CN102230861A - Method of digesting, settling and separating tungsten-based samples and detection method for tungsten-based samples - Google Patents
Method of digesting, settling and separating tungsten-based samples and detection method for tungsten-based samples Download PDFInfo
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Abstract
The invention discloses a method of digesting, settling and separating tungsten-based samples and a detection method for tungsten-based samples. The method of digesting, settling and separating tungsten-based samples comprises the following steps: putting a tungsten-based sample in a container, adding water and nitric acid into the container, keeping the container airtight, carrying out microwave digestion and settlement-separation on the sample under gradient temperatures, and restarting microwave for rinsing and deposition after the temperature of the solution decreases and is close to the boiling point of water so as to obtain a sample solution for detection and precipitates of tungstic acid. The detection method for tungsten-based samples in the invention is to analyze the digested sample solution with at least one analytical method selected from the group consisting of inductively coupled plasma mass spectrometry, inductively coupled plasma atomic emission spectrometry, flame atomic absorption spectrometry, graphite oven atomic absorption spectrometry and spectrophotometry so as to obtain the content of elements in the tungsten-based sample.
Description
Technical field
The present invention relates to a kind of detection method with sedimentation method for separating and a kind of tungsten base class sample cleared up of tungsten base class sample.Specifically, the present invention relates to a kind ofly adopting microwave and nitric acid to clear up method and a kind of method that solution after clearing up is detected of tungsten base class sample under the high-pressure sealed condition.
Background technology
Tungsten and alloy thereof are one of important functional material very during modern industry, national defence and new and high technology are used, and are widely used at numerous areas such as Aero-Space, atomic energy, boats and ships automobile, electric, petrochemical complex, metal processing, device fabrication and war industrys.Tungsten is mainly used to produce wimet and ferrotungsten, can make cutter, automobile crane cylinder barrel, gas turbine, radiation shield, electron tube, metal surface hardened material, pigment dye, illuminating equipment, heat-resisting steel and make firearms, satelite rocket, aircraft naval vessel etc.Along with economic development and scientific-technical progress, the tungsten range of application constantly enlarges, and kind is increasing, has greatly satisfied the needs of economic construction and national defense and military.
Tungsten is a refractory metal, and hardness is big, density is high, elevated temperature strength is good.Be difficult under the normal temperature being corroded, can be dissolved in the acid mixture of nitric acid and hydrofluorite, be dissolved in acid mixture and separate out with the wolframic acid precipitation form afterwards by acid, alkali and chloroazotic acid.
Tungsten carbide (WC, Wolfram Carbide) is a primary raw material of producing wimet, and hardness and adamas are close.Metal tungsten powder and carbon black are mixed in proportion, and the graphite boat of packing into makes tungsten carbide with carbon-tube oven or the charing at a certain temperature of high medium-frequency induction furnace, ball milling, screening.Carbon atom embeds tungsten metal lattice gap and does not destroy original metal lattice, forms interstitial solid solution, also claims calking (or insertion) compound.Tungsten carbide is suitable at high temperature to carry out machining, can make cutting tool, furnace construction material, jet engine, gas turbine etc.Pure tungsten carbide is frangible, can mix a little amount of titanium, cobalt etc. to reduce fragility; Also often add titanium carbide, tantalum carbide or its potpourri to improve the antiknock ability.The tungsten carbide stable in properties is insoluble to hydrochloric acid, nitric acid, sulfuric acid, is dissolved in the acid mixture of nitric acid and hydrofluorite.
Because high concentration tungsten easy form precipitation with wolframic acid in acid medium is separated out, so for the solution manufacturing method of clearing up high concentration tungsten sample with the molten wet method of acid, there are two kinds of distinct methods in the prior art, promptly, the method of precipitation or extract and separate tungsten basal body, and the method for complexing to avoid the tungsten basal body precipitation to separate out.
Only just adopt with regard to the method for precipitate and separate tungsten basal body of constructed route with the present invention, prior art is to open wide the suspension solution of in the system tungsten base class sample being cleared up and obtained separating out the wolframic acid precipitation in the mode of agent combination such as hydrofluorite-nitric acid, hydrogen peroxide, hydrogen peroxide-nitric acid at electric hot plate, to suspension solution shift, after the operational processes such as dilution and constant volume, come the separating tungsten matrix by modes such as natural placement, gravity settling, filtration or centrifugings again, to overcome the interference of high concentration tungsten.This type of methods analyst flow process is oversize, operates very loaded down with trivial detailsly and complicated, and reagent dosage is big, detects the cost height, and hand labor intensity is big.In addition, it is slow that these class methods form the grain growth speed of wolframic acid precipitation, deposit seed is tiny, the space is bigger between the particle, the sedimentation that not only is not easy to reunite separates with solution, and easy residual element to be measured in the suspension that forms when Specimen eliminating, and also easily causes wolframic acid particle and element to be measured formation co-precipitation in subsequently solution dilution constant volume and precipitate and separate link, thereby cause element recovery rate to be measured lower, testing result is inaccurate.
In addition, in the method for prior art, only have the agent combination of hydrofluorite-nitric acid can clear up samples such as tungsten carbide, tungsten effectively fully, agent combination such as remaining hydrogen peroxide, nitric acid, hydrogen peroxide-nitric acid electric hot plate open wide clear up under the system invalid to clearing up of samples such as tungsten carbide.Though hydrofluorite-nitric acid combination can be cleared up sample, but because hydrofluorite is to the detecting instrument seriously corroded, therefore require detecting instrument must use the parts of unconventional ability HF corrosion instead, use this base part to cause the detection performance of analytical instrument seriously to descend usually, further had a strong impact on precision, sensing range and the accuracy of measurement result.In addition, hydrofluorite is very severe to the erosion of glass container and human body.In addition, utilize when clearing up sample in the unlimited system of hydrofluorite on electric hot plate, silicon combines with hydrofluorite and forms SiF
4Volatilization is overflowed, so can not be used to detect the Si element.
According to prior art, use HF-HNO earlier
3Decomposing metal tungsten or tungsten carbide coupon add behind the nitric acid evaporate to dryness once more then again, so repeatedly add the nitric acid operation of evaporate to dryness then repeatedly, impel tungsten to separate out with the form of wolframic acid precipitation, measure filtrate with ICP-AES after the isolated by filtration.This method complex operation, sense cycle is long, and reagent dosage is big, thereby has increased blank background, does not use HClO
4Deng higher boiling reagent, thereby can't drive most hydrofluorite, washing wolframic acid precipitation not yet in effect, being adsorbed element can not be influenced the recovery by wash-out.
In a word, tungsten base class samples such as still unresolved tungsten carbide of prior art and tungsten clears up the technical barrier that detects with element.
Summary of the invention
Be directed to the problems that exist in the prior art, the invention provides a kind of method that tungsten base class sample is cleared up.Digestion procedure of the present invention utilizes microwave technology, only use measuring a small amount of nitric acid of disturbing effect minimum, under high-pressure sealed condition, utilize the micro-wave digestion sample synchronously or in succession, microwave radiation rapid precipitation separating tungsten matrix and microwave washing wolframic acid precipitation are to be reduced to the sample solution of element loss to be measured, thereby realized tungsten carbide, tungsten such as tungsten or wimet Base Metal or alloy type sample efficient, fast, Specimen eliminating completely, separation and washing that the wolframic acid precipitation is separated out and precipitated, need not solution is shifted, dilution, operations such as constant volume, omitted and carried out centrifugal precipitation, sedimentation or filtration etc. separate step, directly the solution to microwave treatment detects, thereby accurately detects tungsten carbide, tungsten or wimet etc. are Fe in the metal or alloy class sample of main matrix composition with tungsten, Mn, Mg, Si, Co, Ni, V, As, Ti, Mo, Nb, Cr, Zn, Cu, constants such as Ta, trace, the content of trace element.
Clearing up with sedimentation method for separating of tungsten base class sample of the present invention may further comprise the steps: get tungsten base class sample in container, in container, add entry and nitric acid, container is airtight, by the staged heating mode sample is carried out micro-wave digestion and sedimentation separation, restart the microwave washing precipitation again drop near the boiling point of water at solution temperature after, thereby obtain detecting used sample solution and wolframic acid precipitation.
According to the present invention, described tungsten base class sample is for being the metal or alloy class sample of main matrix composition with tungsten, comprises at least a in tungsten carbide, tungsten and the wimet.Preferably, when the quality of sample was 0.1000g～0.5000g in adding container, the amount that adds the nitric acid in the container was 4.0mL～10.0mL, and wherein, the mass percent concentration of described nitric acid can be 65%～68%.The water yield that adds in container can be 15.0～25.0mL.
According to the present invention, the pressure in micro-wave digestion and the settling process in the container is arranged on below the 800psi, and described micro-wave digestion and sedimentation separation step comprise: in 3～5min the solution in the container is warming up to 170～190 ℃, and is incubated 8～12min; In 1～2min, the solution in the container is warming up to 200～220 ℃ and be incubated 1～3min then; After closing microwave and cooling solution to 95～105 ℃, open again microwave heat up behind 0.5～1min to solution temperature be 115～125 ℃, and be incubated 3～5min.
The present invention also provides a kind of method that detects the impurity content in the tungsten base class sample, said method comprising the steps of: the solution for preparing tungsten base class sample as mentioned above; Utilize in inductively coupled plasma mass spectrometry, ICP-AES, flame atomic absorption spectrometry, GFAAS (graphite furnace atomic absorption spectrometry), the spectrophotometric method at least a method that the constituent content in the tungsten base class sample is measured.
According to the present invention, can analyze the content of at least a element among the Ta in the sample solution, Fe, V, Ti, Mn, Mg, Si, Co, Ni, As, Nb, Cr, Zn, Cu, the Mo.
According to the present invention, microwave reaction finishes the back and directly the sample solution in the microwave container is measured.
Embodiment
The method that the object of the present invention is to provide impurity element in the preparation method of tungsten basal body metal or alloy class sample detection solution such as a kind of tungsten carbide, tungsten, wimet and the test sample or add the content of element.The method of the invention can make tungsten basal body separate with detection solution automatically with the wolframic acid precipitation form and precipitate the loss that can not cause element to be measured, avoids high concentration tungsten basal body interference impurity element and influences measurement result; And the Specimen eliminating solution of the present invention preparation is suitable for various modern analytical instrument and chemical analysis method to detecting the technical requirement of solution, can adopt analytical approachs such as ICP-AES, GF-AAS, F-AAS, ICP-MS and photometry, electrochemical process to analyze, can detect concentration range Co, the Ni in Fe, Mn, Mg, Si, V, As, Ti, Mo, Nb, Cr, Zn, Cu element and 0.001%～6% scope, Ta element in 0.001%～1% scope in the tungsten basic pattern product of various purity.
The method for preparing sample solution according to the embodiment of the invention has only been used nitric acid.More particularly, according to the method for preparing sample solution of the embodiment of the invention at existing HF-HNO
3Electric hot plate opens wide to be cleared up on the system basis, abandons using Specimen eliminating reagent hydrofluorite the most key in the former method, has avoided introducing a series of unfavorable factors that hydrofluorite causes, as the corrosion instrument, can not to be used to measure elements Si, testing result inaccurate etc.
The present invention is owing to introduced microwave technology, under high-pressure sealed and specific controlled variable, only add nitric acid and realized that promptly the quick and complete of sample such as tungsten carbide, tungsten and wimet clear up, and uncombined carbon or carbonide complete oxidation are decomposed, do not have residual any sample insolubles; Though the present invention adopts micro-wave digestion, but be different from conventional microwave sample digestion procedure, usually micro-wave digestion just utilizes the thermal effect of microwave, but the present invention is under high-pressure sealed hydrothermal condition, the electromagnetic radiation of comprehensive utilization microwave field, heating, effects such as stirring, automatically finishing the high concentration tungsten basal body with stored program control system synchronously or afterwards in the Specimen eliminating reaction separates out with the wolframic acid form, precipitation crystal grain is grown up fast, deposit seed is reunited and sedimentation separation fast, the ageing of precipitation high temperature, the operation of a whole set of precipitate and separate tungsten basal body such as washing of precipitate is different from existing electric hot plate and opens wide the generation and the manually-operated that separates of clearing up wolframic acid precipitation in the system.
Prior art is only used the reagent and the combination thereof of nitric acid or other no hydrofluorite, and high concentration tungsten basal body samples such as tungsten carbide, wimet are cleared up the equal extreme difference of effect.For example use common agents such as nitric acid, hydrogen peroxide, sulfuric acid, phosphoric acid, hydrochloric acid and acid mixture thereof all can't clear up tungsten carbide, just can clear up sample after must adding hydrofluorite.And add acid, evaporate to dryness mode with repeated multiple times and separate out the wolframic acid precipitation, tungsten separates incomplete and element loss to be measured is big, the recovery is low, multiple influence factor stack finally has a strong impact on testing result, former method complex operation, sense cycle is long, and the big and skilled operation level of hand labor intensity can influence testing result.
Sample solution preparation manipulation simple and fast of the present invention, it is minimum to the influence that the possibility of result causes that operating personnel grasp the proficient of method, the present invention only needs the artificial operation that claims sample, adds entry and nitric acid of carrying out, operations such as all the other Specimen eliminatings, precipitate and separate and washing are all controlled automatically according to preset program and are finished, and operations such as the solution behind the microwave reaction also need not manually to shift, dilution, constant volume, filtration are directly measured with the ICP-AES method and are got final product.Therefore, the present invention can accurately control and each operation link of repetition, improved the technical performance index such as accuracy, precision of testing result greatly, and labour intensity reduces, operation steps reduces, round of visits shortens, analysis speed improves, in conjunction with instrument analytical methods such as ICP-AES, more can satisfy check and analysis control is carried out in modern industry fast pace production scene to the quality of raw material, sample needs with the interior whole analysis process that can easily finish sample solution preparation and element detection in 1～1.5 hour.
Below in conjunction with embodiment clearing up with sedimentation separation and detection method of tungsten base class sample of the present invention further described.
The method that detects the used sample solution of samples such as tungsten carbide, tungsten, wimet according to preparation of the present invention may further comprise the steps: taking by weighing tungsten carbide, tungsten or wimet etc. is that the metal or alloy sample of main matrix composition is in container with tungsten, quantitatively add entry and nitric acid, carry out microwave high pressure airtight digestion sample, and with the microwave radiation rapid precipitation with separate wolframic acid (H
2WO
4), and use the microwave washing precipitation, cooling solution to room temperature promptly prepares sample detection solution.
After tungsten carbide prepared in accordance with the present invention, tungsten, wimet etc. with tungsten are the used test sample solution of the metal or alloy class sample of main matrix composition, utilize the ICP-AES method simultaneously or measure one by one to elements such as the Fe in the sample solution, Mn, Mg, Si, Co, Ni, V, As, Ti, Mo, Nb, Cr, Zn, Cu, Ta.Used ICP-AES can fly your iCAP6300 of company type of generation and compose direct-reading inductively coupled plasma atomic emissions spectrometer (being ICP-AES) entirely for U.S.'s match is silent.
Micro-wave digestion instrument of the present invention can be microwave airtight digestion jar, but is not limited to this, also can use acidproof withstand voltage other container that is suitable for microwave heating.
In an embodiment of the present invention, solution behind the microwave reaction no longer shifts, dilution and constant volume, the sample solution final volume is exactly the water of adding before the reaction and the summation of nitric acid, therefore require water also must accurately quantitatively add, and the addition of water is determining the dilution ratio of solution to a great extent, according to the consumption of target setting water such as the sensitivity of follow-up selected instrumental analysis or chemical analysis method, detection limit, acidity requirement.In embodiments of the present invention, the adding mode of described water is for adopting along the mode of chamber wall flushing, amount of water is 15.0～25.0mL, add nitric acid dosage, the cumulative volume of prepared sample solution is 19.0～35.0mL, but be not limited to this, can suitably increase or reduce the water volume that adds according to the needs of analytical approach.Certainly, also can be with solution dilution, be settled to 50～100mL.
The addition of described nitric acid is according to the quality decision of tungsten base testing sample, and for the sample of 0.1000g～0.5000g, the nitric acid amount that adds in container is 4.0mL～10.0mL, and the mass percent concentration of described nitric acid is 65%～68%.
According to method of the present invention, pressure in micro-wave digestion and the settling process in the container is arranged on below the 800psi, described micro-wave digestion and sedimentation separation step comprise: in 3～5min the solution in the container is warming up to 170～190 ℃, and is incubated 8～12min; In 1～2min, the solution in the container is warming up to 200～220 ℃ and be incubated 1～3min then; After closing microwave and cooling solution to 95～105 ℃, open again microwave heat up behind 0.5～1min to solution temperature be 115～125 ℃, and be incubated 3～5min.The microwave phase one has finished Specimen eliminating and has begun to separate out the wolframic acid precipitation; By microwave subordinate phase higher temperature and microwave radioradiation, utilize " the alternating electromagnetic field generated electromagnetic agitation of microwave ", realization wolframic acid deposit seed is grown up fast, avoid element to be measured to be wrapped, precipitation is more closely reunited (or caking) and is fallen to container bottom, separate fully with solution to be measured, rocking of medium dynamics can not cause precipitating dispersion or being suspended in the solution yet.High temperature guarantees that more the carbon of various forms is decomposed by complete oxidation simultaneously; Solution temperature drops near water boiling point (95～105 ℃), restart microwave and may be reentered solution by the element wash-out to be measured of wolframic acid co-precipitation or absorption by the phase III, improve element recovery rate and testing result accuracy, this step is similar to the wash-out and the aging step of traditional chemical precipitate and separate.
All micro-wave digestions and sedimentation flow process are all carried out under the airtight hydrothermal condition of microwave high pressure, and Specimen eliminating, wolframic acid precipitation are separated out and the reunion sedimentation separation that precipitates all is to carry out under the state of temperature that raises step by step with step-wise manner synchronously; Only after Specimen eliminating and precipitate and separate have been finished, the microwave washing of precipitate reaction of carrying out in succession is to carry out in temperature presents the process of obvious downtrending.Especially it may be noted that, be different from common microwave sample digestion procedure, the present invention has realized clearing up fully of indissoluble sample with a kind of simple reagent with microwave, be that more the present invention is under high-pressure sealed hydrothermal condition, the radiation of comprehensive utilization microwave electromagnetic, heating, effects such as stirring, automatically finishing the high concentration tungsten basal body with stored program control system synchronously or afterwards in the Specimen eliminating reaction separates out with the wolframic acid form, precipitation crystal grain is grown up fast, deposit seed is reunited and sedimentation separation fast, the ageing of precipitation high temperature, the operation of a whole set of precipitate and separate tungsten basal body such as washing of precipitate is different from existing electric hot plate fully and opens wide the generation of clearing up wolframic acid precipitation in the system and manually-operated such as separate.
Method of the present invention comprises that also washing wolframic acid precipitation is to reduce element loss to be measured.The washing of precipitate operation that improves element recovery rate is to close microwave after preceding two temperature rise periods finish, treat that solution temperature drops to about the boiling point of water, restart microwave heating and keep solution in the temperature that is approximately full response flow process intensification process 2/3rds, utilize the microwave electromagnetic radiation to be entered solution, be cooled to room temperature at last by the element to be measured of wolframic acid precipitation absorption wash-out again.Preparation process is no longer carried out precipitate and separate operations such as conventional solution transfer, dilution, constant volume, natural subsidence, centrifugal or filtration.Microwave reaction finishes the back and directly the sample solution in the microwave container is measured.
The method of impurity content may further comprise the steps in the metal or alloy class sample that a kind of detection according to the present invention is main matrix composition with tungsten: clear up and sedimentation separation tungsten basic pattern product preparation tungsten basic pattern product solution according to clearing up of tungsten basic pattern product of the present invention and sedimentation method for separating; Utilize one or more methods in inductively coupled plasma mass spectrometry (ICP-MS), ICP-AES (ICP-AES), flame atomic absorption spectrometry (F-AAS), GFAAS (graphite furnace atomic absorption spectrometry) (GF-AAS), spectrophotometric method and the electrochemical process that this sample solution is measured, to obtain the content of each element such as Fe, Mn, Mg, Si, Co, Ni, V, As, Ti, Mo, Nb, Cr, Zn, Cu, Ta in the metal or alloy class sample that tungsten carbide, tungsten or wimet etc. are main matrix composition with tungsten.
Embodiment 1
Clearing up and sedimentation separation of tungsten sample
Take by weighing 0.1000g tungsten powder sample (FWI-I, W＞99.9%, Zhuzhou Hard Alloy Plant is produced) (hereinafter being called sample No. 1) in micro-wave digestion jar in, accurately add 15.0mL water along interior jar of tank skin quantitatively in the mode of washing earlier, and the sample that tank skin may attach all washed, add red fuming nitric acid (RFNA) 4.0mL then.Put outer jar then, build lid and tighten, to guarantee good seal with torque spanner.By the instrumentation step good seal outer canned gone into microwave and clear up in the stove, connect temperature, pressure transducer.Carry out micro-wave digestion by set micro-wave digestion heating schedule.The microwave reaction modes that present embodiment adopt to divide three ladder steps to heat up with the slope, pressure control are below 800psi (1psi=6.895KPa), and the microwave heating program is set to material in the container is warming up to 170 ℃ and be incubated 8min with 3min; 1min is warming up to 200 ℃ and be incubated 1min then; After closing microwave and cooling solution to 95 ℃, open microwave again and be warming up to 115 ℃ and be incubated 3min with 0.5min.
After the microwave reaction EOP (end of program), wait for that solution is to room temperature in the air cooling jar, take out the counteracting tank and the nut of in fuming cupboard, slowly outwarding winding and discharge surplus pressure, be deposited in container bottom through the resulting wolframic acid of microwave reaction in the container, the settled solution on precipitation top is the check and analysis sample solution that makes with precipitating complete tight agglomeration.
Detect tungsten Specimen eliminating solution with ICP-AES
Prepared tungsten Specimen eliminating solution as detection means, directly, simultaneously carries out assay determination to Fe, Mn, Mg, Si, Co, Ni, V, As, Ti, Mo, Nb, Cr, Zn, Cu, the Ta element that contains in the sample with ICP-AES.The ICP-AES determination step carries out basically in the usual way, and this method is removed owing to the complete precipitated separation of tungsten basal body, element to be measured and small amount of residual nitric acid are only arranged in the solution, form simple, need not to adopt matrix coupling, interior calibration just waiting method that interference is proofreaied and correct, promptly when the working curve standard solution of preparation assay method, be medium with nitric acid and get final product according to the mixed standard solution that sensing range is prepared each element debita spissitudo to be measured on demand.The detectable concentration scope of present embodiment working curve is: 0.001%～1% Fe, Mn, Mg, Si, V, As, Ti, Mo, Nb, Cr, Zn, Cu, and 0.001%～6% Co, Ni, Ta.
Embodiment 2
Sample to be cleared up is 0.5000g tungsten powder sample (Zhuzhou Hard Alloy Plant is produced for FWI-I, W＞99.9%) (hereinafter being called sample No. 2), adds 25.0mL water and 10.0mL red fuming nitric acid (RFNA), and microwave procedure: 5min is warming up to 190 ℃ and be incubated 12min; 2min is warming up to 220 ℃ and be incubated 3min; Behind the cooling solution to 105 ℃, restart microwave 1min and be warming up to 125 ℃ and be incubated 5min.In addition, clear up this tungsten sample and detect supernatant liquor by the method identical with ICP-AES with embodiment 1.
Embodiment 3
Sample to be cleared up is 0.1000g tungsten carbide sample (FWC-1, WC＞99.8% hereinafter are called sample No. 3), adds 20.0mL water and 5.0mL red fuming nitric acid (RFNA), and microwave procedure: 4min is warming up to 180 ℃ and be incubated 10min; 2min is warming up to 210 ℃ and be incubated 2min; Behind the cooling solution to 95 ℃, restart microwave 1min and be warming up to 120 ℃ and be incubated 4min.In addition, clear up this tungsten carbide sample according to the method identical and carry out the ICP-AES detection with the method for embodiment 1.
Embodiment 4
Sample to be cleared up is 0.5000g tungsten carbide sample (FWC-1, WC＞99.8% hereinafter are called sample No. 4), adds 20.0mL water and 9.0mL red fuming nitric acid (RFNA).In addition, clear up this tungsten carbide sample according to the method identical and carry out the ICP-AES detection with the method for embodiment 1.
Embodiment 5
Sample to be cleared up is 0.2500g tungsten carbide sample (FWC-2, WC＞99.7% hereinafter are called sample No. 5), adds 25.0mL water and 8.0mL red fuming nitric acid (RFNA).In addition, clear up this tungsten carbide sample according to the method identical and carry out the ICP-AES detection with the method for embodiment 1.
Embodiment 6
Sample to be cleared up is 0.2000g wimet sample (hereinafter being called sample No. 6), adds 15.0mL water and 6.0mL red fuming nitric acid (RFNA).In addition, clear up this wimet sample according to the method identical and carry out the ICP-AES detection with the method for embodiment 1.
Embodiment 7
Sample to be cleared up is 0.4000g wimet sample (hereinafter being called sample No. 7), adds 25.0mL water and 9.0mL red fuming nitric acid (RFNA).In addition, clear up this wimet sample according to the method identical and carry out the ICP-AES detection with the method for embodiment 1.
Embodiment 8
Sample to be cleared up is 0.3000g tungsten carbide sample (the regeneration tungsten carbide hereinafter is called sample No. 8), adds 20.0mL water and 8.0mL red fuming nitric acid (RFNA).In addition, clear up this tungsten carbide sample according to the method identical and carry out the ICP-AES detection with the method for embodiment 1.
Embodiment 9
Take by weighing 0.1500g tungsten carbide sample (the regeneration tungsten carbide hereinafter is called sample No. 9), add 15.0mL water and 7.0mL red fuming nitric acid (RFNA).In addition, clear up this tungsten carbide sample according to the method identical and carry out the ICP-AES detection with the method for embodiment 1.
Embodiment 10
Take by weighing 0.4500g tungsten carbide sample (hereinafter being called sample No. 10), add 20.0mL water and 10.0mL red fuming nitric acid (RFNA).In addition, clear up this tungsten carbide sample according to the method identical and carry out the ICP-AES detection with the method for embodiment 1.
By embodiment 1-10, a plurality of type tungsten carbides, tungsten, wimet sample have been selected, with the performance of different test condition checking the present invention to preparation sample solutions such as the clearing up of actual sample, precipitate and separate.The present invention is very good to the clearing up of all kinds of samples, precipitate and separate and clean result, is all cleared up the noresidue sample completely by the not labile uncombined carbon of the method for prior art or other carbonide.Wolframic acid precipitation tight agglomeration (or caking) also falls to container bottom, separates fully with solution, and the rocking of medium dynamics can not stirred precipitation yet and be made it floating or be suspended in the solution, and the solution clear has satisfied each class methods fully and detected needs.
Show that thus the present invention has good and extensive applicability has the good ability of clearing up for sample, prepared sample solution is fit to the requirement that the modern precision analytical instrument detects.
Embodiment 11
No. 4 tungsten carbides, No. 6 wimet and No. 8 regeneration tungsten carbide actual production samples are carried out 8 the independently preparation and the assay determinations of test sample solution respectively, 8 measurement results are carried out statistical treatment, and (RSD) assesses precision of the present invention according to relative standard deviation.Measurement result sees Table 1.
Table 1 analytical approach precision (n=8) (%)
Table 1 as seen, the element of result＞1.0%, its RSD＜1%; 0.01%-1.0% element as a result, RSD＜4%; 0.001%-0.01% element as a result, RSD＜5%.Precision is good, easy grasp simple to operation, and except that artificial title sample, add the acid, all the other preparation process are automatically performed according to setting program by microwave digestion system, the sample solution measurement result unanimity of independent operation preparation repeatedly, repeatability, repeatability are good.
Embodiment 12
Detect the content of W element in the 1-10 sample solution prepared among the embodiment 1-10 respectively with the ICP-AES method, the residual content of W element in the solution per sample is in order to the effect of assessment precipitate and separate tungsten of the present invention.Measurement result sees Table 2.
The efficient (%) of table 2 sample solution preparation method precipitate and separate tungsten basal body
As seen from Table 2, the W content maximum that residues in the sample solution is no more than 1.75%, the effect that shows matrix separation tungsten of the present invention is obvious, the tungsten basal body overwhelming majority in the sample is separated out separated going out with precipitation form, the W that residues in the solution is few, thereby has eliminated influence factors such as the matrix effect that matrix tungsten may cause, spectrum interference.
Embodiment 13
The recovery to the standard substance that adds is measured, the concentration value of designed element in the primary sample is cleared up and measured to the first step, second step is the artificial known normal concentration value that adds respective element in primary sample, the concentration value of respective element after the artificial adding standard was cleared up and measured to the 3rd step, then that the 3rd pacing is fixed concentration value deducts the concentration value that the first step is measured, difference is again divided by the artificial normal concentration value that adds of second step, can calculate and add the target recovery, common accuracy in order to scaling method.
Present embodiment has carried out determination of recovery rates to No. 5 samples and No. 7 samples, because analytical error influence, the recovery is a value range, usually for microanalysis, it is qualified to be between the recovery is controlled at 80%～120%, and as shown in Table 3, the recovery of method of the present invention is between 90.0%～114.0%, show that the standard substance that is added all can contamination-freely reclaim fully in free of losses, analysis result has higher accuracy and reliability.
Table 3 recovery test (%)
According to the method for preparing sample solution of the embodiment of the invention, its advantage is:
(1) utilize microwave technology to come disposablely to finish Specimen eliminating, separate out wolframic acid precipitation, reunion sedimentation and reactions such as precipitation separation and washing precipitation innovatively, faster efficient and thoroughly complete, the indissoluble material that comprises carbonide, uncombined carbon etc. is all cleared up fully enters solution, do not have any undissolved residue, solved tungsten carbide and cleared up a difficult problem.And only use a spot of nitric acid, do not use corrosivity hydrofluorite, handling safety and pieces of inspection equipment do not had specific (special) requirements, instrument there is not corrosive attack, can use the conventional high performance unit of using,, improve the detection performance as adopting the best of breed parts of concentric atomizer of glass and quartzy eddy flow fog chamber among the ICP-AES, can give full play to instrument performance, and the element silicon in the energy test sample.
(2) broken through the mode of traditional precipitate and separate and washing, adopt the diverse microwave precipitation of a kind of technology such as gravity settling, filtration or centrifuging to separate the wolframic acid precipitation with washing technology with common employing, not only realized the automatic control of process, reduced operation link, the sample solution preparation can be finished in 1-1.5 hour with detection, and had improved result's accuracy.
(3) be different from and conventional prepare the method for sample solution with microwave digestion technology, the present invention also utilizes synchronously microwave to finish wolframic acid precipitation rapid subsidence under high-pressure sealed hydrothermal condition and separates and washing when utilizing microwave technology to carry out Specimen eliminating; Specimen eliminating and precipitate and separate whole process are carried out in closed system, and reagent is without any loss, and the sample detection liquor capacity is exactly the summation that adds entry and nitric acid when clearing up; Precipitate and separate tungsten basal body efficient height of the present invention in addition, residual W concentration is no more than 1% in the sample solution, having eliminated tungsten basal body effect and spectrum fully disturbs, prepared sample solution is formed simple, only residual a small amount of nitric acid, total dissolved solid (TDS) is extremely low, can set the sample solution volume neatly to reach the purpose of the element to be measured of enrichment simply and effectively according to continued selected analytical approach performance and needs.The present invention has omitted and precipitation is carried out centrifugal, sedimentation or filtration etc. has separated operation, directly microwave treatment solution is detected, and step not only simplifies the operation, shorten analytical cycle, improve analysis speed, the more important thing is enrichment element to be measured, improved trace, trace element testing result accuracy.Certainly, also can the sample solution of preparation suitably be diluted.
(4) separated fully substantially owing to tungsten basal body, residual quantity less than 1%, and this is a kind of to measuring simple experiment of disturbing effect minimum only to have used a small amount of nitric acid, and technical indicator aspects such as the density of prepared sample solution, viscosity, total salt amount, blank, matrix have satisfied the requirement of instrument detecting method such as ICP-AES, GF-AAS, F-AAS, ICP-MS and chemical analysis methods such as spectrophotometric method, electrochemical process better.
Although illustrated and described the present invention, the invention is not restricted to this in conjunction with exemplary embodiment.Under the situation that does not break away from spirit of the present invention and instruction, can make amendment and be out of shape embodiment.Scope of the present invention is limited by claim and equivalent thereof.
Claims (9)
1. clearing up and sedimentation method for separating of a tungsten base class sample is characterized in that said method comprising the steps of:
Get tungsten base class sample in container, in container, add entry and nitric acid, container is airtight, by the staged heating mode sample is carried out micro-wave digestion and sedimentation separation, restart the microwave washing precipitation again drop near the boiling point of water at solution temperature after, thereby obtain detecting used sample solution and wolframic acid precipitation.
2. method according to claim 1 is characterized in that described tungsten base class sample for being the metal or alloy class sample of main matrix composition with tungsten, comprises at least a in tungsten carbide, tungsten and the wimet.
3. when method according to claim 1, the quality that it is characterized in that sample in adding container were 0.1000g～0.5000g, the amount that adds the nitric acid in the container was 4.0mL～10.0mL.
4. method according to claim 3, the mass percent concentration that it is characterized in that described nitric acid is 65%～68%.
5. method according to claim 1 is characterized in that the water yield that adds is 15.0～25.0mL in container.
6. method according to claim 1, it is characterized in that the pressure in the container is arranged on below the 800psi in micro-wave digestion and the settling process, described micro-wave digestion and sedimentation separation step comprise: in 3～5min the solution in the container is warming up to 170～190 ℃, and is incubated 8～12min; In 1～2min, the solution in the container is warming up to 200～220 ℃ and be incubated 1～3min then; After closing microwave and cooling solution to 95～105 ℃, open again microwave heat up behind 0.5～1min to solution temperature be 115～125 ℃, and be incubated 3～5min.
7. method that detects the impurity content in the tungsten base class sample is characterized in that said method comprising the steps of:
According to the solution for preparing tungsten base class sample as claim 1 any described method of claim to the claim 6;
Utilize at least a method in inductively coupled plasma mass spectrometry, ICP-AES, flame atomic absorption spectrometry, GFAAS (graphite furnace atomic absorption spectrometry), the spectrophotometric method that the constituent content in the tungsten base class sample is measured.
8. method according to claim 7 is characterized in that middle Ta, Fe, V, Ti, Mn, Mg, Si, Co, Ni, As, Nb, Cr, Zn, the Cu to sample solution, the content of at least a element among the Mo analyzes.
9. method according to claim 7 is characterized in that microwave reaction finishes the back and directly the sample solution in the microwave container measured.
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