that prescan obtains
Dynamic, then in sample to be analyzed, add Fluohydric acid. by several times, after often adding a Fluohydric acid., again carry out prescan,
Until the hafnium isotope signal that prescan obtains is steady, subsequently into step 2)；
Situation three, after sample to be analyzed is carried out prescan, if although the hafnium isotope signal that prescan obtains is put down
Steady but176Hf signal numerical value is less than or equal to 10 times of detection limits, then add Fluohydric acid. in sample to be analyzed by several times,
Often add after a Fluohydric acid. supersound process 1～5 minutes, and the most again carry out prescan, until
Prescan obtains176Hf signal numerical value is more than 10 times of detection limits, subsequently into step 2)；
2) through step 1) after, according to analyzing the concentration of hafnium standard sample solution used in sample to be analyzed
The concentration of hafnium is adjusted coupling；
Described adjustment coupling specifically includes following steps:
Through step 1) after, if the concentration of hafnium is more than 300ppb in sample to be analyzed, then will with mixed acid solution
In sample to be analyzed, the concentration dilution of hafnium is to 100～300ppb, the volume fraction of nitric acid in described mixed acid solution
Being 2%, the volume fraction of Fluohydric acid. is 0.1%.
A kind of method utilizing mass spectrograph test hafnium isotope, it is characterised in that:
Described mixed acid solution uses high purity water, formulated through Fluohydric acid. and the nitric acid of sub-boiling distillation purification.
A kind of method utilizing mass spectrograph test hafnium isotope, it is characterised in that:
In situation two and situation three, the single addition of Fluohydric acid. is 5 μ L, and the volume fraction of Fluohydric acid. is 50%,
The Fluohydric acid. of volume fraction 50% uses high purity water and formulated through the Fluohydric acid. of sub-boiling distillation purification.
A kind of method utilizing mass spectrograph test hafnium isotope, it is characterised in that:
Through step 2) after, in sample to be analyzed, the volume fraction of Fluohydric acid. controls less than or equal to 2%.
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| CN108459071B (en) * | 2018-03-02 | 2019-05-24 | 中国科学院地质与地球物理研究所 | A kind of method of lutetium-hafnium isotope mass spectrometric measurement |
| CN109580761B (en) * | 2018-11-27 | 2020-05-05 | 中国科学院广州地球化学研究所 | Device and method suitable for absolute micro-area in-situ analysis of hafnium isotope and uranium-lead age |
| CN110596231B (en) * | 2019-11-04 | 2022-03-11 | 中国核动力研究设计院 | Method for measuring hafnium isotope abundance by thermal ionization mass spectrometer |
| CN113219110A (en) * | 2021-03-31 | 2021-08-06 | 国核锆铪理化检测有限公司 | Method for determining content of boron and uranium elements in hafnium-based material |
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| US5110546A (en) * | 1991-05-07 | 1992-05-05 | The United States Of America As Represented By The Secretary Of The Interior | Method for locating metallic nitride inclusions in metallic alloy ingots |
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