CN108414607A - A kind of detection method measuring polymer ultra trace radioactive background - Google Patents
A kind of detection method measuring polymer ultra trace radioactive background Download PDFInfo
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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Abstract
The invention belongs to analytical chemistry fields, are related to a kind of detection method measuring ultra trace radioactive background in polymer.The present invention uses the pretreatment mode of dry ashing method, establishes the analysis method that ICP MS measure ultra trace radioactive background, realizes the analysis of ultratrace element in organic glass.The detection method detection limit of the present invention is up to 1pg/g hereinafter, in addition, the method for the present invention also has easy to operate, fast and accurately advantage.
Description
Technical field
The invention belongs to analytical chemistry fields, are related to a kind of detection side measuring ultra trace radioactive background in polymer
Method.
Background technology
(1) research background that radioactive background measures
Particle physics are as one of most important subject in front line science research, by the extensive concern of researcher.
Wherein, neutrino research is play an important role in the research of international particle physics, is uniquely to have surpassing for experimental evidence so far
The more new physics of particle physics master pattern, the origin to understand microscopic species structure and macrocosm provide abundant card with differentiation
According to.So neutrino research becomes the object of modern scientific research worker research.The Chinese Daya Gulf neutrino experiment hair after 2012
After a kind of existing new neutrino concussion, second neutrino experiment plan will start to construct and implement in the end of the year 2014, the experiment work
Make station the best site selection and be located at Jiangmen, is dedicated to making the neutrino detection of full accuracy, minimum background, maximum-norm in the world
Device, thoroughly to open the mystery of neutrino mass sequence.
Currently, neutrino experiment station in Jiangmen is planned in the 700 meters of construction in underground, one large-scale experimental provision, including an appearance
Receive 20kt liquid scintillators organic glass central detector and a small amount of corollary equipment.Organic glass spherical surface by 500 with
On stainless steel support node, outer layer has nearly 20000 photomultipliers observation neutrinos and liquid scintillator medium mutual
Act on the faint optical signal generated.It is prevalent in due to natural radioactive element in the surroundings of our lives, atom
Core shakiness is permanent to be radiated with form of energy such as alpha ray, β rays and gamma-rays, meanwhile, there is also a large amount of in environment
Cosmic ray, for the optical signal that the two generates considerably beyond neutrino signal, the detection of the micro- subsignal of centering causes serious background
Interference.Therefore, it is necessary to the surrounding enviroment to neutrino detector to propose high request：1) it is built in very deep underground, passes through rock
Layer stops a large amount of cosmic ray；2) intermediate using ultra-pure water as shielded layer, naturally radioactive in environment is stopped by water
The decay ray of element.
In addition to this, in nuclear physics, particle physics, these fields of astroparticle physics, abundant experimental results show right
For almost all of experiment, detector is the most serious by the interference of device materials radioactive background, such as U-238, Th-232,
K-40, Co-60 etc..Alpha and beta decays can occur within the quite a long time for these radioactive isotopes, with production
The optical signals such as raw gamma rays, such radioactive decay will become background example, it is sensitive to restrict neutrino detector naturally
Degree and working efficiency, influence to test expected physical result.Obviously, complicated detector assembly is by organic glass, stainless steel
The materials such as connector, photomultiplier and cable are built.And radioactive isotope U-238 in these materials, Th-232,
K-40 and Co-60 have due to being prevalent in environment in links such as material production, processing, transport, detector assembly
It may be introduced into.Currently, effective control about material for detector background also faces huge challenge, meanwhile, measure detection
The radioactive background of device a variety of materials, and it will be a key subjects to filter out qualified material.
Under based on this research background, it is necessary to subterranean laboratory infrastructure and neutrino experiment detector system for we
Material therefor carries out the measurement and assessment of radioactive background, provides advisory opinion for the selection of neutrino detector, searches out most
Suitable material is as neutrino detection device.
(2) current situation of radioactive element measurement method
Since the nineties in 19th century finds radioactivity, radioactive element has important research valence in numerous subjects
Value, such as：Life science, environmental science, geochronology and core application etc..Currently, about radioactive element measurement method
Have very much, mainstream there are two big technologies：1) traditional radiometric analysis technology；2) on-radiation measures analytical technology：With
Based on mass spectral analysis.
Traditional radiometric analysis technology is frequently used all the time, includes mainly following three aspects：α is counted
Number, β are counted, γ is counted.For the measurement about ultra trace radioactive background in material of this subject study, the above method is all deposited
In common drawback：1) instrumental sensitivity and detection limit limit the measurement of ultra trace radioactive background；2) analytical cycle is longer；
3) background noise is big；4) amount of samples is big；5) counting rate is low.Therefore, it fast and accurately measures and pays no attention in ultratrace element
Think.
Method based on mass spectral analysis has very much, includes mainly：Spark source mass spectrometry (SSMS), laser ionization mass spectrography
(LIMS), glow discharge spectrometry (GDMS), accelerator mass spectrometry (AMS), thermal ionization mass spectrometry (TIMS), secondary ion
Mass spectrography (SIMS), resonance ionization mass spectrometry (RIMS) and inductively coupled plasma mass spectrometry (ICP-MS) etc..Wherein,
ICP-MS has the characteristics that shirtsleeve operation mode and sampling system and rapid multi-element analysis, deep in actual analysis work
Liked by analysis tester.ICP-MS is as the part in Inorganic Mass Spectrometry technology, because it has point of Ion Counting
Analysis ability, to expand radioactive element analysis method.In general, radioactivity survey method obtain be sample radioactivity live
Degree, that reflects the atomicities that radionuclide decays in the unit interval, are denoted as A, and unit is Becquerel (Bq).In fact,
What radioactivity survey method measured is the product during nuclear rearrangement, rather than radionuclide itself.This method and mass spectrum
The radionuclide concentration of measurement is completely different, however, due to nuclear rearrangement be by it is a kind of it is predictable in a manner of occur, so two kinds
It can be established and be connected each other by following formula (1-1 or 1-2) between method.
In formula：M-element quality, g or gL-1
A-radioactive activity (rate of disintegration) Bq or BqL-1
M-molal weight, gmol-1
NA- Avgadro constant
λ-decay coefficient, s-1
t1/2- half-life period, s
ICP-MS, that is, inductively coupled plasma mass spectrometry (Inductively Coupled Plasma-Mass
Spectrometry), find that ICP is superior light source from early 1970s, to the ICP eighties with the powerful excellent of ion source
The gesture advantage few with mass spectrograph high sensitivity, interference is combined, and it is inorganic to become a kind of trace ultra trace being acknowledged as most advantage
Element analysis technology.It can be seen that ICP-MS technologies have been obtained for adequately agreeing from the academic article quantity emerged in multitude out
It is fixed, while the development of the technology also reaches its maturity.From initially the research application of geology department be rapidly spread to environment, metallurgy,
Numerous ambits such as oil, biology, medicine, semiconductor, nuclear material.Although ICP-MS technologies comparative maturity, related
The research of Instrumental Analysis performance never stopped, and still had prodigious application prospects and development space.
ICP-MS analyzes the basic principle of radioactive activity：Sample introduces as a solution, is brought by carrier gas (argon gas)
Atomization system is atomized, and the axial passage of center quarter bend is entered with aerosol form, the quilt under high temperature and atmosphere of inert gases
Fully evaporation, dissociation, atomization and ionization, ion extract through lens system, enter mass analyzer, mass analyzer after focusing
It is detached according to the different mass-to-charge ratio of ion.Ion signal is received by electron multiplier, amplified to be detected.According to ion
Characteristic mass can the qualitative detection element presence or absence, and the ion intensity of flow of element is directly proportional to the concentration of the element,
It can determine the quality of the element in sample.The quality (m) of target isotope is calculated by natural isotopic abundance, known
The decay coefficient (λ) or half-life period (t of each radionuclide1/2) in the case of, it is converted by formula (1-1) or (1-2) required
Radioactive activity (A).
ICP-MS analyzes advantage：Why ICP-MS is widely used in the measurement of radioactive element, with the distinctive analysis of instrument
Performance is undivided：
1) high sensitivity, background are low, detection limit is low.As Modern Instrument Analytical Technique is studied and is improved, instrument is created
Superior analytical performance.Such as：In terms of hot plasma high sensitivity pattern, ion lens focusing system and electron multiplier
Improvement, not only substantially increase the sensitivity of instrument, but also background noise is also effectively reduced.Just because of sensitivity
It is greatly reduced with the detection limit of the improvement of background, instrument.Therefore, this method is analyzed particularly suitable for trace and ultra trace elements.
2) ability of Simultaneous multi element analysis.Quadrupole rod mass analyzer, which provides, jumps peak scanning and multichannel scan mode,
Multiple elements in same sample can be scanned and data acquire, substantially increased analysis efficiency, shorten analytical cycle.
3) relatively simple sample pre-treatments.ICP-MS uses the input mode of solution form, needs to carry out letter to sample
The processing such as single acid is molten, clears up or melts.
4) sample feeding volume is few.The quick analysis etc. of the promotion of peristaltic pump, high nebulization efficiency and detector makes
It is few to complete sample size needed for a sample analysis, about several milliliters.
5) linear dynamic range is wide.Modern instrument uses the discontinuous dynode electron multiplier of double mode, with pulse and mould
Quasi- aspect measures same sample low concentration and the constituent content of high concentration simultaneously.The dynamic linear response range accurately detected is reachable
The 8-9 order of magnitude brings great convenience to actual analysis test.
6) interference is few.The mass spectrogram of ICP-MS is fairly simple, and each element only generates single electricity of one or several isotopes
Charge ions peak.But still have a small amount of double-charge ion and simple Polyatomic ion.Modern instrument is in addition in software
Increase outside the measures such as interference correction formula and quality monitoring in design, advanced design is also taken in instrument hardware, for example adopt
With technologies such as cold plasma, shielding torch, collision/reaction tanks.
Compared with radioactivity survey method, analytical technique of mass spectrum has its superiority.Table 1 composes mass spectrum and α to radioactivity
Nucleic226Ra and239,240The measurement of Pu compares.Data can clearly be seen that from table：Analytical technique of mass spectrum is detecting
There is significant advantage in the performances such as limit, sample analysis duration, amount of samples.
1 mass spectrum of table is composed with α to radionuclide226Ra and239,240The analytical performance of Pu[1]
(3) radioactive element present Research is measured about ICP-MS
Make a general survey of refer to both at home and abroad about radioactive element measurement method, inductively coupled plasma mass spectrometry (ICP-MS)
Shown one's talent in numerous methods with the advantage of highly sensitive, low detection limits, quick Simultaneous multi element analysis etc..In the past to radioactivity
The measurement of element is mostly trace analysis, and traditional radioactivity survey technology can achieve the goal.However, such as neutrino detection
Device adjacent material radioactive background has had exceeded the measurement range of traditional radioactivity survey technology, goes out from the angle of technology
Hair, traditional radioactivity survey method are difficult to meet the requirements.In addition conventional radioactive measurement method analytical cycle is long, amount of samples
Greatly, operation is relative complex, and from the point of view of economic benefit, conventional method even has many insufficient places, in contrast,
ICP-MS has more advantage on analytical performance.Therefore, in the measurement of long half-life radioisotopes element, ICP-MS can be used as one kind
Important auxiliary and the means of supplementing out economy.It can not only ensure the accurate and reliable of experimental result, but also be different from conventional method, simplify
Analysis process.For being analyzed especially for trace and ultra trace elements, it can substantially reduce and pollute and damage in sample handling processes
Mistake problem.ICP-MS is established to the measuring study of material radioactive background, either technology or the problem of economic aspect all may be used
Effectively to be solved, work is measured for the analysis of actual sample and is of great significance.
In the prior art, existing to measure radioactive background using ICP-MS, the laboratory as where inventor has utilized existing
U, Th that some instrument ICP-MS complete ng/g levels in Fe-based amorphous carrying material are measured, and obtain satisfied result.However,
The method that ICP-MS in the prior art is measured cannot still meet the detection for background example in the experiment of such as neutrino detector
It is required that the detection of radioactive element also rests on ng/g, how by the detection level of the metallic elements such as U, Th from ng/g spans to
Pg/g is a stubborn problem.
Invention content
The method of radioactive background of the purpose of the present invention in a kind of measurement organic material using ICP-MS of offer.This hair
Bright purpose also resides in that offer is a kind of easy to operate, and sensitivity is high, the measurement method of radioactive background stablized, and this method can
For in organic matter, the detection of ultra trace radioactive background especially in organic polymer.For the research of such as neutrino detector
Strong reference data is provided, the experimental data that this method obtains is uploaded to and shares achievement in database, it can be to avoid work
Repetition.
The above-mentioned purpose of the present invention is realized by following technological means：
The present invention provides a kind of detection methods of ultra trace radioactive background in measurement polymer, and it includes following steps
Suddenly：
(1) polymer is placed in progress coking processing in silica crucible；
(2) polymer handled through coking is ashed together with crucible to without apparent residue；
(3) ashing postcooling is added in crucible to room temperature and contains HNO3With the aqueous solution of HCl；
(4) heated quartz crucible is to solution slightly boiling；
(5) it is measured with ICP-MS after cooling.
Wherein, the radionuclide of the difficult volatilization of the radioactive background；Preferably, the radioactive background is238U、232Th、60Co、40One or more of K；It is highly preferred that the radioactivity is locally238U、232Th、60One in Co
Kind is several；It is highly preferred that the radioactive background is238U and/or232Th.Wherein,238U、232Th、40The radioactivity of K compared with
Greatly, the object paid close attention to for this field,60Then radioactivity is smaller by Co, and40K is in ICP-MS analyses by isobary40The interference of Ar.
Wherein, the polymer is selected from organic polymer.It is this hair that the organic polymer of processing, which can be ashed, with coking
Bright applicable process object.As exemplary example, these organic polymers such as bio-medical polyester, polyvinylidene fluoride
(PVDF), polymethyl methacrylate etc..In the present invention is as exemplary embodiment, the polymer is selected from poly- first
Base methyl acrylate (is commonly called as organic glass).
Specifically, in method of the invention, in step (1), the sampling amount of polymer is 10~25g；It is preferred that 18~22g；
More preferable 20g.As a preferred embodiment, when sampling, sample quarterlies are sampled.
In step (1), coking processing is carried out on electric furnace；Further, the temperature of coking processing is 200~400 DEG C；Make
To be preferably carried out mode, the temperature of coking processing is 250~350 DEG C；Embodiment more preferably, the temperature of coking processing
Degree is 300 DEG C.Temperature is excessively high, and organic glass melts rapidly, due to containing O in air2, it is easy to catch fire；Temperature is too low, reaction consumption
Duration is unfavorable for coking.As a kind of mode, polymer can be placed in silica crucible, and then crucible is being placed on the electric furnace part of the body cavity above the diaphragm housing the heart and lungs
Change, the coking mode of such opening can also control pyrogenetic reaction convenient for adding substance to be analyzed at any time by adjusting temperature
Speed, and whether compare intuitively observing response complete.
In step (2), the temperature of ashing is 450~600 DEG C；The time of ashing is not less than 30min；Implement as preferred
The temperature of mode, ashing is 500 DEG C；The time of ashing is 30min.
In step (3), contain HNO3In the aqueous solution of HCl, HNO3Volume fraction be 1%~10%；Preferably, it is
2%；The volume fraction of HCL is 0~1%；Preferably, it is 0.5%.
Preferably, in step 3, contain HNO3Volume with the aqueous solution of HCl is 1-2mL.
It should be noted that for containing HNO3Contain HNO with the volume of the aqueous solution of HCl3It is needed with the volume of the aqueous solution of HCl
It strictly to control, which cannot be below ICP-MS test sampling volume 1mL, and the too big corresponding sample concentration of volume can reduce,
The detection limit of instrument, which is not achieved, causes measurement result unreliable, so control is between 1-2mL.
The quality of polymer is set according to expected method detection limit, according to formulaWherein, SD-
The standard deviation of 11 blank solution measured values；M-sampling amount
SD (U)=0.633pg, SD (Th)=1.39pg；It is expected that method detection limit 1pg/g, therefore sampling amount m is not less than
4.18g, to realize that 1pg/g accurate quantitative analysis, method quantitative limit LOQ=3.3LOD, therefore sampling amount m are not less than 13.9g, this
Outside, a greater amount of sampling amounts not only increases the time needed for pre-treatment, but also can consume sample, therefore, considers, preferably takes
Sample amount is 20g.Therefore, it is highly preferred that sampling amount is 20g.
It is also to be noted that the HNO as a preferred embodiment, in step (3)3Preceding elder generation is being used with HCl
Purification is carried out respectively, to remove metal ion and solia particle in acid, to reduce reagent blank.Because through of the invention real
Verification is real, and the acid reagent used in experimentation can bring larger blank if do not purified.The method of purification can be real
Common regent purification method in room is tested, HNO is such as purified using sub-boiling distillation method respectively3And HCl；Embodiment party more preferably
Formula, HNO3Carry out 3 sub-boiling distillation method purifications respectively with HCl.
In step (3), when acid solution is added, sidewall of crucible is uniformly soaked along sidewall of crucible, analysans is made to be dissolved into acid solution
In.
In step (4), the crucible after addition acid solution is placed on electric hot plate, slightly boiling is heated to, further makes to wait for
Analyte is fully dissolved into acid solution, and further, the temperature of heating is 100~200 DEG C；Preferably, heating temperature 150
℃.ICP-MS instrument is may wait for after the completion of heating to be measured.
In step (5), the parameter of ICP-MS is preferably by following matched with inventive substrate and pre-treating method
Scheme, in of the invention, as a preferred embodiment, ICP-MS instrument parameters are used by measuring U, Th；RF power：
1400~1700W；Flow rate of carrier gas：0.8~1.0L/min；Secondary air speed：0.7~0.9L/min；Cooling air flow velocity：13.0~
15.0L/min；CCT flow velocitys：4.0-6.0mL/min；Measurement pattern is one kind in KED or STD.In a preferred embodiment
In, select KED patterns.
It is highly preferred that the parameter of ICP-MS is RF power：1548.6W；Flow rate of carrier gas：0.930L/min；Secondary air speed：
0.795L/min；Cooling air flow velocity：13.88L/min；CCT flow velocitys：4.809mL/min.
For the analysis of the radioactive background of trace, blank value can also be increased by testing residing environment, through of the invention real
Verification is real, and the environment blank of ten thousand grades of toilets is slightly more excellent than the environment blank value of common lab, the difference for the analysis of Th
It is some larger.As a preferred embodiment, the entire detection method of the present invention carries out in ten thousand grades of clean rooms.
In addition, vessel pollution is very important factor, especially in terms of the measurement of super low loading, vessel material is often
Certain influence, such as adsorption loss or capsule contamination etc. can be generated to element to be measured.In experiment, the detection of metal is come
It says, in order to reduce this pollution, can generally use acid bubble, then clean again.In the present invention, and in this way, sample to be tested if any
The container of machine glass, the possible basic sample to be tested such as silica crucible carries out sour bubble, then ultrapure washing before experiment.
Arnquist I J etc. have had measures the U and Th in some polymer using dry ashing method and ICP-MS, so
And in its method, need dry ashing processing of the electroforming copper foil using ultralow background as container progress sample[2].However,
Thus the resin column that also needed to brought removes copper removal, could carry out ICP-MS analyses.And copper foil itself has certain blank value,
Through comparative example 1 of the present invention confirm that resin crosses column and also generate larger blank value, therefore, step is more to bring full procedure blank
The problems such as high, detection limit for height, material damage to be detected etc., for the larger substance to be analyzed of content, this influence can be with
It ignores, but this is totally unfavorable for extremely micro radioactive background analysis.In addition, the side of Arnquist I J
In method,238U、232The detection line of Th can only achieve 1pg/g or more, and cannot reach in neutrino detector material 1pg/g with
This lower measurement request.And in the present invention, the method detection limit of U, Th are below not only 1pg/g, even lower than 0.3pg/g.
Wherein, the detection limit of U is lower compared to Th, down to 0.1pg/g (being shown in Table 3), shows that the method for the present invention has more the detection of U
Advantage some, actual sample analysis in, the relative standard deviation of U is also below Th (table 4).
The present invention uses more easy processing method breakthroughly, obtains lower detection limit instead, this benefit
Ingehious design between each step of the present invention and to the cleverly tradeoff in terms of a variety of materials selection, dosage.
For example, the present invention carries out coking processing as vessel using high-purity silica pot to sample, and multiple times are pure
When the acid solution of change is redissolved, directly with the HNO of specific dosage3It is added in crucible and reheats with the aqueous solution of HCl, this
A little schemes are all especially to study simultaneously ingehious design and selected, so that the present invention obtains detection sensitivity very outstanding
And ease-to-operate.
The advantageous effect of the method for the present invention：
There is following advantage in sample pre-treatments：
1) advantage of the invention is that by polymer, the detection limit of nonvolatile metal is reduced up to 0.X pg/g levels,
This is one for the detection of radioactive background and greatly breaks through because the detection method of the prior art be difficult to meet 1pg/g with
Under measurement request radioactive background is required to be for harsh instrument, is urgent and for such as neutrino detector
It is essential and wants a kind of extremely sensitive detection method.And the method for the present invention, the detection limit of radioactive background is reduced to 0.X
Pg/g is horizontal, by carrying out the measurement to material radioactive background, filters out the detector research and development material for meeting desired physical considerations, can
It is micro- in realization to achieve the purpose that improve neutrino detector signal-to-noise ratio to significantly decrease background example in detector experiment
Effective detection of son makes major contribution for the mankind in the microcosmic particle physics rule of understanding, also will be to cosmology, celestial body object
Reason or even geophysics make major contribution；
2) method of the invention it is simple, quickly, it is accurate, use conventional dry ashing method, entire analytic process only needs 2 small
When；
3) dispensing of sample size is unrestricted, and sample can be replenished in time as needed in open heating on electric furnace；
4) digestion process is few with acid, so reducing the possibility of reagent blank and other pollutions；
5) method of the invention and thinking can provide thinking to carry out the measurement of other types material in detector, such as
Copper fastener, stainless steel water tank, supporting rack etc..
Description of the drawings
Fig. 1 technology paths；
Extraction procedure figure in Fig. 2 comparative examples 1；
HCl and H is successively used in Fig. 3 comparative examples 12C2O4The rate of recovery of elution；
Resolution temperature program in Fig. 4 comparative examples 1, Program A：190 DEG C of holding 15min；Program B：210 DEG C of holdings
15min；Program C：210 DEG C of holding 60min；
Digestion solution adds the variation diagram after water in Fig. 5 comparative examples 1, wherein before (a) plus water：Clear；(b) plus after water：In vain
Color muddiness (program A, B)；(c) plus after water：Clear (program C)；
HNO in Fig. 6 comparative examples 13Repeatedly influence of the purifying to U, Th blank value；
Temperature, pressure, changed power curve in digestion process in Fig. 7 comparative examples 2；
Fig. 8 2%HNO3+ 0.5%HCl is as the eluting solvent before sample introduction, to the elution effect of U, Th.
Specific implementation mode
Below by way of the technical solution that specific embodiment further illustrates the present invention, specific embodiment does not represent to this hair
The limitation of bright protection domain.Other people still fall within this hair according to some nonessential modifications and adjustment that theory of the present invention is made
Bright protection domain.
One of 1 pre-treating method of embodiment：Dry ashing method
Dry ashing method is commonly used for destroying the organic matter in sample, and crucible is usually first placed on electric hot plate by this method to be added
Thermal decomposition carbonization, transfers in Muffle furnace and is ashed, finally dissolve residue, in biological tissue, food, environmental sample
Extensive application.
This experimental selection dry ashing method carries out sample pre-treatments to organic glass, is because organic glass is by organic monomer
The high polymer being polymerized contains a large amount of organic matrix；Secondly, element U, Th of this experimental study are the members of difficult volatilization
Element will not lose because of volatilization；Furthermore this method can increase sampling amount while reduce reagent contamination, therefore this method can
Research for this experiment.This experiment investigates dry ashing method by blank value, the experiment of blank mark-on, from linear, method
Detection limit, method quantitative limit, precision, accuracy angle assess dry ashing method.
Experimental procedure：
(1) Preparatory work of experiment
1) sub-boiling distillation method purifies HNO respectively3And HCl；
2) sample pretreatment；
Organic glass sample (15cm × 2cm × 3mm) is in strip, is cleared up completely to meet sample, it is desirable to obtain volume
Small sample increases the contact area of reaction, and sample knock is granular.Again with 30% nitric acid dousing about 10min, clean table
The mechanical admixture in face, finally uses ultrapure water three times, dries.
(2) dry ashing method is handled：The quality for weighing sky crucible is m1, then accurately weighs 20g samples (being accurate to 0.0001g)
Into silica crucible, on electric furnace (300 DEG C) are slowly heated until sample is gradually carbonized coking bulk, removes and moves to 500 DEG C of horses
Not dry ashing 30min in stove.Without apparent residue residue after dry ashing, it is cooled to room temperature after taking-up.2mL 2% is added dropwise along sidewall of crucible
HNO3After+0.5%HCl solution soaks sidewall of crucible, (150 DEG C) are heated on electric hot plate, wait for that solution slightly boiling is removed immediately, it is cooling
After weigh m2.Solution (Δ m=m2-m1) in crucible is transferred to centrifuge tube, is measured with ICP-MS.After the optimization of ICP-MS
Parameter such as the following table 2.Under pre-treating method and testing conditions after optimization, experiment confirms that the method for the present invention obtains low-down inspection
Rising limit, the in the art ideal rate of recovery and precision.
The running parameter of table 2ICP-MS instruments
Results and discussion
(1) linear, method detection limit and quantitative limit
The preparation of standard working curve：1. U, Th Standard Stock solutions (100 μ g/mL) of 50 μ L are accurately pipetted, with 2%
HNO3+ 0.5%HCl solution is configured to hybrid standard storing solution among 100 μ g/L level-ones；2. accurately pipetting U, Th mono- of 500 μ L
The intermediate hybrid standard storing solution (100 μ g/L) of grade, uses 2%HNO3+ 0.5%HCl solution is configured to mixing mark among 1 μ g/L two levels
Quasi- storing solution；3. accurately pipetting hybrid standard storing solution among 1 μ g/L two levels, 2%HNO is used3+ 0.5%HCl solution is dilute step by step
It releases, is made into the series standard solution of a concentration of 1ng/L, 2ng/L, 5ng/L, 10ng/L, 20ng/L, 50ng/L, 100ng/L.
As shown in table 3, dry ashing method is analyzed, within the scope of defined working curve, the linearly related system of U, Th
Number r is both greater than 0.999, shows good linear relationship, disclosure satisfy that measurement request.The instrument that U, Th are measured in organic glass
Detection limit can carry out ultra trace analysis in 0.1ng/L ranks.U, the method detection limit of Th is respectively 0.10pg/g, 0.21pg/g,
Method quantitative limit is respectively 0.32pg/g, 0.70pg/g, and not only blank value is low for this method, but also sampling amount is big, thus method is examined
Rising limit and quantitative limit can reach very low level, fully meet measurement of this experiment to U, Th in organic glass within 1pg/g
It is required that.
Linear relationship and method detection limit, the quantitative limit (dry ashing method) of table 3U, Th
(2) accuracy and precision
In order to confirm in dry ashing method whether U, Th element pollute or lose, into line blank recovery testu.Take 3 earthenwares
Crucible, every part of addition and comparable U, Th standard of sample size, it is identical as sample handling processes, obtain 3 parts of blank mark-on solution.Together
It manages, as stated above preparation process blank solution, blank recovery of standard addition result such as table 4.
4 rate of recovery of table and precision (dry ashing method)
As shown in Table 4, it is contaminated to illustrate that two kinds of elements are easy for all slightly biased height of the rate of recovery result of two kinds of elements U, Th,
The rate of recovery of middle U is 110%-131%, and the rate of recovery of Th is in 111%-130%, in rate of recovery limit allowable range.And
For the relative standard deviation RSD that two kinds of elements, three Duplicate Samples measure within 10%, precision is preferable.Therefore, dry ashing method
Meet practical measurement request.
(3) sample mark-on reclaims and sample analysis
It is parallel weigh 6 parts, 20g organic glasses sample (being accurate to 0.0001g) evaluates sample result；Meanwhile if
It counts 3 groups of difference mark-on amounts and carries out sample mark-on experiments, it is parallel to weigh 9 parts, 20g organic glasses (being accurate to 0.0001g), every 3 parts
It it is one group, every group of sample sequentially adds basic, normal, high U, Th standard, and (the ratio between basic, normal, high mark-on amount and method quantitative limit control
1,10,100)；Similarly, preparation process blank solution.U, Th content in sample are measured, as shown in table 5.Calculating elements are in difference
The rate of recovery of mark-on amount, the results are shown in Table 6.
As shown in Table 5, the result that dry ashing method measures is above method detection limit, near method quantitative limit, shows to do
The accurate measurement of ultratrace element in this experiment may be implemented in ashing method, and shows significant advantage.It is obtained by calculation organic
The content of U, Th are respectively 0.39pg/g, 0.77pg/g in glass, and in 6 parallel sample measurement results U, Th relative standard
Deviation RSD is respectively 23.3% and 50.5%, and for the measurement of super low loading element, precision of measurement is preferable.Significantly
Find out the precision of Th not as good as U, it may be possible to caused by sample is uneven, can specification sample acquisition method, such as sample quarterlies.
The analysis result of 5 organic glass sample of table
As shown in Table 6, the sample mark-on time 1,10 or 100 is controlled in the ratio between basic, normal, high mark-on amount and method quantitative limit
In yield experiment, the preferable rate of recovery is all shown.Near quantitative limit, the rate of recovery of U, Th are respectively 97.7%, 65.8%,
As a result accuracy is preferable；U, the relative standard deviation RSD of 3 parallel sample measurement results of Th be respectively 24.1%,
35.9%, test precision is preferable.Near high basis weight limit in the recovery testu of (10 times and 100 times), U, Th's returns
Yield is respectively 95.1%-98.0%, 84.7%-91.0%, and this method rate of recovery is fine, while two kinds of elements, 3 Duplicate Samples
For the relative standard deviation RSD of product measurement result within 10%, test precision is also fine.For ultratrace element analysis
Speech, the accuracy of this method and precision are all in tolerance interval.
The result of 6 sample mark-on reclaims of table
Note：What is indicated in bracket is mark-on amount.
This method brief summary：
The pre-treating method for establishing dry ashing method realizes that ICP-MS measures U, Th：Using dry ashing method to organic glass
Treating capacity only needs 2mL, entire processing procedure about 2h up to 20g in overall process with acid amount.As a result it shows：In the concentration model of design
In enclosing, U, Th working curve it is linear good, method detection limit is respectively 0.10pg/g, 0.21pg/g, method quantitative limit difference
For 0.32pg/g, 0.70pg/g, meet the measurement request of ultra trace analysis.U, Th in three parts of standard sample parallel determinations
Relative standard deviation RSD is respectively 8.6%, 8.7%, and test precision is good, and the rate of recovery is respectively 110%-131%, 111%-
130%.It is parallel to weigh 6 parts of samples measurements, as a result show that U, Th content are respectively 0.39 ± 0.16 in organic glass (TC 0#)
(pg/g), 0.77 ± 0.32 (pg/g) realizes the accurate quantitative analysis of ultra trace U, Th in organic glass.Finally, pass through formula (1-
1) it is converted into (1-2)238U、232The radioactive activity of Th is respectively 4.9 ± 2.0 (μ Bq/kg), 7.2 ± 1.3 (μ Bq/kg).
2 testing conditions of embodiment
Parameter such as table 2 after the optimization of ICP-MS.Parameter after optimization is more suitable for the detection of the present invention locally and coordinates
The accurate measurement of object after pre-treating method.Detection accuracy is further promoted.Briefly illustrate detector bar
The comparison of pattern in part.For example, measure mark-on solution (C=61.35ppt) 3 times through investigating STD and KED both of which, gained
The results are shown in Table 7.
The accuracy of U, Th detection, precision are compared under the different detection patterns of table 7.
For detecting U, Th, with KED patterns and particular detection condition, effect more outstanding can be reached in terms of accuracy
Fruit.Especially for the detection of U, accuracy can reach very rare 99.35%.
Eluting solvent is investigated
ICP-MS is surveyed during U, Th, is measured in order to avoid a upper sample carryover influences next sample, and reduce
Testing time uses 2%HNO3+ 0.5%HCl is investigated as eluting solvent, and U, Th elution experiments are as shown in Figure 8.U, Th
Signal can be reduced rapidly in the short period, and close to 0.So this experiment is with 2%HNO3+ 0.5%HCl is molten as eluting
Agent.
The two of 1 pre-treating method of comparative example：Micro-wave digestion-solid phase extraction
Solid Phase Extraction (SPE) grew a lot in recent years as a kind of enrichment method, was increasingly valued by people,
Status in sample pre-treatments also becomes increasingly conspicuous.For two kinds of radioactive elements U, the Th studied in the present invention, have to it
The resin of selective absorption has become commercialization product, and has lot of documents report about abstraction technique in radio chemistry
Application.The technology can handle bulk sample, and can efficiently separation and concentration object.This experiment is carried out using ICP-MS
Detection, in order to meet the Sample introduction mode of solution form, needs to carry out resolution processing to SOLID ORGANIC glass sample.Due to having
Machine glass is a kind of organic polymer polymeric material, and general dissolution method and wet digestion are difficult to achieve the purpose that clear up completely.
Therefore, make every effort to probe into a kind of suitable, effective, complete digestion procedure.With becoming increasingly popular for ICP-MS technologies, micro-wave digestion is close
It is used widely in sample pre-treatments over year, keeps sample quick under higher temperature and pressure condition using microwave heating
Dissolving.
Trial is handled it with micro-wave digestion inventor in an experiment, currently, laboratory possesses CEM MARS6 high
Flux microwave dissolver can run 40 counteracting tanks simultaneously, and since each counteracting tank carrying sample size is limited, high throughput can batch
Sample is handled, then the solution after resolution is mixed, to realize the purpose for increasing quantity of sample handling.Later, it selects solid
Mutually the solution cleared up is carried out selective enrichment by the method for extraction (SPE), to improve the concentration of object element (U, Th), to
Realize accurate detection.
This method has probed into the content in terms of following four：
Optimum condition in extraction process, the extraction process can be divided into four steps：Cleaning, absorption, purification, elution,
In, it is the emphasis of this Solid Phase Extraction research to select suitable absorption and elution requirement.
Experimental procedure：The UTEVA resins that there is selective absorption to U, Th are selected, SPE columns are fabricated to, by extraction procedure figure
Shown in 2, with 3M HNO3U, Th standard specimen for preparing 1 μ g/L known concentrations determine best extraction conditions by rate of recovery experiment.
Results and discussion
1) adsorption conditions
This experimental selection 3M HNO3As solution medium, 1 μ g/L mixed standard solutions solution after SPE column extractings is measured
Concentration CInspection, calculate the adsorption percentage of U, Th in 1 μ g/L mixed standard solutions of UTEVA resins pair.Known to its result such as table 8：
UTEVA resins to the absorption of U, Th close to 100%, therefore, with 3M HNO3As this experiment adsorption conditions, it can be achieved that U,
Effective absorption of Th.
U, Th concentration in solution after UTEVA resins of table 8
2) elution requirement
Priority 0.02M HCl and 0.03M H are investigated2C2O4The effect of elution.The results are shown in Figure 3, for U,
It can only be eluted completely with 0.02M HCl, the rate of recovery is up to 98%.And HCl at this time only has the elution of Th
81%, remaining 13% needs oxalic acid to continue to elute.Therefore, it draws the following conclusions：For the Th, the HCl of low concentration of 1 μ g/L levels
Elution effect be not highly desirable, it is also necessary to oxalic acid further elutes.In this experiment, it is remaining why oxalic acid can elute
Th is eluted because of complex compound is formed between oxalic acid and Th.However, the introducing of oxalic acid makes U, Th blank value (be shown in Table
9) it obviously increases, this is because caused by oxalic acid reagent purity factor, this experiment is measured and generates larger background interference.Synthesis is examined
Consider：Although oxalic acid can improve the rate of recovery of Th, reagent blank is introduced simultaneously, runs counter to the measurement of this experiment low concentration.
Therefore, select 0.02M HCl as the eluent of U and Th.
Table 9 priority HCl and H2C2O4Elute the blank value introduced
The sample size and corresponding micro-wave digestion program of each counteracting tank, by temperature, time, power in resolution program
Optimization realize organic glass thoroughly clear up.
Experimental procedure：
1) sample pretreatment
Organic glass sample (15cm × 2cm × 3mm) is in strip, is cleared up completely to meet sample, it is desirable to obtain volume
Small sample increases the contact area of reaction, and sample knock is granular.Again with 30% nitric acid dousing about 10min, clean table
The mechanical admixture in face, finally uses ultrapure water three times, dries.
2) Specimen eliminating
The sample size of counteracting tank is related with sample type, the requirement of instrument usage criteria：Organic sample should be limited in 1g/ appearances
Device.Organic glass is the polymer of methyl methacrylate monomer, it is more difficult to clear up, be cleared up using Microwave Digestion.It is grasped
Make as follows：1. weighing the organic glass of 0.1g or so in polytetrafluoroethylene (PTFE) counteracting tank, 10mL concentrated nitric acids are added, places and disappears in advance
Solution；2. tighten lid without significant reaction in pre- digestion process and be put into microwave dissolver, be arranged different micro-wave digestion programs into
Row resolution；3. taking out counteracting tank after having cleared up, can opening, solution shows that Specimen eliminating is complete in clear；Acid is caught up with 4. being put into
Acid is caught up in (180 DEG C) heating of instrument.
Results and discussion
Microwave dissolver is worked with temp-controled mode, since organic glass is mainly organic principle, it is contemplated that resolution
Vigorous reaction may occur for process, and therefore, instrument Classic modes, manual setting Gradient program, it then follows such as are taken in this experiment
Lower using priciple：Temperature ramping rates are no more than 10 DEG C/min, and power is determined according to the number of jar, pressure pan highest work temperature
Degree is 210 DEG C (tolerable temperature is 260 DEG C).Establish three groups of gradient increased temperature programs, in order to slow down the violent of resolution reaction
Degree.As shown in Fig. 4 programs A, B, C, after the completion of resolution, the case where digestion solution, is as shown in Figure 5.
It is analyzed in conjunction with Fig. 4 and Fig. 5, clear (a) is all presented in three groups of temperature programs A, B, C solution after having cleared up, but
Add and found in water transfer process, white opacity (b) occurs in program A, B digestion solution, and clear (c) is presented in program C digestion solutions, very
Obviously under the conditions of program A, B, organic glass fails thoroughly to clear up, the reason is that temperature and retention time are arranged in program A, B also
It is insufficient to allow sample to clear up completely.For program C by increasing temperature and extending the time, clear (c) is presented in digestion solution, therefore selects
Select resolution programs of the program C (table 10) as this experiment.
10 micro-wave digestion program of table
The analysis method for establishing micro-wave digestion-Solid Phase Extraction, from blank value, method detection limit and quantitative limit, assessment
The validity that this method measures this experiment.
Experimental procedure
Weigh 6 parts, the organic glass sample (being accurate to 0.0001g) of every part of about 0.1g, respectively in 6 counteracting tanks, often
10mL concentrated nitric acids are added in part, and the resolution program probed by the second part clears up sample, and acid is caught up with after having cleared up, and evaporate
5mL 3M HNO are used after to close do3Multiple rinse counteracting tank, and the solution after 6 parts of rinses is merged and is collected, then through SPE columns
(UTEVA resins) extracts, and is extracted with reference to the extraction conditions for the SPE columns that first part probes into.Finally, by eluent catch up with acid,
Constant volume obtains a sample solution, waits for examination with computer to 1mL.Similarly, parallel sample solution is made as stated above and process is empty
White solution, and analyzed.
Results and discussion
Linear relationship and method detection limit, the quantitative limit (micro-wave digestion-solid phase extraction) of table 11U, Th
Note：It is that be 1mL calculate 0.6000g constant volumes that method detection limit and quantitative limit, which are by sampling amount, in this experiment.
By data analysis in table 11, micro-wave digestion-solid phase extraction is in the concentration range of design, the linear correlation of U, Th
Coefficient r is both greater than 0.999, shows in the concentration range, and instrument is all fine to the linear response of U, Th.U, Th in this method
Instrument detection limit can reach 0.1ng/L, show that instrument is to can be achieved on ng/L horizontal measurements in theory, but method detection limit
It is up to tens or hundreds of pg/g with quantitative limit, cannot be satisfied to U, Th content in organic glass in the accurate quantitative analysis of 1pg/g or so.
It investigates and optimizes three factors (vessel, environment and reagent) for influencing blank value.
Above-mentioned sample-pretreating method is further investigated, the original for causing experimental result to be unable to reach target is analyzed
Cause.It is analyzed for this experiment ultratrace element, blank value is the key factor for influencing measurement result, is heavily dependent on
The process and method of sample pre-treatments.The above-mentioned extraction probed into and Specimen eliminating process belong to sample pre-treatments, due to ICP-
MS high sensitivities, so environment, the blank of vessel and reagent and pollution problem seem especially prominent in sample preparation procedure.
On the basis of the resolution and extraction of foundation, the blank value introduced to sample pretreatment process measures.According to measurement result, specifically
Analyze cause blank value higher factor, mainly from the aspect of environment, vessel and reagent three, and take appropriate mode into
Row improves.Therefore, this trifle investigates the influence of reagent, environment and vessel to blank value respectively.
1) reagent
HNO3The maximum reagent of dosage in being both digestion solution and adsorbing medium or experimentation.Using sub-boiling distillation
Method can remove metal ion and solia particle in nitric acid liquid, and to reduce reagent blank, this method is normal in laboratory
Regent purification method.Similarly, hydrochloric acid can also further be purified using sub-boiling distillation method, but due to hydrochloric acid dosage seldom and
Hydrochloric acid used has been OPTIMA ranks, therefore the influence to blank value can be ignored.This trifle high spot reviews are nitric acid
Through repeatedly after purification to the influence of blank value.The results are shown in Figure 6.As seen from the figure, it is purified by 3 times, U, Th blank value have bright
Aobvious downward trend, shows that sub-boiling distillation method can reduce reagent blank to a certain extent, non-to the measurement of super low loading element
It is often significant.
2) environment
The natural radioactive element that this experiment measures has the characteristic of generally existing, is often distributed in the experiments such as air, dust
In environment.Since sample pretreatment process is not completely enclosed, laboratory environment is certain to also will produce for blank value
It influences.The blank value that two different experiments rooms are handled is compared by this trifle, as a result as shown in table 12, in ten thousand grades of clean rooms
Obtained blank value is slightly better than common lab, therefore, it may be considered that (such as hundred grades of the higher laboratory of purity requirements
Clean room) inner room completion sample treatment, so that experimental measurements is effectively improved.
The comparison of blank value under 12 different experiments environment of table
3) vessel
Vessel pollution is very important factor, and especially in terms of the measurement of super low loading, vessel material is often right
Element to be measured generates certain influence, such as adsorption loss or capsule contamination etc..Therefore, it is necessary to also be carried out to vessel for this experiment
It investigates.Table 13 compares the concentration of U, Th in solution before and after resolution, as can be seen from the table, the U in solution after resolution
Concentration increase a magnitude, the concentration of Th also has to be increased by a small margin.It is obvious that the polytetrafluoroethylene (PTFE) used in this experiment disappears
The pollution that solution tank introduces in digestion process, makes measurement result generate larger systematic error, ultimately causes entire measure and is attributed to mistake
It loses.Take 30%HNO3The cleaning methods such as soaked overnight, slack tank resolution attempt to improve the pollution problem that counteracting tank introduces, but all
Have no significant results.Its reason may be that polytetrafluoroethylene (PTFE) high molecular material is porous structure, has wrapped up some impurity and has caused height
It is constantly precipitated when warm reaction under high pressure.
Table 13 clears up the variation of U, Th blank value in front and back solution
This method brief summary：
The pre-treating method for establishing micro-wave digestion-Solid Phase Extraction realizes that ICP-MS measures U, Th：Utilize Solid Phase Extraction skill
Art can improve the concentration of element, so as to improve method detection limit.The fiber material for selecting UTEVA resins to be enriched with as U, Th,
Absorption and elution requirement are optimised, and are identified as 3M HNO3With 0.02M HCl.It is organic to design the progress of micro-wave digestion program
Glass is cleared up, and finally found that 10mL concentrated nitric acids are added with 0.1g samples keeps 1h that can reach what sample was cleared up completely at 210 DEG C
Purpose.In the method, the detection limit of U, Th are respectively 109pg/g, 13.4pg/g, and therefore, U, Th are not detected in organic glass.
Investigate the influences of the factors to blank value such as environment, vessel, reagent, wherein the pollution that counteracting tank material (polytetrafluoroethylene (PTFE)) introduces
It is the key factor for limiting this experiment measurement.
The three of 2 pre-treating method of comparative example：Super microwave method
Super microwave (UltraCLAVE) is the important technical innovation obtained in terms of micro-wave digestion in recent years, from
Since the super microwave of First enters China within 2008, favored by many users.This is known as microwave best in the world
Resolution instrument has broken the various limitations of conventional microwave resolution, is had the advantage that in terms of sample pre-treatments：1) sample handled
Amount greatly increases：By single counteracting tank maximum sample amount up to 25g, or (77) realizations of large batch of sample are cleared up simultaneously；
2) sample of other digestion procedure difficulty resolutions can be cleared up under the conditions of high temperature, high pressure (260 DEG C, 200bar)；3) with a batch resolution
Different types of sample can be handled；4) with acid amount, there is no limit small with acid amount；5) digestion tube does not need pressure resistance, common examination
Pipe, colorimetric cylinder can also be used；6) reaction is in high pressure N2It is carried out in atmosphere, avoids liquid boiling and element loss, contamination
The generation of phenomenon.
Why this experiment selects super microwave to carry out sample pre-treatments, compares comparative example 1, super microwave list tank sampling amount
Big sampling amount may be implemented in high an order of magnitude, not only increases analyte concentration, and the counteracting tank quantity needed is few,
Reduce the blank value of container introducing.It is also reduced with acid amount simultaneously, reduces reagent blank.Super microwave method has superior point
Performance is analysed, the blank value for solving the problems, such as to encounter in the practical measurement of comparative example 1 is expected to, finally realizes the accurate detection of U, Th.Table
14 list the analytical performance of conventional microwave and super microwave.
The comparison of 14 conventional microwave of table and super microwave analysis performance
For the organic glass sample of this experimental study, resolution processing is carried out using super microwave, it is also necessary to further visit
Study carefully its maximum sampling amount, measured with acid, resolution program (temperature, pressure and time).Since super microwave is (heatproof, resistance to digestion tube
Pressure energy power, mechanical strength) less-restrictive, it is contemplated that the blank interference that the counteracting tank of front polytetrafluoroethylene (PTFE) material introduces compared with
Greatly, this section is in addition to choosing polytetrafluoroethylene (PTFE) material counteracting tank, and the counteracting tank for also having chosen high purity quartz material carries out analysis and examines
It examines.Meanwhile U, Th measurement in organic glass are applicable in from blank value, method detection limit and quantitative limit to evaluate super microwave method
Property.
This method has probed into the content of following three aspects：
For the organic glass sample of this experimental study, resolution processing is carried out using super microwave, further probes into it most
Big sampling amount is measured, resolution program (temperature, pressure and time) with acid.
It is cleared up using super microwave.Its operating procedure is as follows：
1) sample of about 5.0000g is weighed in polytetrafluoroethylene (PTFE) counteracting tank, and 35mL concentrated nitric acids and 20mL ultra-pure waters is added,
Place pre- resolution；
2) close the lid and be put into reaction under high pressure chamber without significant reaction in pre- digestion process, to cavity in be filled with N2Make just
Beginning pressure is shown as 40bar, and resolution program is cleared up in setting table 15.
3) counteracting tank is taken out after having cleared up, is uncapped, drives oxides of nitrogen gas away, solution shows that sample disappears in clear
Solution is complete.Temperature, pressure, changed power curve are as shown in Figure 7 in reaction process.
4) solution cleared up is put into and (180 DEG C) heating of sour instrument is caught up with to use 2%HNO when being evaporated to close dry3+ 0.5%HCl
Constant volume is to be measured to 1mL.
The resolution program of 15 super microwave of table
The analysis method for establishing super microwave evaluates super microwave method from blank value, method detection limit and quantitative limit
The applicability that U, Th in organic glass are measured.
Experimental procedure
2 parts are weighed, the organic glass sample (precise is accurate to 0.0001g) of every part of about 5g is cleared up at 2 respectively
In tank, every part is added 35mL concentrated nitric acids and 20mL ultra-pure waters, is cleared up to sample by " 3.4.2 Specimen eliminatings ", and 2 parts are cleared up
Solution afterwards mixes, and catches up with acid, and 2%HNO is used after being evaporated to close do3+ 0.5%HCl constant volumes are to be measured to 1mL.Similarly, it presses
Parallel sample solution and process white solution is made in the above method, and is analyzed.
Results and discussion
When with super microwave treatment, the working curve of U, Th are as shown in table 16, and linearly dependent coefficient r is all higher than 0.999,
Coincidence measurement requirement.The instrument detection limit that U, Th are obtained using this method is respectively 0.154ng/L, 0.370ng/L, method detection
Limit is respectively 4.97pg/g, 8.88pg/g, and method quantitative limit is respectively 16.5pg/g, 29.6pg/g.Compared to micro-wave digestion-solid phase
Extraction, the detection limit and quantitative limit of super microwave method have the tendency that being substantially reduced, and main cause is that sample size increases from 0.6g
It is added to 10g, improves a most magnitude, therefore downward trend is apparent.But this method still fails to meet this experiment measurement and wants
It asks.
Linear relationship and method detection limit, the quantitative limit (super microwave method) of table 16U, Th
Note：It is that be 1mL calculate 10g constant volumes that method detection limit and quantitative limit, which are by sampling amount, in this experiment.
Since super microwave is to the less-restrictive of digestion tube (heatproof, voltage endurance capability, mechanical strength), it is contemplated that front poly- four
The blank interference that the counteracting tank of vinyl fluoride material introduces is larger, and this method is also selected in addition to choosing polytetrafluoroethylene (PTFE) material counteracting tank
The counteracting tank of high purity quartz material has been taken to carry out analysis and investigation.
Using super microwave method measure the results show that polytetrafluoroethylene (PTFE) counteracting tank introduce pollution problem, be to cause sky
The increased principal element of white value, to make method detection limit be deteriorated.Since super microwave requires less the material of counteracting tank, because
This, considers to use the counteracting tank of high purity quartz material instead and be investigated to its blank value, as a result as shown in table 17, polytetrafluoroethylene (PTFE)
Therefore tank uses quartzy tank instead with quartzy ullage white value no significant difference, blank value also fails to be effectively improved.
Influence of the 17 counteracting tank material of table to blank value
This method brief summary：
The pre-treating method for establishing super microwave realizes that ICP-MS measures U, Th：Super microwave overcomes traditional microwave pair
Sour dosage and analysis time have been saved in the limitation of sample size and temperature.After optimizing resolution condition, 35mLHNO is added in 5g samples3With
20mLH2O, temperature, can be complete by Specimen eliminating less than 1h up to 255 DEG C.In the method, the detection limit of U, Th are respectively
4.97pg/g, 8.88pg/g, although detection limit is substantially reduced, not up to target.Investigate the blank value of this method, hair
Existing counteracting tank (polytetrafluoroethylene (PTFE)) is still the limited resource of this method.The investigation that quartz digestion tank carries out blank value is chosen,
It is not affected significantly.
It summarizes：
As people go deep into tera incognita exploration, the electronic device that R ＆ D design comes out constantly is broken through in performance
And innovation, it is measured including material radioactive background.Material radioactive background is often that constraint device sensitivity and work are imitated
The key factor of rate, the measurement accordingly, with respect to radioactive background are operated in research from now on and can become increasingly conspicuous.Due to traditional
Radioactivity survey sensitivity is relatively low, background bothers that big, the sample treatment period is long, the big equal difference of amount of samples analytical performance,
It can not be obtained in actual measurement satisfied as a result, can be made up to the measurement of material radioactive background using ICP-MS methods above-mentioned
Deficiency realizes simple, quick, accurate analysis.
Inventor during the experiment, to multiple experiment parameters of three kinds of pre-treating methods and each pre-treating method and
Experiment condition has all carried out a large amount of analysis work, as a result, in three kinds of methods, only dry ashing method is by maximum sampling amount and most
Low blank value meets the measurement request of ultra trace radioactive background.In the course of the research, inventor has found, in micro-wave digestion-
In solid phase extraction and super microwave method, the counteracting tank of polytetrafluoroethylene (PTFE) can bring larger blank value, even if using high-purity stone
English counteracting tank, in super microwave method, blank value also fails to be effectively improved, and in dry ashing method, silica crucible to blank
The influence of value is little.The reason of this is likely to be is that super microwave is carried out in the state of high temperature and pressure, at this time under concentrated acid
Solution is fully acted on container, is increased the precipitation of container background, is increased blank.In addition, compared to micro-wave digestion-solid phase extraction and
Super microwave method, dry ashing method have the superior analytical performances such as easy to operate, time saving and accuracy, precision be good, especially
It is suitble to the measurement of ultratrace element in this experiment organic glass, substantive reference meaning is provided for ultralow sample-out count work
See.Table 18 shows the comparison of three kinds of pre-treating methods, wherein the pre-treating method sensitivity of dry ashing method down to 1pg/g with
Under, have for the radioactive background detection in material radioactive background especially neutrino detector material extremely important prominent
Broken property progress, and analysis duration is most short in three kinds of pre-treating methods, only 2h.
Measurement for ultratrace element, especially sensitivity are down to 1pg/g analysis methods below, not only analysis method
Selection, such as the selection of pre-treatment, the selection of analytical instrument；In addition, every single stepping in analysis method is likely to dividing
The result of analysis causes strong influence, as sample size number, eluting solvent selection, the selection of container and residing analysis
Environment etc. can all have an impact.Therefore, it is one of key that reasonably selection pre-treatment and analytical instrument, which are analysis methods, it
Afterwards, especially reasonable design and linking are required to for each processing step, to realize accurate ultra trace analysis, these details
The step of property, equally successfully plays a decisive role to ultra trace analysis.
18 3 kinds of pre-treating methods of table compare
Bibliography：
1.Lariviere D,Taylor V F,Evans R D,et al.Radionuclide determination
in environmental samples by inductively coupled plasma mass spectrometry[J]
.Spectrochimica Acta Part B:Atomic Spectroscopy,2006,61(8):877-904.
2.Arnquist I J,Hoppe E J,Bliss M,et al.Mass Spectrometric
Determination of Uranium and Thorium in High Radiopurity Polymers Using Ultra
Low Background Electroformed Copper Crucibles for Dry Ashing[J].Analytical
Chemistry,2017,89(5):3101-3107.
Claims (10)
1. a kind of detection method measuring ultra trace radioactive background in polymer, it is characterised in that comprise the steps of：
(1) polymer coking in silica crucible is placed in handle；
(2) polymer handled through coking is ashed together with crucible to without apparent residue；
(3) ashing postcooling is added in crucible to room temperature and contains HNO3With the aqueous solution of HCl；
(4) heated quartz crucible is to solution slightly boiling；
(5) it is measured with ICP-MS after cooling.
2. according to the method described in claim 1, it is characterized in that, the radioactive nucleus of the difficult volatilization of the radioactive background
Element；
Preferably, the radioactive background is238U、232Th、60Co、40One or more of K；It is highly preferred that described puts
Penetrating property background is238U、232Th、60One or more of Co；It is highly preferred that the radioactive background is238U and/or232Th。
3. according to the method described in claim 1, it is characterized in that, the polymer is selected from organic polymer；Preferably, institute
Any one of the organic polymer stated in bio-medical polyester, polyvinylidene fluoride, polymethyl methacrylate；
Preferably, the polymer is selected from polymethyl methacrylate.
4. according to the method described in claim 1, it is characterized in that, in step (1), the sampling amount of polymer is 10~25g；
It is preferred that 18~22g；More preferable 20g；
Preferably, sampling uses sample quarterlies.
5. according to the method described in claim 1, it is characterized in that, in step (1), coking processing is carried out on electric furnace；
Preferably, the temperature of coking processing is 200~400 DEG C；It is highly preferred that the temperature of coking processing is 250~350 DEG C；
It is highly preferred that the temperature of coking processing is 300 DEG C；
Preferably, in step (1), crucible is placed in progress coking processing on electric furnace.
6. according to the method described in claim 1, it is characterized in that, in step (2), the temperature of ashing is 450~600 DEG C, ash
The time of change is not less than 30min；Preferably, the temperature of ashing is 500 DEG C；The time of ashing is 30min.
7. according to the method described in claim 1, it is characterized in that, in step (3), with containing HNO3Aqueous solution with HCl is along quartz
Sidewall of crucible is added, and uniformly soaks sidewall of crucible；
Preferably, contain HNO3In the aqueous solution of HCl, HNO3Volume fraction be 1%~10%；It is highly preferred that being 2%；
The volume fraction of HCl is 0~1%；It is highly preferred that being 0.5%；
Preferably, in step (3), contain HNO3Volume with the aqueous solution of HCl is 1-2mL；
Preferably, the HNO in step (3)3It is first purified respectively using preceding with HCl；Preferably, it is purified using sub-boiling distillation method
HNO3And HCl；It is highly preferred that HNO3Carry out 3 purifications respectively with HCl.
8. according to the method described in claim 1, it is characterized in that, in step (4), the temperature of heating is 100~200 DEG C；
Preferably, temperature is 150 DEG C；
Preferably, it is heated on electric hot plate.
9. according to the method described in claim 1, it is characterized in that, the parameter of ICP-MS is RF power：1400~1700W；It carries
Gas velocity：0.8~1.0L/min；Secondary air speed：0.7~0.9L/min；Cooling air flow velocity：13.0~15.0L/min；
CCT flow velocitys：4.0-6.0mL/min；Measurement pattern is one kind in KED or STD；
Preferably, the parameter of ICP-MS is RF power：1548.6W；Flow rate of carrier gas：0.930L/min；Secondary air speed：
0.795L/min；Cooling air flow velocity：13.88L/min；CCT flow velocitys：4.809mL/min；
Preferably, measurement pattern KED.
10. according to any methods of claim 1-9, which is characterized in that whole experiment process in ten thousand grades of clean rooms into
Row.
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Inventor after: Liu Hongtao Inventor after: Li Mengting Inventor after: Tang Jian Inventor after: Wang Xiangyue Inventor after: Feng Shunqing Inventor after: Liang Minsi Inventor after: Chen Yuxin Inventor before: Liu Hongtao |