CN102539207A - Method for preparing standard sample for testing content of hard-alloy components and method for testing content of hard-alloy components - Google Patents
Method for preparing standard sample for testing content of hard-alloy components and method for testing content of hard-alloy components Download PDFInfo
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Abstract
The invention discloses a method for preparing a standard sample for testing the content of hard-alloy components by adopting the X-ray fluorescence spectrometry and a method for testing the content of hard-alloy components by adopting the X-ray fluorescence spectrometry. The method for preparing the standard sample comprises the following steps: preparing a variety of high-purity single oxide glass fuse pieces under the same condition of preparing glass fuse pieces of the sample under test; grinding the high-purity single oxide glass fuse pieces into powder and filling the powder into bottles respectively; weighting the powder of the high-purity single oxide glass fuse pieces, which comprises a variety of elements under test in the sample under test, to prepare the standard sample, wherein the range of the content of a variety of elements of the standard sample covers the range of the content of a variety of elements of the sample under test; and finally preparing the glass fuse pieces of the standard sample according to the method. A working curve is made by using the glass fuse pieces of the standard sample, and then the content of a variety of elements of the hard alloy sample under test are tested by adopting the X-ray fluorescence spectrometry. Due to the adoption of the standard sample prepared by using the method of the invention, the limit to the detection method of the hard alloy, which is caused by the standard sample, can be eliminated, the accuracy of the result can be improved, and the application range of the X-ray fluorescence spectrometry can be expanded.
Description
Technical field
The invention belongs to the X-ray fluorescence spectra analysis technical field; Specifically; Relate to a kind of method of X-ray fluorescence spectra working sample and the preparation method of employed standard model thereof; More particularly, relate to a kind of X-ray fluorescence spectra and measure the method for wimet composition and the preparation method of employed standard model thereof.
Background technology
The trade mark of wimet is numerous; The constituent content dimensional discrepancy of various product grades is bigger; And the content of each composition directly has influence on the usability of hard alloy finished product; Therefore, mensuration is particularly important like the content of each metallic element in preceding compound of the sintering of wimet such as tungsten base cemented carbide and the hart metal product quickly and accurately.X ray fluorescence spectrometry is fast because of analysis speed, precision is high, but the simple multielement of sample preparation detects simultaneously, can avoid the wimet wet-way analysis, and sample digestion can use deep-etching such as hydrofluorite acid and be used widely.Yet, because the X-ray fluorescence spectra analysis is relative method, promptly analyze through the intensity that compares element to be measured in testing sample and the standard model, so the direct impact analysis result's of the preparation of standard model accuracy.At present, the standard model of tungsten base cemented carbide lacks, and the application of x ray fluorescence spectrometry is restricted.
Use x-ray fluorescence spectrometry wimet pre-burning compound and hart metal product composition in the prior art and relate to the preparation of x-ray fluorescence spectrometry with standard model; Like document " X-ray fluorescence spectra is measured iron and nickel in the high density tungsten alloy ", " wimet-x-ray fluorescence spectrometry metal element content-fusion method ", " X-ray fluorescence spectra is analyzed preparation method's progress of iron alloy samples ", " niobium, aluminium, titanium in the fusion sample preparation x-ray fluorescence spectrometry ferrocolumbium " etc.; And " GB/T 26050-2010 wimet XRF is measured metal unit and belonged to content-fusion method " of present up-to-date enforcement adopt under no standard model situation is to produce the labor standard sample with the flow process of working method unanimity, carries out chemical definite value then.
In a word, the X-ray fluorescence spectra preparation of measuring recruitment composition line standard sample is at present mainly adopted following several method: a, standard model is arranged, and testing sample quantity adopts for a long time and takes by weighing each standard model and intersect the required standard model of preparation; B, no standard model generally adopt the consistent flow process of working method to produce the labor standard sample, carry out chemical definite value then; C, main secondary element select for use corresponding high pure oxide to add, and trace element selects for use corresponding standard solution to add.
Yet said method is for the detection of wimet especially tungsten base cemented carbide, and is not enough below still existing:
1. since the most elements utmost point indissoluble of tungsten base cemented carbide separate, need to use the hydrofluorite of very corrosive and at normal temperatures extremely difficulty clear up, can introduce unnecessary impurity element and add standard solution, also must the oven dry sample, operation requires high.
2. must adopt the chemical method definite value after producing the labor standard sample by the consistent flow process of working method, workload is bigger.After the product content range, must produce the labor standard sample by the consistent flow process of working method once more, still must carry out the chemical method definite value afterwards, cost is high, length consuming time.
3. directly take by weighing the method for high pure oxide preparation standard model, its sample weighting amount is too little, causes error bigger; But prepare if increase sample weighting amount, just need high pure oxide be ground to evenly, and high pure oxide is difficult even, grind consuming time oversize and stain easily.
So far, prior standard sample preparation technique still can not overcome the above problems.
Summary of the invention
But the standard model that the X-ray fluorescence spectra mensuration wimet composition that the object of the present invention is to provide a kind of independent assortment preparation easy and simple to handle is prepared with the preparation method and the use of standard model carries out the X-ray fluorescence spectra method for measuring to the wimet composition.
To achieve these goals; One side of the present invention provides a kind of X-ray fluorescence spectra to measure the preparation method of wimet composition with standard model; Said preparation method comprises the steps: a) to take by weighing the single oxide of certain mass, adds flux according to 1: 10～1: 100 dilution ratio, and adding quality simultaneously is 0.1～1 times flux of flux quality and the release agent of 0.1～2g; Put into the molten automatically model machine of muffle furnace or high frequency after mixing; Be heated to 700 ℃～1200 ℃ fusion 5～40min, place the cooling automatic demoulding afterwards and obtain single oxide glass fuse piece, prepare multiple single oxide glass fuse piece as required; Wherein, it is identical with the preparation condition of testing sample glass fuse piece to control the preparation condition of said single oxide glass fuse piece; B) various single oxide glass fuse pieces are weighed; The quality of the single oxide that is comprised in the unit of account quality single oxide glass fuse piece; Vibrate mortar with single oxide glass fuse piece abrasive dust with tungsten carbide simultaneously, single oxide glass fuse piece powder is bottled respectively according to the kind of single oxide; C) take by weighing the multiple single oxide glass fuse piece powder that comprises multiple element to be measured in the testing sample with the preparation standard model; The quality that takes by weighing the single oxide in quality=multiple single oxide glass fuse piece powder that takes by weighing quality=every kind of single oxide that need satisfy testing sample when taking by weighing add with, and make the content range of each element of standard model cover the content of each element in the testing sample; D) in the above-mentioned multiple single oxide glass fuse piece powder that comprises each element of testing sample that takes by weighing, sneak into 0.1～2g release agent, the heating condition according to above-mentioned preparation single oxide glass fuse piece after mixing prepares standard model glass fuse piece.
Measure the preparation method of wimet composition with standard model according to X-ray fluorescence spectra of the present invention, said wimet is the tungsten base cemented carbide.
Measure the preparation method of wimet composition with standard model according to X-ray fluorescence spectra according to the present invention, said single oxide is at least a in the high pure oxide of cobalt, nickel, iron, chromium, tantalum, niobium and tungsten.
Measure the preparation method of wimet composition with standard model according to X-ray fluorescence spectra of the present invention, the purity of every kind of single oxide reaches 4N or 3N.
Measure the preparation method of wimet composition with standard model according to X-ray fluorescence spectra of the present invention, said flux is lithium tetraborate, and said flux is a lithium carbonate, and said release agent is an ammonium iodide.
Measure the preparation method of wimet composition according to X-ray fluorescence spectra of the present invention with standard model; Before to every kind of single oxide glass fuse piece abrasive dust; Single oxide glass fuse piece of the same race with prepared beforehand cleans said tungsten carbide vibration mortar and uses alcohol wipe earlier, puts into single oxide glass fuse piece to be ground again, the identical milling time of each abrasive dust control; Milling time is 5～60s, the single oxide glass fuse piece powder after the bottling is put into exsiccator preserve.
Another aspect of the present invention provides a kind of X-ray fluorescence spectra to measure the method for wimet composition, may further comprise the steps: a) according to according to aforementioned preparation method's preparation standard sample, with Xray fluorescence spectrometer make, the quantitative test working curve; B) take by weighing the testing sample of certain mass; Add flux according to 1: 10～1: 100 dilution ratio; Adding quality simultaneously is 0.1～1 times flux of flux quality and the release agent of 0.1～2g; Put into the molten automatically model machine of muffle furnace or high frequency after mixing, be heated to 700 ℃～1200 ℃ fusion 5～40min, place the cooling automatic demoulding afterwards and obtain testing sample glass fuse piece; C) working curve that obtains of combined standard sample is measured above-mentioned testing sample glass fuse piece with Xray fluorescence spectrometer.
According to the method for X-ray fluorescence spectra mensuration wimet composition of the present invention, said wimet is the tungsten base cemented carbide, and said flux is lithium tetraborate, and said flux is a lithium carbonate, and said release agent is an ammonium iodide.
It is a kind of based on high pure oxide fused salt fine powder that the present invention adopts new thought to propose, and prepares X-ray fluorescence spectra through second melting and measure the method for wimet composition with standard model.The present invention compared with prior art; Method is easy and simple to handle; Shortened the flow process and the time of producing standard model greatly, avoided simultaneously existing standard model compound method definite value loaded down with trivial details, introduce unnecessary impurity element and the oxide amount of taking by weighing that is used to prepare too little and bring defective such as error.Because but high pure oxide fused salt fine powder is convenient to produce and long preservation, can arbitrarily conversion proportioning when preparing follow-up required standard model obtain adapting to the standard model of analyzing and testing product content area requirement, this makes the preparation of standard model simple and efficient.Adopt the standard model of the final preparation of the present invention; Can remove because of obtaining the restriction that the X-ray fluorescence spectra analysis causes with standard model, improve the scope of application that analytical accuracy also can greatly be expanded the X-ray fluorescence spectra analyzing and testing the wimet detection means.
Embodiment
Face the method for X-ray fluorescence spectra mensuration wimet composition of the present invention and the preparation method of its used standard model down and carry out detailed description.
Thinking of the present invention is to adopt the glass fuse piece powder of multiple high-purity single oxide, prepares X-ray fluorescence spectra through second melting again after each the constituent content preparation according to testing sample and measures the standard model that wimet is used.Then; The standard model that utilizes this preparation method to make; Content through each metallic element such as Co, Ni, Fe, Cr, Ta, Nb, W etc. in x-ray fluorescence spectrometry wimet presintering material and the hart metal product; And making mensuration can trace back to the transmission of quantity value thinking of primary standard substance, the realization wavelength dispersion X-ray fluorescence spectrometry is accurately measured the purpose of primary and secondary quantitative elements content in the wimet.
According to an aspect of the present invention, X-ray fluorescence spectra mensuration wimet composition comprises following step with the preparation method of standard model.
The first step: the single oxide that takes by weighing certain mass; Add flux according to 1: 10～1: 100 dilution ratio; Be incorporated as the flux of 0.1～1 times of flux quality and the release agent of 0.1～2g simultaneously, put into the molten automatically model machine of muffle furnace or high frequency after mixing, be heated to 700 ℃～1200 ℃ fusion 5～40min; Place the cooling automatic demoulding afterwards and obtain single oxide glass fuse piece, prepare multiple single oxide glass fuse piece as required.Preferably, with the potpourri of single oxide and flux, cosolvent, release agent at 1150 ℃ of fusion 25min of temperature.If put into muffle furnace and heat, need to take out during then and shake once; Heat if put into the molten automatically model machine of high frequency, then need not take out, machine can be accomplished automatically and shake.Wherein, It should be noted that; Need the preparation condition of control single oxide glass fuse piece identical with the preparation condition of testing sample glass fuse piece, the dilution ratio when for example preparing testing sample glass fuse piece is 20, and the dilution ratio when then preparing single oxide glass fuse piece also should be 20; Parameter such as heat time heating time, heating-up temperature also should be consistent, but be not limited thereto.
Dilution ratio is to treat the mass ratio of fusion sample and flux.Adding flux is to treat the mobile of fusion sample and reduce melt temperature that flux is generally carbonate and addition is little in order to increase, and generally do not count in the dilution ratio most of the decomposition when high temperature.The addition of flux is generally flux: flux=0.1～1, the adding mode for directly take by weighing the back before the fusing sample and add in the crucible and with treat that the fusion sample mix is even.Adding release agent is the demoulding for the ease of glass sample.Particularly, flux can be diboron trioxide with Lithia by any than the potpourri flux that mixes, metaborate (like kodalk, lithium metaborate), tetraborate (like sodium tetraborate, lithium tetraborate), metaphosphate (like sodium metaphosphate, lithium metaphosphate) etc.; Flux can be any carbonate of not impact analysis element determination to be measured, for example lithium carbonate; Release agent can be any halogenide (like bromide, iodide, chloride etc.), for example ammonium iodide.
According to the present invention; Single oxide can be in the high pure oxide of cobalt, nickel, iron, chromium, tantalum, niobium and tungsten such as cobalt sesquioxide, nickel sesquioxide, di-iron trioxide, chrome green, tantalum pentoxide, niobium pentaoxide and the tungstic acid a kind of, and the purity of single oxide need reach 4N or 3N.
Second step: various single oxide glass fuse pieces are weighed; The quality of the single oxide that is comprised in the unit of account quality single oxide glass fuse piece; Vibrate mortar with single oxide glass fuse piece abrasive dust with tungsten carbide simultaneously, single oxide glass fuse piece powder is bottled respectively according to the kind of single oxide.
In second step, each piece single oxide glass fuse piece is carried out accurate weighing, weighing precision is ± 0.0001g.The quality of the single oxide that is comprised in the weighing Mass Calculation unit mass single oxide glass fuse piece according to the weighing quality/single oxide glass fuse piece of single oxide.Preferably; Before to every kind of single oxide glass fuse piece abrasive dust, the single oxide glass fuse piece of the same race with prepared beforehand cleans tungsten carbide vibration mortar and with after the alcohol wipe, puts into single oxide glass fuse piece to be ground again earlier; The identical milling time of each abrasive dust control; Milling time is 5～60s, according to the kind of single oxide single oxide glass fuse piece powder is bottled respectively afterwards, and the single oxide glass fuse piece powder after will bottling is again put into exsiccator and preserved.
The 3rd step: take by weighing the multiple single oxide glass fuse piece powder that comprises multiple element to be measured in the testing sample with the preparation standard model; The quality that takes by weighing the single oxide in quality=multiple single oxide glass fuse piece powder that takes by weighing quality=every kind of single oxide that need satisfy testing sample when taking by weighing add with, and make the content range of each element of standard model cover the content of each element in the testing sample.
The purpose of this step is that the standard model of preparing the mixed powder of standard model and guaranteeing preparation has identical scaling loss and sheet to weigh with testing sample, and the sheet method of double differences of this method accounts for the heavy ratio of sheet and is about 0.01～0.3%.
The 4th step: in the multiple single oxide glass fuse piece powder that comprises each element of testing sample that takes by weighing, add 0.1～2g release agent, the heating condition according to above-mentioned preparation single oxide glass fuse piece after mixing prepares standard model glass fuse piece.
So far, promptly accomplished X-ray fluorescence spectra and measured of the preparation of wimet composition with standard model.Particularly, said wimet can be the tungsten base cemented carbide, and it comprises tungsten base cemented carbide pre-burning material and tungsten base cemented carbide product.The prepared standard model that obtains can be used for the Determination of Metal Elements of the said goods among the present invention, but is not limited to this.
The method that X-ray fluorescence spectra is according to a further aspect of the invention measured the wimet composition comprises following step.
At first, measure the preparation method preparation standard sample of wimet composition with standard model according to above-mentioned X-ray fluorescence spectra, and with Xray fluorescence spectrometer making, quantitative test working curve.
Then; Take by weighing the testing sample of certain mass; Add flux according to 1: 10～1: 100 dilution ratio, be incorporated as the flux of 0.1～1 times of flux quality and the release agent of 0.1～2g simultaneously, put into the molten automatically model machine of muffle furnace or high frequency after mixing; Be heated to 700 ℃～1200 ℃ fusion 5～40min, place the cooling automatic demoulding afterwards and obtain testing sample glass fuse piece.Same, if putting into muffle furnace heats, need to take out during then and shake once; Heat if put into the molten automatically model machine of high frequency, then need not take out, machine can be accomplished automatically and shake.And, need the preparation condition of control single oxide glass fuse piece identical with the preparation condition of testing sample glass fuse piece, repeat no more at this particularly.
At last, the working curve that the combined standard sample obtains is measured above-mentioned testing sample glass fuse piece with Xray fluorescence spectrometer, can obtain the wherein content of primary and secondary quantitative elements Co, Ni, Fe, Cr, Nb, Ta, W etc.
Do further description below in conjunction with the embodiment specific embodiments of the invention.
Use specpure high pure oxide in an embodiment of the present invention: cobalt sesquioxide, nickel sesquioxide, di-iron trioxide, chrome green, tantalum pentoxide, niobium pentaoxide, tungstic acid, purity are 3N.And, use in an embodiment of the present invention: analyze pure lithium tetraborate, analyze pure lithium carbonate, analyze pure ammonium iodide; 20mL Pt-Au crucible, tungsten carbide mortar.In addition, also use the Japanese ZSX100e of company wavelength dispersion X-ray fluorescence spectrometer of science, Japanese company of science vibromill model machine, Japanese controllable temperature muffle furnace of science.
Embodiment 1
The preparation of single oxide three oxidations two tantalum glass fuse piece powder
With single oxide three oxidations two tantalums is preparation process and the advantage that example is explained single oxide glass fuse piece powder among the standard model preparation method of the present invention.
A, take by weighing high-purity three oxidations, two tantalums of 0.2000g; The lithium tetraborate that adds 4.000g according to 1: 20 dilution ratio; The 0.400g lithium carbonate that is incorporated as 0.1 times of lithium tetraborate flux quality simultaneously as release agent, is put into muffle furnace after mixing as the ammonium iodide of flux and 0.5g, is heated to 1150 ℃ of fusion 25min; Take out during this time and shake once, place the cooling automatic demoulding afterwards and obtain three oxidations, two tantalum glass fuse pieces.This three oxidations, two tantalum glass fuse pieces of weighing; The quality of three oxidations, two tantalums that comprised in the unit of account quality three oxidations two tantalum glass fuse pieces; With tungsten carbide vibration mortar three oxidations, two tantalum glass fuse pieces are ground 15s simultaneously; Three oxidations, two tantalum glass fuse piece powder bottling back sealing is for use, these three oxidations, two tantalum glass fuse piece powder are called sample No. 1.
B, take by weighing high-purity three oxidations, two tantalums of 0.4000g; The lithium tetraborate that adds 8.000g according to 1: 20 dilution ratio; The 0.800g lithium carbonate that is incorporated as 0.1 times of lithium tetraborate flux quality simultaneously as release agent, is put into muffle furnace after mixing as the ammonium iodide of flux and 0.5g, is heated to 1150 ℃ of fusion 25min; Take out during this time and shake once, place the cooling automatic demoulding afterwards and obtain three oxidations, two tantalum glass fuse pieces.This three oxidations, two tantalum glass fuse pieces of weighing; The quality of three oxidations, two tantalums that comprised in the unit of account quality three oxidations two tantalum glass fuse pieces; With tungsten carbide vibration mortar three oxidations, two tantalum glass fuse pieces are ground 15s simultaneously; Three oxidations, two tantalum glass fuse piece powder bottling back sealing is for use, these three oxidations, two tantalum glass fuse piece powder are called sample No. 2.
C, take by weighing high-purity three oxidations, two tantalums of 0.4000g; The lithium tetraborate that adds 4.000g according to 1: 10 dilution ratio; The 0.400g lithium carbonate that is incorporated as 0.1 times of lithium tetraborate flux quality simultaneously as release agent, is put into muffle furnace after mixing as the ammonium iodide of flux and 2g, is heated to 1150 ℃ of fusion 25min; Take out during this time and shake once, place the cooling automatic demoulding afterwards and obtain three oxidations, two tantalum glass fuse pieces.This three oxidations, two tantalum glass fuse pieces of weighing; The quality of three oxidations, two tantalums that comprised in the unit of account quality three oxidations two tantalum glass fuse pieces; With tungsten carbide vibration mortar three oxidations, two tantalum glass fuse pieces are ground 15s simultaneously; Three oxidations, two tantalum glass fuse piece powder bottling back sealing is for use, these three oxidations, two tantalum glass fuse piece powder are called sample No. 3.
D, take by weighing high-purity three oxidations, two tantalums of 0.1000g; The lithium tetraborate that adds 10.000g according to 1: 100 dilution ratio; The 1.000g lithium carbonate that is incorporated as 0.1 times of lithium tetraborate flux quality simultaneously as release agent, is put into muffle furnace after mixing as the ammonium iodide of flux and 0.1g, is heated to 1150 ℃ of fusion 25min; Take out during this time and shake once, place the cooling automatic demoulding afterwards and obtain three oxidations, two tantalum glass fuse pieces.This three oxidations, two tantalum glass fuse pieces of weighing; The quality of three oxidations, two tantalums that comprised in the unit of account quality three oxidations two tantalum glass fuse pieces; With tungsten carbide vibration mortar three oxidations, two tantalum glass fuse pieces are ground 60s simultaneously; Three oxidations, two tantalum glass fuse piece powder bottling back sealing is for use, these three oxidations, two tantalum glass fuse piece powder are called sample No. 4.
The test findings of above-mentioned 1-4 sample all obtains the satisfactory demoulding that is easy to, and transparent glass fuse piece is specifically as shown in table 1.
The test findings of table 1 three oxidations two tantalum glass fuse piece powder preparation
Can know that with the test findings in the table 1 preparation method of standard model of the present invention is simple by embodiment 1, and can change dilution ratio, press the proportional expansion glass of dilution ratio fuse piece quality with preparation single oxide glass fuse piece powder.Can know that the sample weighting amount that the preparation of the second melting of standard model of the present invention contains same content concentration of element to be measured is 25 times of former pure-oxide sample weighting amount for back four from table, this makes the low concentration preparation become possibility, and can reduce weighing error.
Embodiment 2
The preparation of standard model
The tungsten base cemented carbide standard model of producing two trades mark is with the preparation steps among the explanation standard model preparation method of the present invention.
Take by weighing the single oxide of 0.2000g; The lithium tetraborate that adds 4.000g according to 1: 20 dilution ratio; The 0.400g lithium carbonate that is incorporated as 0.1 times of lithium tetraborate flux quality simultaneously as release agent, is put into muffle furnace after mixing as the ammonium iodide of flux and 0.5g, is heated to 1150 ℃ of fusion 25min; Take out during this time and shake once, place the cooling automatic demoulding afterwards and obtain single oxide glass fuse piece.In the present embodiment, cobalt sesquioxide glass fuse piece, nickel sesquioxide glass fuse piece, di-iron trioxide glass fuse piece, chrome green glass fuse piece, tantalum pentoxide glass fuse piece, niobium pentaoxide glass fuse piece, tungstic acid glass fuse piece have been prepared.
The above-mentioned every kind of single oxide glass fuse piece of weighing; The quality of the single oxide that is comprised in the unit of account quality single oxide glass fuse piece; Vibrate mortar with single oxide glass fuse piece abrasive dust with tungsten carbide simultaneously, according to the kind of single oxide single oxide glass fuse piece powder is bottled respectively, wherein; Through calculating, the quality of the oxide that is comprised in every kind of oxide glass fuse piece of unit mass is 0.04590mg/mg.
Constituent content according to testing sample takes by weighing various oxide glass fuse piece powder.What need to satisfy is that the quality that takes by weighing the single oxide in quality=multiple single oxide glass fuse piece powder that takes by weighing quality=every kind of single oxide of testing sample adds and=0.2000g=200mg.With the Co element is example, if Co content is 8wt% in the testing sample, and then can be according to formula m
The glass fuse piece opaque amount of cobalt sesquioxide* 0.04590 * M
The atomic percent of Co=200mg * 8% calculates the quality of required cobalt sesquioxide glass fuse piece powder; By that analogy, can calculate the quality of required nickel sesquioxide glass fuse piece powder, di-iron trioxide glass fuse piece powder, chrome green glass fuse piece powder, tantalum pentoxide glass fuse piece powder, niobium pentaoxide glass fuse piece powder, tungstic acid glass fuse piece powder respectively.
At last, in the above-mentioned multiple single oxide glass fuse piece powder that comprises each element of testing sample that takes by weighing, sneak into the 0.5g ammonium iodide, the condition according to above-mentioned preparation single oxide glass fuse piece after mixing prepares two standard sets mother glass fuse piece.
Particularly, the wimet to be measured of two trades mark is WC-Co and WC-Ni, and its each constituent content is as shown in table 2 with the application quantity mutually of each oxide glass fuse piece powder, and respectively corresponding two standard models is called No. 5 samples and No. 6 samples.
The preparation consumption of table 2 standard model
Test findings by in embodiment 2 and the table 2 shows; The loss on ignition of each normal glass fuse piece can control it as unanimity artificially; And the content range of each element can change arbitrarily to meet the content range of each element in the testing sample, and the simple and convenient preparation of standard model of the present invention is feasible.
Embodiment 3
Describe X-ray fluorescence spectra of the present invention through complete embodiment below and measure the method for wimet composition and the preparation method of its used standard model.
The high-purity single oxide that takes by weighing 0.2000g is in platinum crucible; The flux lithium tetraborate that adds 4.000g ± 0.001g according to dilution ratio at 1: 20; 0.400g the flux lithium carbonate of ± 0.001g and the release agent ammonium iodide of 0.5g are put into muffle furnace after mixing, at 1150 ℃ of fusion 25min of temperature; Take out during this time and shake once, place the cooling automatic demoulding afterwards and obtain single oxide glass fuse piece.Prepare each 6 of cobalt sesquioxides, nickel sesquioxide, di-iron trioxide, chrome green, tantalum pentoxide glass fuse piece respectively, and 10 of tungstic acid glass fuse pieces.Each oxide glass fuse piece of difference weighing, the quality of the single oxide that is comprised in the unit of account quality single oxide glass fuse piece.
Each oxide glass fuse piece is ground 15s with the vibromill model machine respectively, according to the kind of different oxidation thing glass fuse piece powder it is bottled immediately then and put into exsiccator and preserve.Before each oxide glass fuse piece abrasive dust, must clean mortar; Promptly use alcohol wipe with same a kind of the treating of preparation in advance again behind the abrasive dust oxide glass fuse piece ground and cleaned mortar earlier; Discard powder; Carry out the grinding of this kind oxide glass fuse piece powder again, prepare the oxide glass fuse piece powder that contains 0.04590 milligram of oxide in every milligram of oxide glass fuse piece powder by above flow process successively.Take by weighing each oxide glass fuse piece powder; By each oxide resultant in the oxide glass fuse piece powder is the principle of 0.2000g; Make 14 standard models; Each constituent content scope in each standard model is Co (1-30wt%), Ni (0.2-15wt%), Fe (0.2-1wt%), Cr (0.25-1wt%), Nb (0.2-1wt%), Ta (0.2-1wt%), W (36-79wt%), to the demanding sample of uniformity coefficient, can distinguish independent preparation 11 times.Put into muffle furnace after afterwards pulverous standard model and 0.5g release agent ammonium iodide being mixed,, make standard model glass fuse piece with identical before condition heating and melting and after treating its cooling.Select one of them standard model glass fuse piece that contains 7 kinds of oxide glass fuse piece powder preparing to some extent and specifically test, measure its X ray intensity and SS deviation, this sample is called sample No. 7, its test findings is as shown in table 3.
The precision of table 3 standard model
Visible by table 3, the preparation precision of this standard model is good, can satisfy fully to be used for the preparation work curve; Carry software with Xray fluorescence spectrometer and carry out matrix correction, each element working curve correction factor is greater than 0.9999, and accuracy＜0.01 is satisfied the mensuration requirement of sample fully.
Then, selected four kinds of WC-Co wimet trades mark: the CMS032 that Z-TEK wimet company of Sichuan section produces, 11YG15,11YG6A, YT5 that the Sichuan Zigong Hard Alloy Foundry is produced.Above-mentioned four kinds of wimet testing samples are carried out pre-oxidation, and (pre-oxidation is operated according to GB/T 26050-2010; 800 ℃ of oxidation 1h); The testing sample that takes by weighing then after the 0.2000g pre-oxidation places platinum crucible, adds the flux lithium tetraborate of 4.000g ± 0.001g, and the flux lithium carbonate of 0.400g ± 0.001g and 0.5g release agent ammonium iodide; Put into muffle furnace after mixing; Be heated to fusion 25min under 1150 ℃ of temperature, during take out and shake once, place cooling back automatic demoulding and obtain testing sample glass fuse piece.According to above-mentioned preparation condition the wimet of every kind of trade mark is prepared 2 testing sample glass fuse pieces.The working curve that the standard model for preparing with the present invention then obtains is measured testing sample, and test findings is as shown in table 4.
The testing sample composition of table 4 actual measurement and the data contrasts (wt%) of set-point
Can know by table 4; The prepared standard model according to the present invention and the working curve for preparing in the tolerance scope of GB/T 26050-2010 " the wimet XRF is measured metal unit and belonged to content-fusion method ", show that the analysis result of the standard model that the present invention is prepared has higher accuracy and reliability to the error of the mensuration result of wimet sample to be measured and results of comparison.
In sum; The preparation method that X-ray fluorescence spectra of the present invention is measured the wimet constituent reference standard sample prepares standard model through using multiple high-purity single oxide glass fuse piece powder; The sample preparation favorable reproducibility of standard model not only; And oxide glass fuse piece powder is easy to preserve, but the various standard models of flexible configuration.The standard model glass fuse piece that to prepare completion according to the present invention is used for various wavelength dispersion X-ray fluorescence spectrometers and measures wimet making quantitative test working curve, can realize the high-efficiency reliable of metal element content in tungsten base cemented carbide such as wimet pre-burning material and the hart metal product is measured.
The invention is not restricted to the foregoing description, under the situation that does not break away from claim protection domain of the present invention, can carry out various distortion and modification.
Claims (8)
1. an X-ray fluorescence spectra is measured the preparation method of wimet composition with standard model, it is characterized in that said preparation method comprises the steps:
A) take by weighing the single oxide of certain mass; Select 1: 10～1: 100 dilution ratio to add flux; Adding quality simultaneously is 0.1～1 times flux of flux quality and the release agent of 0.1～2g, puts into the molten automatically model machine of muffle furnace or high frequency after mixing, and is heated to 700 ℃～1200 ℃ fusion 5～40min; Place the cooling automatic demoulding afterwards and obtain single oxide glass fuse piece; Prepare multiple single oxide glass fuse piece as required, wherein, the preparation condition of controlling said single oxide glass fuse piece is identical with the preparation condition of testing sample glass fuse piece;
B) various single oxide glass fuse pieces are weighed; The quality of the single oxide that is comprised in the unit of account quality single oxide glass fuse piece; Vibrate mortar with single oxide glass fuse piece abrasive dust with tungsten carbide simultaneously, single oxide glass fuse piece powder is bottled respectively according to the kind of single oxide;
C) take by weighing the multiple single oxide glass fuse piece powder that comprises multiple element to be measured in the testing sample with the preparation standard model; The quality that takes by weighing the single oxide in quality=multiple single oxide glass fuse piece powder that takes by weighing quality=every kind of single oxide that satisfies testing sample when taking by weighing add with, and make the content range of each element of standard model cover the content of each element in the testing sample;
D) in the above-mentioned multiple single oxide glass fuse piece powder that comprises each element of testing sample that takes by weighing, sneak into 0.1～2g release agent, the heating condition according to above-mentioned preparation single oxide glass fuse piece after mixing prepares standard model glass fuse piece.
2. X-ray fluorescence spectra according to claim 1 is measured the preparation method of wimet composition with standard model, it is characterized in that said wimet is the tungsten base cemented carbide.
3. X-ray fluorescence spectra according to claim 1 is measured the preparation method of wimet composition with standard model, it is characterized in that, single oxide is at least a in the high pure oxide of cobalt, nickel, iron, chromium, tantalum, niobium and tungsten.
4. X-ray fluorescence spectra according to claim 1 is measured the preparation method of wimet composition with standard model, it is characterized in that the purity of every kind of single oxide reaches 4N or 3N.
5. X-ray fluorescence spectra according to claim 1 is measured the preparation method of wimet composition with standard model, it is characterized in that said flux is lithium tetraborate, and said flux is a lithium carbonate, and said release agent is an ammonium iodide.
6. X-ray fluorescence spectra according to claim 1 is measured the preparation method of wimet composition with standard model; It is characterized in that; Before to every kind of single oxide glass fuse piece abrasive dust; Single oxide glass fuse piece of the same race with prepared beforehand cleans said tungsten carbide vibration mortar and uses alcohol wipe earlier, puts into single oxide glass fuse piece to be ground again, the identical milling time of each abrasive dust control; Milling time is 5～60s, the single oxide glass fuse piece powder after the bottling is put into exsiccator preserve.
7. an X-ray fluorescence spectra is measured the method for wimet composition, it is characterized in that may further comprise the steps:
A) according to according to any described preparation method's preparation standard of claim sample in claim 1 to the claim 6, with Xray fluorescence spectrometer make, the quantitative test working curve;
B) take by weighing the testing sample of certain mass; Add flux according to 1: 10～1: 100 dilution ratio; Adding quality simultaneously is 0.1～1 times flux of flux quality and the release agent of 0.1～2g; Put into the molten automatically model machine of muffle furnace or high frequency after mixing, be heated to 700 ℃～1200 ℃ fusion 5～40min, place the cooling automatic demoulding afterwards and obtain testing sample glass fuse piece;
C) working curve that obtains of combined standard sample is measured said testing sample glass fuse piece with Xray fluorescence spectrometer.
8. X-ray fluorescence spectra according to claim 7 is measured the method for wimet composition, it is characterized in that said wimet is the tungsten base cemented carbide, and said flux is lithium tetraborate, and said flux is a lithium carbonate, and said release agent is an ammonium iodide.
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