CN102928271A - Sample treatment method for measuring niobium, tungsten and zirconium in steel - Google Patents
Sample treatment method for measuring niobium, tungsten and zirconium in steel Download PDFInfo
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- CN102928271A CN102928271A CN2012104080985A CN201210408098A CN102928271A CN 102928271 A CN102928271 A CN 102928271A CN 2012104080985 A CN2012104080985 A CN 2012104080985A CN 201210408098 A CN201210408098 A CN 201210408098A CN 102928271 A CN102928271 A CN 102928271A
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Abstract
The invention provides a sample treatment method for measuring niobium, tungsten and zirconium in steel. The method comprises the following steps of: 1) preparing a sample acid by mixing 1 part of 1.84g/mL sulfuric acid and 4 parts of deionized water; 2) preparing a 4g/L ammonium oxalate complexing agent; 3) dissolving the sample: namely weighing 0.1000 to 0.2000g of steel scrap sample, putting the scrap sample into a conical flask, adding 20 to 25mL of sample acid, heating, dissolving, dropping nitric acid to oxidize until the solution is clarified, continuously heating until smokes of the sulfuric acid come out, precipitating salts, taking down the salts, slightly cooling, adding 10 to 15mL of ammonium oxalate complexing agent, heating, dissolving and taking the salts, cooling to room temperature, transferring the solution into a 50mL volumetric flask, diluting the solution to the scale by using deionized water, and uniformly mixing. By the method, hydrofluoric acid is not used, and the accuracy of an analysis result is not influenced; phosphoric acid is not used, and phosphorus pollution of the system is avoided; and moreover, the introduction of lots of salts is controlled, so that the matrix effect interference, spectral line interference and background interference are reduced, and blockage of an atomization system and an inductively coupled plasma (ICP) torch is avoided.
Description
Technical field
The invention belongs to field of measuring technique, relate to the disposal route of measuring the sample of niobium, tungsten, zirconium in the steel, especially a kind of sample processing method that can be applicable to niobium, tungsten, zirconium in the ICP-AES analysis steel.
Background technology
Niobium, tungsten, zirconium are alloying elements in the steel, and what have a significant impact the character of steel niobium, tungsten, zirconium content.Niobium can make the grain refinement of steel, reduces superheated susceptivity and the temper brittleness of steel; Tungsten can improve the creep strength of steel, is again the powerful accelerator of carbonide in the steel; Zirconium can improve intensity and the hardness of steel, especially can improve steel creep rupture strength, improve the welding performance of steel etc.Therefore, to niobium in the steel, tungsten, zirconium content fast, Accurate Determining is particularly important.
The content of niobium, tungsten, zirconium is usually lower in the steel, and traditional analytical approach is photometry.Niobium often adopts GB/T 223.39-94 steel and alloy chemical analysis method chlorosulfophenol S spectrphotometric method for measuring niobium amount; Tungsten adopts GB 223.66-89 thiocyanate-chlorpromazine hydrochloride-chloroform extraction spectrphotometric method for measuring tungsten amount; Zirconium adopts the p-bromine mandelic acid precipitate and separate of GB/T 223.30-94 steel and alloy chemical analysis method-arsenazo Ⅲ Spectrophotometric Determination of Zirconium amount.Pertinent literature has " the quick spectrophotometric method of niobium in the low alloy steel " (" Jiangxi Metallurgical " 6 phases in 2005) such as Wu Wanqin, Chen Guosong etc. " spectrophotometric Chemical Measurement method is measured trace amount Ti, molybdenum and tungsten simultaneously " (" metallurgical analysis " 5 phases in 1999), Dou Cheng etc. " titanium, molybdenum and tungsten in the genetic neural network SIMULTANEOUS DETERMINATION low alloy steel " (" physical and chemical inspection-chemical fascicle " 11 phases in 2008), this type of methods analyst time is long, complex operation, be difficult to satisfy modern enterprise to the research and production check sample fast, the requirement of accurate analysis.
Inductively coupled plasma atomic emission (ICP-AES) analyzes that to have an accuracy good, the method detection limit is low, the wide dynamic range of measuring, matrix effect is little, precision is high, but the characteristics such as multielement simultaneous determination are applied to the analysis of constant, micro constitutent in iron and steel and the various material more and more widely.Existing people utilizes this technology to measure niobium in the steel, tungsten, zirconium content, as: after Zhang Guang etc. " the ICP-AES method is measured zirconium and niobium in the low alloy steel simultaneously " (" metallurgical analysis " the 1st phase of the 24th volume in 2004) adopt the dilute sulfuric acid dissolution sample, through the sulphur phosphoric acid tartrate dissolved salts of smoldering, the decomposition sample has adopted mixture of sulfuric phosphoric acid to be fuming and has then introduced a large amount of P elements in the sample introduction system, causes sampling system phosphorus to pollute; Zhang Jiaxiang " the ICP method is measured the technical Analysis of micro-Nb in the steel " (the 3rd phase of " Sichuan non-ferrous metal " September in 2006) adopts hydrochloric acid, nitric acid, perchloric acid and the dissolving of hydrofluorite nitration mixture and emits the perchloric acid cigarette, the tartrate dissolved salts, owing to all needing to add a certain amount of hydrofluorite in the sample pretreating process, and all need to add approximately 2 gram tartrate dissolved saltses after every sample acid dissolving, analyze total dissolved solid (TDS) height in the test solution, easily cause the obstruction of atomization system and ICP torch.Said method all because of the defective of sampler-dissolving method, therefore is difficult to popularize in the research and production check.
Summary of the invention
The object of the invention is to overcome the existing deficiency of above-mentioned prior art, the sample processing method of niobium, tungsten, zirconium in a kind of measurement steel of well protection instrument sampling system is provided.
The present invention is achieved in that the sample processing method of niobium, tungsten, zirconium in this measurement steel may further comprise the steps:
1, the preparation of molten sample acid
Measure 100 mL sulfuric acid (density is as the sulfuric acid of 1.84 g/mL) take 100 mL measuring cups, fill it in 1 L beaker of 400 mL deionized waters along the glass bar impouring, stir and evenly mix gently with glass bar, after solution is cooled to room temperature, pour in the 1 L wide-mouth port grinding bottle, obtaining sulfuric acid concentration is sulfuric acid: water=1:4(1 part density is that the sulfuric acid of 1.84 g/mL mixes with 4 parts of deionized waters) the acid of molten sample, stand-by.
2, the preparation of ammonium oxalate complexing agent
Take by weighing 4.0 g ammonium oxalate in counter balance and be added in the 1 L beaker that fills 1000 mL deionized waters, with glass bar stir gently make its dissolve complete after, pour in the 1 L wide-mouth port grinding bottle, obtain concentration and be 4 g/L ammonium oxalate complexing agents, stand-by.
3. sample dissolving
Accurately weighing 0.1000～0.2000 g steel cuttings sample places conical flask, the molten sample acid of adding 20～25 mL (concentration is sulfuric acid: water=1:4), heating for dissolving on electric hot plate, dripping nitric acid oxidation to solution clarifies, continuing to be heated to sulfuric acid smolders, salt takes off after separating out, slightly cold, (concentration is 4 g/L) to add 10～15 mL ammonium oxalate complexing agents again, in taking off behind the heating for dissolving salt on the electric hot plate, be cooled to room temperature, move into again in the 50 mL volumetric flasks, be diluted to scale with deionized water, mix.
Sample processing method of the present invention is compared with prior art, has following beneficial effect:
1. avoided use hydrofluorite in the dissolution sample process, routine testing scientific research, production sample can adopt the standard quartz sampling system, need not to change HF acid resistant device again, in order to avoid reduce sensitivity of analytical method, impact analysis result's accuracy.
2. avoid use phosphoric acid in the dissolution sample process, avoided system's phosphorus to pollute.Thereby can not affect the testing of P elements in daily scientific research, the production sample.
3. every sample has only used the ammonium oxalate enveloping agent solution of the ammonium oxalate amount of solid that is equivalent to 0.04～0.06 g to dissolve the salt that sulfuric acid is smoldered and separated out in processing procedure, avoided the introducing of a large amount of salts, reduce total dissolved solid in the analysis test solution, thereby reduced the matrix effect interference; Spectral line disturbs and background interference; Avoided the obstruction of atomization system and ICP torch.
Embodiment
The present invention is described further below by embodiment.
Embodiment 1 adopts the present invention to the mensuration of niobium, tungsten, zirconium content in the middle-low alloy steel standard model.Concrete grammar is as follows:
1, the molten sample acid of preparation
Measure 100 mL sulfuric acid (density is as the sulfuric acid of 1.84 g/mL) take 100 mL measuring cups, it is filled in the 1 L beaker of 400 mL deionized waters along the glass bar impouring, stir and evenly mix gently with glass bar, after solution is cooled to room temperature, pour in the 1 L wide-mouth port grinding bottle, obtain molten sample acid, stand-by.
2, preparation ammonium oxalate complexing agent
Take by weighing 4.0 g ammonium oxalate in counter balance and be added in the 1 L beaker that fills 1000 mL deionized waters, with glass bar stir gently make its dissolve complete after, pour in the 1 L wide-mouth port grinding bottle, obtain concentration and be the ammonium oxalate complexing agent of 4 g/L, stand-by.
3, dissolved samples
Accurately take by weighing middle-low alloy steel (YSBC11217-94) 0.1000 g and place 125 ml conical flasks, (concentration is sulfuric acid: water=1:4), heating for dissolving to add the acid of the molten sample of 20 mL, drip nitric acid oxidation, continue to be heated to sulfuric acid and smolder, take off after salt is separated out, slightly cold, (concentration is 4 g/L) to add 10 mL ammonium oxalate complexing agents again, take off behind the heating for dissolving salt, be chilled to room temperature, move in the 50 mL volumetric flasks, be diluted to scale with deionized water, mix.
4, drawing curve
Take by weighing respectively 5 part of 0.1000 g high-purity iron powder, place respectively 125 ml conical flasks, (concentration is sulfuric acid: water=1:4) to add the acid of the molten sample of 20 mL, divide and get niobium, tungsten, zirconium mark liquid (content from low to high), heating for dissolving, drip nitric acid oxidation, continue to be heated to sulfuric acid and smolder, salt is separated out and is taken off, slightly cold, (concentration is 4 g/L), take off behind the heating for dissolving salt, is chilled to room temperature to add 10 mL ammonium oxalate complexing agents again, move into respectively in the 50 mL volumetric flasks, be diluted to scale with deionized water, mix, make series standard solution.As shown in table 1.
Table 1 standard series ω/%
5, instrument condition of work
Instrument: IRIS Advantage ER/S inductive coupling plasma emission spectrograph (U.S. TJA company).
The instrument condition of work is as shown in table 2.
Table 2 instrument condition of work
6, the precision of method, recovery checking
Choose 1 # sample, METHOD FOR CONTINUOUS DETERMINATION is 11 times respectively, calculates its relative standard deviation, and result of calculation shows: RSD≤2%, precision is good.For the accuracy of verification method, to do standard with the 1# sample and add recovery test, the recovery is between 96.2%～101.7%.As shown in table 3.
Table 3 recovery, precision
7, measure
At niobium 319.498 nm; Tungsten 207.911 nm; Under the zirconium 257.139 nm wavelength, measure at the working curve of drawing, the result is as shown in table 4.
Table 4 standard model measured value and standard value result contrast %
Above standard specimen use the present invention processes sample and is consistent with standard value by detecting the gained measurement result, all in national standard tolerance scope.
Embodiment 2 is the mensuration that adopts niobium, tungsten, zirconium content in the alloy steel sample of the present invention.Concrete grammar is as follows:
1, the molten sample acid of preparation (as embodiment 1)
2, preparation ammonium oxalate complexing agent (as embodiment 1)
3, dissolved samples
Accurately take by weighing 1# sample 0.2000g and place 125 ml conical flasks, (concentration is sulfuric acid: water=1:4), heating for dissolving to add the acid of the molten sample of 25 mL, drip nitric acid oxidation, continue to be heated to sulfuric acid and smolder, salt is separated out and taken off, and is slightly cold, (concentration is 4 g/L) to add 15 mL ammonium oxalate complexing agents again, take off behind the heating for dissolving salt, be chilled to room temperature, move in the 50 mL volumetric flasks, be diluted to scale with deionized water, mix.
4, drawing curve
Take by weighing respectively 5 part of 0.2000 g high-purity iron powder, place respectively 125 ml conical flasks, the molten sample acid of adding 25mL (concentration is sulfuric acid: water=1:4), divide and get niobium, tungsten, zirconium mark liquid (content from low to high), heating for dissolving, drip nitric acid oxidation, continue to be heated to sulfuric acid and smolder, salt is separated out and is taken off, slightly cold, (concentration is 4 g/L), take off behind the heating for dissolving salt, is chilled to room temperature to add 15 mL ammonium oxalate complexing agents again, move into respectively in the 50 mL volumetric flasks, be diluted to scale with deionized water, mix, make series standard solution.As shown in table 1.
5, instrument condition of work (as embodiment 1)
6, measure
At niobium 319.498 nm; Tungsten 207.911 nm; Under the zirconium 257.139 nm wavelength, measure at the working curve of drawing, the result is as shown in table 5.
Table 5 sample measurement value and national standard method measured value result contrast %
Above sample employing the present invention processes sample and is consistent with GB photometric measurement result by detecting the gained measurement result, all in national standard tolerance scope.
Claims (1)
1. sample processing method of measuring niobium in the steel, tungsten, zirconium, it is characterized in that may further comprise the steps: 1) the molten sample acid of preparation---a certain amount of concentrated sulphuric acid is blended in the beaker that fills deionized water, after stirring evenly, cooling off, the molten sample acid that the sulfuric acid that to obtain 1 part of density be 1.84 g/mL mixes with 4 parts of deionized waters, stand-by; 2) preparation ammonium oxalate complexing agent---take by weighing a certain amount of ammonium oxalate and dissolve in the beaker that fills deionized water, after the stirring and dissolving, obtain concentration and be the ammonium oxalate complexing agent of 4 g/L, stand-by; 3) dissolved samples---take by weighing 0.1000～0.2000g steel cuttings sample and place conical flask, add the molten sample acid of 20～25 mL, heating for dissolving, dripping nitric acid oxidation to solution clarifies, continue to be heated to sulfuric acid and smolder, take off after salt is separated out, slightly cold, add again 10～15 mL ammonium oxalate complexing agents, take off behind the heating for dissolving salt, be cooled to room temperature, move into again in the 50 mL volumetric flasks, be diluted to scale with deionized water, mixing gets final product.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104597037A (en) * | 2015-01-09 | 2015-05-06 | 江苏省沙钢钢铁研究院有限公司 | Method for determining zirconium content in silicon-zirconium alloy |
| CN105277533A (en) * | 2015-09-28 | 2016-01-27 | 内蒙古包钢钢联股份有限公司 | Method for determining content of zirconium in steel |
| CN106018384A (en) * | 2016-06-20 | 2016-10-12 | 长春黄金研究院 | Method for measuring content of tungsten and molybdenum in ore |
| CN106770199A (en) * | 2016-11-29 | 2017-05-31 | 金堆城钼业股份有限公司 | A kind of method that application ICP AES determine W content in molybdenum-iron |
| CN107219200A (en) * | 2017-05-26 | 2017-09-29 | 马鞍山钢铁股份有限公司 | The method that inductively coupled plasma atomic emission spectrometry determines W content in molybdenum-iron |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104597037A (en) * | 2015-01-09 | 2015-05-06 | 江苏省沙钢钢铁研究院有限公司 | Method for determining zirconium content in silicon-zirconium alloy |
| CN105277533A (en) * | 2015-09-28 | 2016-01-27 | 内蒙古包钢钢联股份有限公司 | Method for determining content of zirconium in steel |
| CN106018384A (en) * | 2016-06-20 | 2016-10-12 | 长春黄金研究院 | Method for measuring content of tungsten and molybdenum in ore |
| CN106770199A (en) * | 2016-11-29 | 2017-05-31 | 金堆城钼业股份有限公司 | A kind of method that application ICP AES determine W content in molybdenum-iron |
| CN107219200A (en) * | 2017-05-26 | 2017-09-29 | 马鞍山钢铁股份有限公司 | The method that inductively coupled plasma atomic emission spectrometry determines W content in molybdenum-iron |
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Application publication date: 20130213 |