CN100501389C - Quantitative method for elements contained in sample with active metal - Google Patents
Quantitative method for elements contained in sample with active metal Download PDFInfo
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- CN100501389C CN100501389C CNB031491693A CN03149169A CN100501389C CN 100501389 C CN100501389 C CN 100501389C CN B031491693 A CNB031491693 A CN B031491693A CN 03149169 A CN03149169 A CN 03149169A CN 100501389 C CN100501389 C CN 100501389C
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Abstract
The present invention provides the method of safely and precisely analyzing the elements in sample of RE-Fe-B ferromagnetic alloy, RE-Ni alloy for secondary battery and other alloy with active metal. The quantitative analysis method includes crushing the sample, which contains RE metal, alkali metal, alkali earth metal, transition metal and other active metal, with disc crusher or through hydrogenating crushing to D50=10-40 microns, pressing formation to make sample for analysis and fluorescent X-ray analysis.
Description
Technical field
The present invention relates to adopt the fluorescent X-ray method, can be easily, quantitatively have a quantivative approach of the element in the sample contained element of sample, that have active metal such as alloy, metal mixture of active metal with good precision analysis.
Background technology
As with the contained element quantitative methods in the unknown sample, known fluorescent x-ary analysis.As the method for making that adopts the quantitative assay sample of this fluorescent x-ary analysis, for example can carry out with following method, i.e. acid dissolving unknown sample penetrates into the drop method in the filter paper; Acid dissolving unknown sample is sealing into solwution method in the special-purpose liquid clamper with solution; After unknown sample is dissolved in direct or acid, acid dissoluting liquid is adsorbed onto on the adsorbent of filter paper powder, roasting, make oxide, after perhaps making precipitation of hydroxide, make oxide, then with the gained oxide dissolution in the alkali-metal flux of boric acid, make to analyze with the beaded glass (glass bead method of ガ ラ ス PVC-ト); The roasting direct unknown sample is made oxide, perhaps behind the acid dissolving unknown sample, acid dissoluting liquid is adsorbed onto in the adsorbent of filter paper powder, oxide is made in roasting, perhaps make precipitation of hydroxide after, make oxide, then with the gained oxide micropowder broken after, press molding perhaps adds bonding agent in the broken front and back of micro mist, press molding obtains analyzing the oxide press forming method with the formed body sample; At unknown sample is the occasion of metal or alloy, with its dissolving, after casting with mold, cuts off, and grinds, and obtains the alloy polishing of assay sample sheet; Unknown sample is crushed to press molding after the degree below the about 5 μ m of granularity, perhaps adds bonding agent in the broken front and back of micro mist, press molding obtains analyzing the powder forming process with the shaping sample.
Above-mentioned drop method and solwution method are owing to use strong acid in pre-treatment, and be dangerous and miscellaneous, and owing to can not fully obtain fluorescent X-ray intensity, have the problem that lacks repeatability.In addition, aforementioned glass bead method and oxide press forming method, same because strong acid is used in pre-treatment, dangerous and miscellaneous, skilled owing to needing again for analysis, depend on the skill level of analyzing the undertaker and the very such problem of mistake is arranged so produce analysis result.And owing to the unevenness of forming, the alloy composition of the abrasive surface of irradiation X ray is different with whole alloy composition mostly, has the low problem of repeatability when casting for aforementioned alloy polishing.
On the other hand, though the aforementioned powder forming process has pre-treatment to be very easy to such advantage,, need micro mist to be broken to below the about 5 μ m of granularity in order to prevent so-called mineral effect.
; the occasion that in assay sample, contains active metal with ignitability; carry out the broken powder forming process below above-mentioned about 5 μ m of micro mist because the dangerous height that catches fire need carry out atmosphere control in order to prevent to catch fire, producing needs main equipment and the such problem of labour.
Therefore, after in the spy opens 2001-No. 56273 communiques, having proposed to contain the assay sample of active metal with non-oxidizing utmost point liquefied gas at low temp cooling, the disposal route of the assay sample of pulverizing.But, in the method, also need to use the device of the non-oxidizing utmost point liquefied gas at low temp of injection and special reducing mechanism, in addition, pulverize the back and catch fire in order to prevent, also need to carry out the quick shaping operation and turn back to normal temperature until sample.
In the powder forming process, broken in order to carry out above-mentioned micro mist, in assay sample, for example under the low situation in the tissue of being present in mutually of the mechanicalness intensity that contains the rare earth metal element morely, the low phase of this mechanicalness intensity of miniaturization optionally.For this reason, optionally its recovery of the phase that the intensity of miniaturization is low becomes difficult, and is often different with assay sample for the composition of the regenerant of analyzing.
Because above aspect in order to analyze the unknown sample with active metal, seldom adopts above-mentioned pre-treatment to be easy to the powder forming process, adopt the dangerous and miscellaneous oxide press forming method of pre-treatment usually.
, for the result from the x-ray fluorescence analysis of the assay sample made of above-mentioned each side method contain element quantitatively, utilize calibration curve method or underlying parameter method (FP method) usually.The analytic target of aforesaid standards curve method is an element, is based on to form known standard analysis sample production typical curve, utilizes this typical curve to carry out quantitative methods, and the FP method is the method for calculating from the theoretical X-ray intensity meter of calculating in advance.
When using the aforesaid standards curve to contain element quantitative,, used based on the typical curve that adopts and assay sample means of the same race are made, the known standard analysis of composition is made with sample in the past.For example, assay sample is that standard analysis is used same alloy with the making of powder forming process with sample when using the alloy of aforementioned powder forming process making.And, for the production standard curve, standard analysis sample with acid dissolving gained alloy, by the plasma luminescence analysis, determine to form, perhaps roasting direct standard analysis sample is made oxide, perhaps acid dissolving standard analysis with sample after, acid dissoluting liquid is adsorbed onto in the adsorbent of filter paper powder etc., oxide is made in roasting, after perhaps making precipitation of hydroxide, make oxide, the broken back of micro mist press molding perhaps adds bonding agent in the broken front and back of micro mist then, press molding is determined to form with fluorescent x-ary analysis.
On the other hand, perform an analysis when using sample,, with regard to the element that constitutes this assay sample, behind the oxide of each element simple substance of weighing, use hybrid shaping and the oxide mixture made for the standard analysis sample with aforesaid oxides press forming legal system.For this reason, this standard analysis just has been determined when the oxide of weighing element simple substance respectively with the composition of sample.So, according to oxide press forming method, standard analysis is determined easily with the constituent content of sample, and can be made the high precision standard curve.
, when making assay sample,, do not use the aforesaid standards assay sample of making by aforesaid oxides press forming method as the standard analysis sample that is used for the production standard curve with the powder forming process in the past.By inference, its reason is because the standard analysis sample when performing an analysis with sample with aforesaid oxides press forming legal system is and potpourri as the different oxide simple substance of the assay sample of alloy, does not think the comparison other thing.
Summary of the invention
The object of the present invention is to provide can be easily and have the quantivative approach of the element in the sample of active metal safely with high accuracy analysis.
The inventor has carried out research with keen determination in order to solve above-mentioned problem.At first, attempt to improve the easy powder forming process in the past of pre-treatment.But, in order to guarantee analysis precision and repeatability etc., carry out being carried out in the past sample is crushed to step below the 5 μ m time, can not solve the ignition issues of active metal contained in the sample.Therefore, the 1st considers to guarantee security, has studied in the pulverising step of sample, by sample being set in specific average particle size range, thereby gets rid of the method for the danger of catching fire.It found that, even sample is not crushed to particle diameter 5 μ m when following, by being set at specified particle size, opposite with expectation, there are not to produce the analysis precision in the past worried and the reduction of repeatability, when preventing to catch fire, fully suppressed the reduction of analysis precision and repeatability, thereby finished the present invention.
Promptly, according to the present invention, the quantivative approach of contained element in a kind of sample with active metal is provided, it is characterized in that, after the sample that will have an active metal was crushed to the scope of D50=10～40 μ m, press molding was made assay sample, with fluorescent x-ary analysis determination and analysis sample, carry out quantitatively.
The best mode that carries out an invention
Below, describe the present invention in detail.
As the required unknown sample of determination object, quantivative approach of the present invention is used the sample with active metal.At this, so-called active metal, the metal that in atmosphere, has ignitability exactly, for example be meant transition metal such as tungsten, titanium, zirconium, rare earth metal, alkaline metal, alkaline-earth metal etc., as sample, can enumerate at least a alloy that contains in these active metals, contain at least a metal mixture in these active metals etc. with active metal.
Have the sample of active metal, as long as have active metal, just there is no particular limitation, but in quantivative approach of the present invention, preferably uses the ignitability height and have the sample that contains rare earth metal of the low phase of mechanicalness intensity in tissue.Wherein, the magnet that uses rare earth metal-iron-boron system, rare earth metal-iron-nitrogen system, terres rares-cobalt system is preferable with alloy etc. with the secondary cell of alloy, rare earth metal-nickel system, rare earth metal-magnesium-nickel system.
Quantivative approach of the present invention is when analytical sample is alloy, and under the situation that the element that contains is evenly distributed in whole sample, high-precision analysis is possible.That is, as the assay sample of alloy, the preferred sample that uses with the micro organization of the fast preparations such as demoulding casting (strip cast) method of cooling velocity.
In quantivative approach of the present invention, at first, the sample that will have above-mentioned active metal is crushed to D50 (cumulative volume mean grain size)=10～40 μ m, the scope of preferred D50=10～25 μ m.When D50 was lower than 10 μ m, the possibility that contained active metal catches fire increased, and can not reclaim the phase of miniaturization from comminutor in addition, and quantitative accuracy probably reduces.On the other hand, if D50 surpasses 40 μ m, the formability variation in subsequent step then, the flatness of the formed body specimen surface after the shaping reduces, and it is many that the diffuse reflection of X ray becomes, and analysis precision and repeatability reduce.
In addition, in order effectively to prevent to catch fire etc., the D10 of the particle diameter of the sample of pulverizing is generally more than the 5 μ m, preferred especially 5～10 μ m.On the other hand, be not subjected to bad influence for making the formability in the subsequent step, D90 is generally below the 200 μ m, particularly below the 120 μ m, and more preferably 50～120 μ m.
Above-mentioned each particle diameter can be measured with commercially available granulometry device.
Pulverizing of mechanicalnesses such as the pulverizing of aforementioned sample for example can be pulverized by bowl mill, disc mill pulverizing, airslide disintegrating mill pulverizing or hydrogenation breaking method etc. carry out.At this, it is after making metal absorption hydrogen make it embrittlement, to pulverize the breaking method of making metal powder with means such as mortar, bruisers that so-called hydrogenation is pulverized, and mechanicalness is pulverized the sample of pulverizing difficulty particularly useful.
In the pulverizing of aforementioned sample, for sample suitably being controlled at above-mentioned specific average particle size range, pulverizing needs the time, crushed material reclaims miscellaneous, compared with adopting inefficent bowl mill to pulverize and the airslide disintegrating mill of the too high and restive particle diameter of grindability is pulverized, adopt the pulverizing of hydrogenation pulverizing and/or disc mill for well.In pulverizing, also aforementioned hydrogenation pulverizing and mechanicalness pulverizing combination can be carried out.
Aforementioned mechanicalness is pulverized and is preferably carried out under non-oxidizing atmosphere, but in fact, because the fire hazard under above-mentioned average particle size range is low, so there is no need the pulverizing atmosphere of strict control main equipment.
In addition, in the pulverising step of reality, be set in above-mentioned specific average particle size range,, carry out pilot study etc., determine that conditions such as pulverizing time are for well according to the kind of the sample that will analyze and the kind of comminuting method in order to make sample.
Secondly, in quantivative approach of the present invention, the pulverizing sample press molding of aforementioned specific mean grain size is made assay sample.
Aforementioned press molding for example evenly is filled into the sample of pulverizing in the metal pattern etc. of desired shape and comes press molding.At this moment, also can be as required, with the sample pulverized and bonding agents such as stearic acid, styrene-maleic acid mixing after, evenly be filled in the metal pattern etc. and come extrusion forming.Also can when pulverizing aforementioned sample, add bonding agent in advance.
When using bonding agent, can make the assay sample that can supply fluorescent x-ary analysis described later as long as pulverize the blending ratio of sample and bonding agent, just there is no particular limitation, and usually, in volumetric ratio, preferably pulverize sample: bonding agent is 1:0.01～1.
Aforementioned pressurization is undertaken by the single shaft compacting usually.Shape during press molding and size are so long as can be for the shape and the size of aftermentioned fluorescent x-ary analysis, and then there is no particular limitation, can suitably select.
Then, in quantivative approach of the present invention, with the assay sample of fluorescent x-ary analysis analysis press molding gained, can be by quantitatively carrying out.Can use conventional fluorescent x-ray analyzer and suitable alternative condition to carry out x-ray fluorescence analysis.
The element of analyzing quantitatively can adopt calibration curve method or FP method.Particularly, when containing element and be the analysis of known sample, the preferred standard curve method.
When using typical curve to contain element quantitative, for example can use the typical curve of making based on the composition of the measurement result of (1) as follows and (2) to carry out.
(1) for and the powder forming process of assay sample means of the same race, will contain component analysis respectively and pulverize the different a plurality of standard analysis samples of composition of the making that are shaped with a plurality of samples of the element of sample, carry out x-ray fluorescence analysis, must be to measurement result.(2) for these a plurality of standard analysis samples, carry out the x-ray fluorescence analysis that plasma luminescence analysis, employing oxide pressing etc. carry out, determine to form.
This method so need not revise the x-ray fluorescence analysis measurement result of assay sample, can be obtained assay value because standard analysis is identical alloy with sample and assay sample.
In addition, prepare the oxide of component analysis with each element simple substance of sample, and weighing, hybrid shaping, to the known a plurality of standard analysis samples of this composition of producing, carry out x-ray fluorescence analysis, can use typical curve to carry out based on this measurement result and composition making.This method is because when the oxide of each element simple substance of weighing, standard analysis is determined with the composition of sample, so, can make making high precision quantitatively become possible typical curve by typical curve with the preceding method of definite constituent contents such as plasma luminescence analysis.
Have again, this method, different with assay sample as alloy, owing to be oxide mixture,, obtain assay value from the typical curve of revising so quantitatively the time, need consider this difference, such correction can be carried out according to known method.
Quantivative approach of the present invention is owing to adopt the sample will have active metal to be ground into the step of specific average particle size range, so can be easily and safety, this constituent content of high accuracy analysis.Particularly, can be with the occasion of the assay sample made with the oxide press forming method of using in the past same or than under its high precision, repeatability be good and easier than said method, it is quantitative to carry out safely.In addition in the present invention, pulverize and/or the hydrogenation pulverizing, can analyze in the shorter time by in pulverising step, adopting disc mill.
In the present invention, by using oxide based on the contained element simple substance of this assay sample of difference weighing, and the known a plurality of standard analysiss of hybrid shaping and the composition made are with the typical curve of sample productions, after adopting the fluorescent x-ary analysis determination and analysis with sample quantitatively, make the easier and high-precision possibility that quantitatively becomes.
Embodiment
Below, illustrate in greater detail the present invention by embodiment and comparative example, but the present invention is not limited to these.
Embodiment 1
50g is put into alloy sample (A) with the magnet of rare earth metal-iron-boron system of demoulding casting preparation in the pulverizing chamber of disc mill of nitrogen purging, pulverize after 90 seconds the recovery sample.Measure the D50 (μ m) of the pulverizing sample that reclaims with granulometry device (day machine dress society system, マ ィ Network ロ ト ラ ッ Network IISRA).The results are shown in the table 1.
Then, 20g is pulverized in the metal pattern of pellet shaping usefulness that sample evenly is filled into diameter 32mm, under the pressure of 60kN, assay sample is made in the single shaft compacting.(motor of science society system SMX-10) is measured the assay sample of gained with fluorescent x-ray analyzer.From this result, use typical curve, obtain the containing ratio (weight %) of neodymium, praseodymium.The results are shown in the table 1.
As typical curve, use oxide based on the contained element simple substance of this assay sample of weighing respectively, and hybrid shaping and 40 known typical curves that standard analysis is made with sample of composition of making.Merge as the error of neodymium, praseodymium containing ratio, this reference value and the measurement result measured with the oxide pressing of reference value and to be shown in Table 1.
Embodiment 2
Will with the magnet of rare earth metal-iron-boron system of demoulding casting preparation with alloy sample (B) put into can controlled atmospher container, make to be hydrogen atmosphere in the container, make sample (B) embrittlement after, make to be atmospheric pressure in the container, reclaim sample (B), pulverize with mortar.Pulverizing sample and embodiment 1 with gained are same, make assay sample, carry out x-ray fluorescence analysis.From this result, adopt and the typical curve of embodiment 1 the same making, determine the containing ratio of neodymium, praseodymium.The results are shown in the table 1.
Embodiment 3～13
As sample, the magnet that uses rare earth metal-iron-boron system with the preparation of demoulding casting with alloy sample (C), (E)～(H), (J), (K), (L), with the secondary cell of rare earth metal-nickel system of demoulding casting preparation with alloy sample (D), (I), except changing into the pulverizing time the time shown in the table 1 and embodiment 1 similarly makes assay sample.Carry out granulometry analysis, x-ray fluorescence analysis.
For the rare earth metal-iron-magnet alloy sample (C) of boron system, (E)～(H), (J), (K), measure the containing ratio of D50 value, neodymium, praseodymium, magnet alloy sample (L) for identical rare earth metal-iron-boron system, measure the containing ratio of D10 value, D50 value, D90 value, neodymium, praseodymium, dysprosium, for secondary cell usefulness alloy sample (D), (I) of rare earth metal-nickel system, the containing ratio of mensuration D50 Zhi, Lanthanum, cerium, cobalt.The results are shown in the table 1.The error of measured value, this reference value and the measurement result that obtains as the employing oxide pressing of reference value is shown in Table 1 in the lump.
Comparative example 1～9
As sample, use the sample (A)～(I) identical with embodiment 1～9, except the pulverizing time was changed into the time shown in the table 2,, carry out granulometry analysis, x-ray fluorescence analysis with the embodiment 1 the same assay sample of making.For the magnet alloy of rare earth metal-iron-boron system, measure the containing ratio of D50 value, neodymium, praseodymium, for the secondary cell alloy of rare earth metal-nickel system, measure the containing ratio of D50 Zhi, Lanthanum, cerium, cobalt.The results are shown in the table 2.The error of measured value, this reference value and the measurement result that obtains as the employing oxide pressing of reference value is shown in Table 2 in the lump.
Have, comparative example 1 has caught fire when the sample that reclaims after pulverizing again.In addition, comparative example 2 can not be with the sample press forming after pulverizing.Also have, maximal value, minimum value, mean value, error range and the standard deviation of maximal value, minimum value, mean value, error range and the standard deviation of each measurement result among the embodiment 1～13 and the error of reference value and the error of each measurement result in the comparative example 3～9 and reference value are shown in Table 3.
Table 1
| The kind of sample | The D50 value | The D10 value | The D90 value | The pulverizing time (second) | The analytic target element | Reference value (%) | Measured value (%) | Error | |
| Embodiment 1 | Sample (A) | 14.98 | - | - | 90 | Nd Pr | 23.87 13.10 | 23.86 13.12 | -0.01 0.02 |
| Embodiment 2 | Sample (B) | 13.16 | - | - | Hydrogen is pulverized | Nd Pr | 23.85 13.08 | 23.88 13.11 | 0.03 0.03 |
| Embodiment 3 | Sample (C) | 14.69 | - | - | 90 | Nd Pr | 23.88 13.08 | 23.88 13.09 | 0.00 0.01 |
| Embodiment 4 | Sample (D) | 17.17 | - | - | 90 | La Ce Co | 10.95 15.53 11.22 | 10.98 15.52 11.22 | 0.03 -0.01 0.00 |
| Embodiment 5 | Sample (E) | 19.34 | - | - | 90 | Nd Pr | 23.80 13.12 | 23.80 13.15 | 0.00 0.03 |
| Embodiment 6 | Sample (F) | 10.16 | - | - | 120 | Nd Pr | 23.84 13.15 | 23.89 13.15 | 0.05 0.00 |
| Embodiment 7 | Sample (G) | 11.40 | - | - | 120 | Nd Pr | 23.81 13.11 | 23.81 13.12 | 0.00 0.01 |
| Embodiment 8 | Sample (H) | 20.71 | - | - | 60 | Nd Pr | 23.85 13.09 | 23.89 13.11 | 0.04 0.02 |
| Embodiment 9 | Sample (I) | 26.07 | - | - | 60 | La Ce Co | 10.93 15.50 11.20 | 10.96 15.50 11.18 | 0.03 0.00 -0.02 |
| Embodiment 10 | Sample (J) | 29.98 | - | - | 60 | Nd Pr | 23.88 13.15 | 23.87 13.19 | -0.01 0.04 |
| Embodiment 11 | Sample (K) | 36.66 | - | - | 60 | Nd Pr | 23.80 13.12 | 23.85 13.14 | 0.05 0.02 |
| Embodiment 12 | Sample (L) | 28.40 | 7.5 | 135.8 | 80 | Nd Pr Dy | 9.94 22.14 23.74 | 9.94 22.15 23.74 | 0.00 -0.01 0.00 |
| Embodiment 13 | Sample (L) | 11.80 | 6.7 | 60.6 | 100 | Nd Pr Dy | 9.94 22.14 23.74 | 9.93 22.12 23.74 | 0.01 0.02 0.00 |
Table 2
| The kind of sample | The D50 value | The pulverizing time (second) | The analytic target element | Reference value (%) | Measured value (%) | Error | |
| Comparative example 1 | Sample (A) | - | 150 | Nd Pr | 23.87 13.10 | - - | - - |
| Comparative example 2 | Sample (B) | 174.23 | 20 | Nd Pr | 23.85 13.08 | - - | - - |
| Comparative example 3 | Sample (C) | 105.22 | 30 | Nd Pr | 23.88 13.08 | 23.21 12.81 | -0.67 -0.27 |
| Comparative example 4 | Sample (D) | 1152 | 40 | La Ce Co | 10.95 15.53 11.22 | 10.42 15.25 10.97 | -0.53 -0.28 -0.25 |
| Comparative example 5 | Sample (E) | 59.43 | 40 | Nd Pr | 23.80 13.12 | 23.33 12.79 | -0.47 -0.33 |
| Comparative example 6 | Sample (F) | 68.02 | 40 | Nd Pr | 23.84 13.15 | 23.46 12.70 | -0.38 -0.45 |
| Comparative example 7 | Sample (G) | 67.71 | 120 | Nd Pr | 23.81 13.11 | 2332 12.53 | -0.49 -0.58 |
| Comparative example 8 | Sample (H) | 51.29 | 50 | Nd Pr | 23.85 13.09 | 23.61 12.89 | -0.24 -0.20 |
| Comparative example 9 | Sample (I) | 80.23 | 40 | La Ce Co | 10.93 15.50 11.20 | 10.38 15.20 10.95 | -0.55 -0.30 -0.25 |
Table 3
| Max value of error | The error minimum value | AME | Error range | Standard deviation (σ) | |
| Embodiment 1-13 | 0.05 | -0.02 | 0.02 | 0.07 | 0.02 |
| Comparative example 3-9 | -0.67 | -0.20 | -0.39 | 0.47 | 0.15 |
Claims (2)
1. the quantivative approach of contained element in the sample with active metal, it is characterized in that, after the magnet that will comprise rare earth metal-iron-boron system is crushed to the scope of D50=10～40 μ m with the sample with active metal of alloy, press molding is made assay sample, use fluorescent x-ary analysis, the determination and analysis sample, prepare the oxide of each element simple substance of this assay sample of formation, and carry out weighing, hybrid shaping and make and form known a plurality of standard analysiss sample, the typical curve that use is made with sample based on institute's standard analysis carries out quantitatively.
2. the described quantivative approach of claim 1 is characterized in that pulverizing and/or the hydrogenation pulverizing by disc mill, carries out aforementioned pulverizing with sample of active metal.
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| CN103389232B (en) * | 2012-05-07 | 2016-06-01 | 广东韶钢松山股份有限公司 | The sample preparation methods of X fluorescence spectrum analysed for powder alloy cast iron |
| CN103592323A (en) * | 2013-11-15 | 2014-02-19 | 株洲硬质合金集团有限公司 | Method for analyzing and detecting solid solubility of tungsten in cemented carbide binding phase |
| JP2016017823A (en) * | 2014-07-08 | 2016-02-01 | 株式会社日立ハイテクサイエンス | Sample plate for x-ray analysis and fluorescent x-ray analyzer |
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| DE102021133467A1 (en) | 2021-12-16 | 2023-06-22 | Endress+Hauser Conducta Gmbh+Co. Kg | Calibration standard, sensor arrangement and use |
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