CN102539207B - 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, the preparation method of the standard model that relates to a kind of method of X-ray fluorescence spectra working sample and use, more particularly, relate to that a kind of X-ray fluorescence spectra is measured the method for wimet composition and the preparation method of the standard model that uses.
Background technology
The trade mark of wimet is numerous, the constituent content dimensional discrepancy of various product grades is larger, and the content of each composition directly has influence on the usability of hard alloy finished product, therefore, measure quickly and accurately as the content of each metallic element in the front compound of sintering of the wimet such as tungsten base cemented carbide and hart metal product particularly important.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 the deep-etching such as hydrofluorite acid and be used widely.Yet, because the X-ray fluorescence spectra analysis is relative method, namely analyze by the intensity that compares element to be measured in testing sample and standard model, so the accuracy of the direct impact analysis result of the preparation of standard model.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 prior art and relate to the preparation that x-ray fluorescence spectrometry is used standard model, as document " X-ray fluorescence spectra is measured iron and nickel in high density tungsten alloy ", " wimet-x-ray fluorescence spectrometry metal element content-fusion method ", " X-ray fluorescence spectra is analyzed the Preparation Progress of iron alloy samples ", " the niobium in melting sample preparation x-ray fluorescence spectrometry ferrocolumbium, aluminium, titanium " etc., to produce the labor standard sample with the consistent flow process of production method and " the GB/T 26050-2010 wimet XRF measure metal unit belong to content-fusion method " of present up-to-date enforcement adopt in without the standard model situation, then carry out chemical definite value.
In a word, the at present X-ray fluorescence spectra preparation of measuring recruitment composition line standard sample is mainly adopted following several method: a, standard model is arranged, and testing sample quantity adopts when many and takes each standard model and intersect the required standard model of preparation; B, without standard model, generally adopt the consistent flow process of production method to produce the labor standard sample, then carry out chemical definite value; C, main secondary element select corresponding high pure oxide to add, and trace element selects corresponding standard solution to add.
Yet said method still has the following disadvantages for the detection of wimet especially tungsten base cemented carbide:
1. due to the most elements utmost point indissoluble solution of tungsten base cemented carbide, need to use the extremely strong hydrofluorite of corrosivity and at normal temperatures extremely difficulty clear up, and add standard solution can introduce unnecessary impurity element, also must the oven dry sample, operation requirements is high.
2. must adopt the chemical method definite value after producing the labor standard sample by the consistent flow process of production method, workload is larger.After the product content range, must again produce the labor standard sample by the consistent flow process of production method, still must carry out the chemical method definite value afterwards, cost is high, length consuming time.
3. directly take the method for high pure oxide preparation standard model, its sample weighting amount is too little, causes error larger; If prepare but increase sample weighting amount, just high pure oxide need to be ground to evenly, and high pure oxide is difficult even, grind consuming time oversize and easily stain.
So far, existing standard model 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 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, an aspect of of the present present invention provides a kind of X-ray fluorescence spectra to measure the preparation method that the wimet composition is used standard model, described preparation method comprises the steps: a) to take the single oxide of certain mass, dilution ratio according to 1: 10～1: 100 adds flux, adding simultaneously quality is the flux of 0.1～1 times of flux quality and the release agent of 0.1～2g, put into muffle furnace or high frequency molten model machine automatically after mixing, be heated to 700 ℃～1200 ℃ melting 5～40min, place afterwards cooling automatic demoulding and obtain the single oxide bead, prepare as required multiple single oxide bead, wherein, the preparation condition of controlling described single oxide bead is identical with the preparation condition of testing sample bead, b) various single oxide beads are weighed, the quality of the single oxide that comprises in unit of account quality single oxide bead, vibrate mortar with single oxide bead abrasive dust with tungsten carbide simultaneously, according to the kind of single oxide, single oxide bead powder is bottled respectively, c) take the multiple single oxide bead powder that comprises multiple element to be measured in testing sample with the preparation standard model, the quality that takes the single oxide in quality=multiple single oxide bead powder that takes quality=every kind of single oxide that need satisfy testing sample when taking add and, and make the content range of each element of standard model cover the content of each element in testing sample, d) sneak into 0.1～2g release agent in the above-mentioned multiple single oxide bead powder that comprises each element of testing sample that takes, the heating condition according to above-mentioned preparation single oxide bead after mixing prepares the standard model bead.
Measure according to X-ray fluorescence spectra of the present invention the preparation method that the wimet composition is used standard model, described wimet is the tungsten base cemented carbide.
Measure the wimet composition with the preparation method of standard model according to X-ray fluorescence spectra according to the present invention, described single oxide is at least a in the high pure oxide of cobalt, nickel, iron, chromium, tantalum, niobium and tungsten.
Measure according to X-ray fluorescence spectra of the present invention the preparation method that the wimet composition is used standard model, the purity of every kind of single oxide reaches 4N or 3N.
Measure according to X-ray fluorescence spectra of the present invention the preparation method that the wimet composition is used standard model, described flux is lithium tetraborate, and described flux is lithium carbonate, and described release agent is ammonium iodide.
Measure according to X-ray fluorescence spectra of the present invention the preparation method that the wimet composition is used standard model, before to every kind of single oxide bead abrasive dust, first the single oxide bead of the same race with preparation in advance cleans described tungsten carbide vibration mortar and uses alcohol wipe, put into again single oxide bead to be ground, each abrasive dust is controlled identical milling time, milling time is 5～60s, the single oxide bead powder after 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, comprises the following 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 the testing sample of certain mass, dilution ratio according to 1: 10～1: 100 adds flux, adding simultaneously quality is the flux of 0.1～1 times of flux quality and the release agent of 0.1～2g, put into muffle furnace or high frequency molten model machine automatically after mixing, be heated to 700 ℃～1200 ℃ melting 5～40min, place afterwards cooling automatic demoulding and obtain the testing sample bead; C) working curve that obtains of combined standard sample, measure above-mentioned testing sample bead with Xray fluorescence spectrometer.
Measure the method for wimet composition according to X-ray fluorescence spectra of the present invention, described wimet is the tungsten base cemented carbide, and described flux is lithium tetraborate, and described flux is lithium carbonate, and described release agent is 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 that the wimet composition is used standard model.The present invention compared with prior art, method is easy and simple to handle, greatly shortened flow process and the time of producing standard model, avoided simultaneously existing standard model compound method definite value loaded down with trivial details, introduce unnecessary impurity element and be used for the oxide amount of taking of preparation too little and bring the defective such as error.Because but high pure oxide fused salt fine powder is convenient to produce and long preservation, can arbitrarily conversion proportioning during the follow-up required standard model of preparation 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, the restriction to the wimet detection means that causes with standard model because obtaining the X-ray fluorescence spectra analysis be can remove, the accuracy of analysis result and the scope of application that detects of Extended X-ray fluorescent spectroscopy greatly improved.
Embodiment
X-ray fluorescence spectra of the present invention is measured the method for wimet composition to the below and the preparation method of its standard model used is described in detail.
Thinking of the present invention is to adopt the bead powder of multiple high-purity single oxide, prepares X-ray fluorescence spectra through second melting again after each 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 by each metallic element such as Co, Ni, Fe, Cr, Ta, Nb, W etc. in x-ray fluorescence spectrometry wimet presintering material and hart metal product, and make mensuration can trace back to the transmission of quantity value thinking of primary standard substance, realize the purpose of primary and secondary quantitative elements content in wavelength dispersion X-ray fluorescence spectrometry Accurate Determining 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 certain mass, dilution ratio according to 1: 10～1: 100 adds flux, be incorporated as simultaneously the flux of 0.1～1 times of flux quality and the release agent of 0.1～2g, put into muffle furnace or high frequency molten model machine automatically after mixing, be heated to 700 ℃～1200 ℃ melting 5～40min, place afterwards cooling automatic demoulding and obtain the single oxide bead, prepare as required multiple single oxide bead.Preferably, with the potpourri of single oxide and flux, cosolvent, release agent at 1150 ℃ of melting 25min of temperature.Heat if put into muffle furnace, need during to take out and shake once; If put into high frequency automatically molten model machine heat, need not take out, machine can automatically be completed and shake.Wherein, it should be noted that, need the preparation condition of control single oxide bead identical with the preparation condition of testing sample bead, dilution ratio when for example preparing the testing sample bead is 20, dilution ratio when preparing the single oxide bead also should be 20, the parameter such as heat time heating time, heating-up temperature also should be consistent, but be not limited to this.
Dilution ratio is to treat the mass ratio of melting sample and flux.Adding flux is in order to increase the mobility for the treatment of the melting sample and to reduce melt temperature, and flux is generally carbonate and addition is little, and most of the decomposition, generally do not count in dilution ratio when high temperature.The addition of flux is generally flux: flux=0.1～1, add mode for add after directly taking before fusing sample in crucible and with treat that the melting sample mix is even.Adding release agent is the demoulding for the ease of glass sample.Particularly, flux can be the potpourri flux that is mixed by any ratio of diboron trioxide and Lithia, metaborate (as kodalk, lithium metaborate), tetraborate (as sodium tetraborate, lithium tetraborate), metaphosphate (as 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 (as 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 tungstic acid a kind of, and the purity of single oxide need reach 4N or 3N.
Second step: various single oxide beads are weighed, the quality of the single oxide that comprises in unit of account quality single oxide bead, vibrate mortar with single oxide bead abrasive dust with tungsten carbide simultaneously, according to the kind of single oxide, single oxide bead powder is bottled respectively.
In second step, each piece single oxide bead is carried out accurate weighing, weighing precision is ± 0.0001g.The quality of the single oxide that comprises in the weighing Mass Calculation unit mass single oxide bead according to the weighing quality of single oxide/single oxide bead.Preferably, before to every kind of single oxide bead abrasive dust, first with the single oxide bead cleaning tungsten carbide vibration mortar of the same race of preparation in advance and with after alcohol wipe, put into again single oxide bead to be ground, each abrasive dust is controlled identical milling time, milling time is 5～60s, according to the kind of single oxide, single oxide bead powder is bottled respectively afterwards, then the single oxide bead powder after bottling is put into the exsiccator preservation.
The 3rd step: take the multiple single oxide bead powder that comprises multiple element to be measured in testing sample with the preparation standard model, the quality that takes the single oxide in quality=multiple single oxide bead powder that takes quality=every kind of single oxide that need satisfy testing sample when taking add and, and make the content range of each element of standard model cover the content of each element in 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: add 0.1～2g release agent in the multiple single oxide bead powder that comprises each element of testing sample that takes, the heating condition according to above-mentioned preparation single oxide bead after mixing prepares the standard model bead.
So far, namely complete X-ray fluorescence spectra and measured the preparation that the wimet composition is used standard model.Particularly, described wimet can be the tungsten base cemented carbide, and it comprises tungsten base cemented carbide Preburning material and tungsten base cemented carbide product.In the present invention, preparation-obtained standard model can be used for the mensuration of the metallic element of the said goods, 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 wimet composition with preparation method's preparation standard sample of standard model according to above-mentioned X-ray fluorescence spectra, and with Xray fluorescence spectrometer make, the quantitative test working curve.
Then, take the testing sample of certain mass, dilution ratio according to 1: 10～1: 100 adds flux, be incorporated as simultaneously the flux of 0.1～1 times of flux quality and the release agent of 0.1～2g, put into muffle furnace or high frequency molten model machine automatically after mixing, be heated to 700 ℃～1200 ℃ melting 5～40min, place afterwards cooling automatic demoulding and obtain the testing sample bead.Same, heat if put into muffle furnace, need to take out during and shake once; If put into high frequency automatically molten model machine heat, need not take out, machine can automatically be completed and shake.And, need the preparation condition of control single oxide bead identical with the preparation condition of testing sample bead, do not repeat them here particularly.
At last, the working curve that the combined standard sample obtains is measured above-mentioned testing sample bead with Xray fluorescence spectrometer, can obtain the wherein content of primary and secondary quantitative elements Co, Ni, Fe, Cr, Nb, Ta, W etc.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described.
Use in an embodiment of the present invention specpure high pure oxide: 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 Rigaku ZSX100e of company wavelength dispersion X-ray fluorescence spectrometer, Rigaku company vibromill model machine, Rigaku controllable temperature muffle furnace.
Embodiment 1
The preparation of single oxide three oxidation two tantalum bead powder
Preparation process and the advantage of single oxide bead powder in take single oxide three oxidation two tantalums as example illustrates preparation of standard sample method of the present invention.
A, take high-purity three oxidation two tantalums of 0.2000g, the lithium tetraborate that adds 4.000g according to the dilution ratio of 1: 20, the 0.400g lithium carbonate that is incorporated as simultaneously 0.1 times of lithium tetraborate flux quality as the ammonium iodide of flux and 0.5g as release agent, put into muffle furnace after mixing, be heated to 1150 ℃ of melting 25min, take out during this time and shake once, place afterwards cooling automatic demoulding and obtain three oxidation two tantalum beads.This three oxidations, two tantalum beads of weighing, the quality of three oxidation two tantalums that comprise in unit of account quality three oxidation two tantalum beads, with tungsten carbide vibration mortar, three oxidation two tantalum beads are ground 15s simultaneously, sealing after three oxidation two tantalum bead powder bottlings is stand-by, these three oxidations, two tantalum bead powder are called sample No. 1.
B, take high-purity three oxidation two tantalums of 0.4000g, the lithium tetraborate that adds 8.000g according to the dilution ratio of 1: 20, the 0.800g lithium carbonate that is incorporated as simultaneously 0.1 times of lithium tetraborate flux quality as the ammonium iodide of flux and 0.5g as release agent, put into muffle furnace after mixing, be heated to 1150 ℃ of melting 25min, take out during this time and shake once, place afterwards cooling automatic demoulding and obtain three oxidation two tantalum beads.This three oxidations, two tantalum beads of weighing, the quality of three oxidation two tantalums that comprise in unit of account quality three oxidation two tantalum beads, with tungsten carbide vibration mortar, three oxidation two tantalum beads are ground 15s simultaneously, sealing after three oxidation two tantalum bead powder bottlings is stand-by, these three oxidations, two tantalum bead powder are called sample No. 2.
C, take high-purity three oxidation two tantalums of 0.4000g, the lithium tetraborate that adds 4.000g according to the dilution ratio of 1: 10, the 0.400g lithium carbonate that is incorporated as simultaneously 0.1 times of lithium tetraborate flux quality as the ammonium iodide of flux and 2g as release agent, put into muffle furnace after mixing, be heated to 1150 ℃ of melting 25min, take out during this time and shake once, place afterwards cooling automatic demoulding and obtain three oxidation two tantalum beads.This three oxidations, two tantalum beads of weighing, the quality of three oxidation two tantalums that comprise in unit of account quality three oxidation two tantalum beads, with tungsten carbide vibration mortar, three oxidation two tantalum beads are ground 15s simultaneously, sealing after three oxidation two tantalum bead powder bottlings is stand-by, these three oxidations, two tantalum bead powder are called sample No. 3.
D, take high-purity three oxidation two tantalums of 0.1000g, the lithium tetraborate that adds 10.000g according to the dilution ratio of 1: 100, the 1.000g lithium carbonate that is incorporated as simultaneously 0.1 times of lithium tetraborate flux quality as the ammonium iodide of flux and 0.1g as release agent, put into muffle furnace after mixing, be heated to 1150 ℃ of melting 25min, take out during this time and shake once, place afterwards cooling automatic demoulding and obtain three oxidation two tantalum beads.This three oxidations, two tantalum beads of weighing, the quality of three oxidation two tantalums that comprise in unit of account quality three oxidation two tantalum beads, with tungsten carbide vibration mortar, three oxidation two tantalum beads are ground 60s simultaneously, sealing after three oxidation two tantalum bead powder bottlings is stand-by, these three oxidations, two tantalum bead 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 bead is specifically as shown in table 1.
The test findings of table 1 three oxidation two tantalum bead powder preparations
By the test findings in embodiment 1 and table 1 as can be known, the preparation method of standard model of the present invention is simple, and can change dilution ratio, presses the proportional expansion bead of dilution ratio quality with preparation single oxide bead powder.The sample weighting amount that the second melting of standard model of the present invention preparation contains same content concentration of element to be measured is 25 times of former pure-oxide sample weighting amount to from table rear four as can be known, and this makes the low concentration preparation become possibility, and can reduce weighing error.
Embodiment 2
The preparation of standard model
Produce the tungsten base cemented carbide standard model of two trades mark with the preparation steps in explanation preparation of standard sample method of the present invention.
Take the single oxide of 0.2000g, the lithium tetraborate that adds 4.000g according to the dilution ratio of 1: 20, the 0.400g lithium carbonate that is incorporated as simultaneously 0.1 times of lithium tetraborate flux quality as the ammonium iodide of flux and 0.5g as release agent, put into muffle furnace after mixing, be heated to 1150 ℃ of melting 25min, take out during this time and shake once, place afterwards cooling automatic demoulding and obtain the single oxide bead.In the present embodiment, cobalt sesquioxide bead, nickel sesquioxide bead, di-iron trioxide bead, chrome green bead, tantalum pentoxide bead, niobium pentaoxide bead, tungstic acid bead have been prepared.
The above-mentioned every kind of single oxide bead of weighing, the quality of the single oxide that comprises in unit of account quality single oxide bead, vibrate mortar with single oxide bead abrasive dust with tungsten carbide simultaneously, kind according to single oxide is bottled single oxide bead powder respectively, wherein, the quality of the oxide that comprises in every kind of unit mass oxide glass fuse piece as calculated, is 0.04590mg/mg.
Take various oxide glass fuse piece powder according to the constituent content of testing sample.Need to satisfy be the quality that takes the single oxide in quality=multiple single oxide bead powder that takes quality=every kind of single oxide of testing sample add and=0.2000g=200mg.Take the Co element as example, if in testing sample, Co content is 8wt%, can be according to formula m
The bead opaque amount of cobalt sesquioxide* 0.04590 * M
The atomic percent of Co=200mg * 8% calculates the quality of required cobalt sesquioxide bead powder, by that analogy, can calculate respectively the quality of required nickel sesquioxide bead powder, di-iron trioxide bead powder, chrome green bead powder, tantalum pentoxide bead powder, niobium pentaoxide bead powder, tungstic acid bead powder.
At last, sneak into the 0.5g ammonium iodide in the above-mentioned multiple single oxide bead powder that comprises each element of testing sample that takes, the condition according to above-mentioned preparation single oxide bead 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
Shown by the test findings in embodiment 2 and table 2, the loss on ignition of each normal glass fuse piece can control it as unanimously artificially, and the content range of each element can change arbitrarily to meet the content range of each element in testing sample, and the preparation of standard model of the present invention is simple and feasible.
Embodiment 3
Describe X-ray fluorescence spectra of the present invention below by complete embodiment and measure the method for wimet composition and the preparation method of its standard model used.
Take high-purity single oxide of 0.2000g 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, put into muffle furnace after mixing, at 1150 ℃ of melting 25min of temperature, take out during this time and shake once, place afterwards cooling automatic demoulding and obtain the single oxide bead.Prepare respectively each 6 of cobalt sesquioxides, nickel sesquioxide, di-iron trioxide, chrome green, tantalum pentoxide bead, and 10 of tungstic acid beads.Each oxide glass fuse piece of difference weighing, the quality of the single oxide that comprises in unit of account quality single oxide bead.
Each oxide glass fuse piece is ground 15s with the vibromill model machine respectively, then it is bottled immediately and put into exsiccator and preserve according to the kind of different oxide glass fuse piece powder.Must clean mortar before each oxide glass fuse piece abrasive dust, namely first use again alcohol wipe with previously prepared same after abrasive dust oxide glass fuse piece ground and cleaned mortar, discard powder, carry out again the grinding of this kind oxide glass fuse piece powder, prepare successively 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.Take each oxide glass fuse piece powder, by the principle that is 0.2000g of each oxide resultant in oxide glass fuse piece powder, 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, with identical before condition heating and melting and after it is cooling, make the standard model bead.Select one of them standard model bead that contains 7 kinds of oxide glass fuse piece powder preparing to some extent and specifically test, measure its X ray intensity and statistical standard deviation, this sample is called sample No. 7, its test findings is as shown in table 3.
The precision of table 3 standard model
By as seen from Table 3, the preparation precision of this standard model is good, can satisfy for the preparation of working curve fully; 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 Hard alloys: the CMS032 that Sichuan Z-TEK wimet company of section produces, 11YG15,11YG6A, YT5 that the Zigong, Sichuan cemented carbide works is produced.Above-mentioned four kinds of wimet testing samples are carried out pre-oxidation, and (pre-oxidation operates according to GB/T 26050-2010,800 ℃ of oxidation 1h), then the testing sample that takes after 0.2000g pre-oxidation is placed in platinum crucible, the flux lithium tetraborate that adds 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 melting 25min at 1150 ℃ of temperature, take out during this time and shake once, place cooling rear automatic demoulding and obtain the testing sample bead.According to above-mentioned preparation condition, the wimet of every kind of trade mark is prepared 2 testing sample beads.Then the working curve that the standard model for preparing with the present invention 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
As shown in 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 " wimet XRF measure metal unit belong 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 wimet sample tests result to be measured and results of comparison.
In sum, X-ray fluorescence spectra of the present invention is measured the preparation method of wimet constituent reference standard sample by preparing standard model with multiple high-purity single oxide bead 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.To prepare according to the present invention the standard model bead of completing and be used for various wavelength dispersion X-ray fluorescence spectrometers mensuration wimet making quantitative test working curves, can realize the mensuration to the high efficient and reliable of metal element content in tungsten base cemented carbide such as wimet Preburning material and hart metal product.
The invention is not restricted to above-described embodiment, in the situation that do not break away from claim protection domain of the present invention, can carry out various changes and modifications.
Claims (8)
1. an X-ray fluorescence spectra is measured the wimet composition with the preparation method of standard model, it is characterized in that described preparation method comprises the steps:
a) take the single oxide of certain mass, select the dilution ratio of 1:10～1:100 to add flux, adding simultaneously quality is the flux of 0.1～1 times of flux quality and the release agent of 0.1～2g, put into muffle furnace or high frequency molten model machine automatically after mixing, be heated to 700 ℃～1200 ℃ melting 5～40min, place afterwards cooling automatic demoulding and obtain the single oxide bead, prepare as required multiple single oxide bead, wherein, the preparation condition of controlling described single oxide bead is identical with the preparation condition of testing sample bead,
B) various single oxide beads are weighed, the quality of the single oxide that comprises in unit of account quality single oxide bead, vibrate mortar with single oxide bead abrasive dust with tungsten carbide simultaneously, according to the kind of single oxide, single oxide bead powder is bottled respectively;
C) take the multiple single oxide bead powder that comprises multiple element to be measured in testing sample with the preparation standard model, the quality that takes the single oxide in quality=multiple single oxide bead powder that takes quality=every kind of single oxide that satisfies testing sample when taking add and, and make the content range of each element of standard model cover the content of each element in testing sample;
D) sneak into 0.1～2g release agent in the above-mentioned multiple single oxide bead powder that comprises each element of testing sample that takes, the heating condition according to above-mentioned preparation single oxide bead after mixing prepares the standard model bead.
2. X-ray fluorescence spectra according to claim 1 is measured the wimet composition with the preparation method of standard model, it is characterized in that, described wimet is the tungsten base cemented carbide.
3. X-ray fluorescence spectra according to claim 1 is measured the wimet composition with the preparation method of standard model, it is characterized in that, single oxide is a kind of 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 wimet composition with the preparation method of 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 wimet composition with the preparation method of standard model, it is characterized in that, described flux is lithium tetraborate, and described flux is lithium carbonate, and described release agent is ammonium iodide.
6. X-ray fluorescence spectra according to claim 1 is measured the preparation method that the wimet composition is used standard model, it is characterized in that, before to every kind of single oxide bead abrasive dust, first the single oxide bead of the same race with preparation in advance cleans described tungsten carbide vibration mortar and uses alcohol wipe, put into again single oxide bead to be ground, each abrasive dust is controlled identical milling time, milling time is 5～60s, the single oxide bead powder after bottling is put into exsiccator preserve.
7. an X-ray fluorescence spectra is measured the method for wimet composition, it is characterized in that comprising the following steps:
A) according to the described preparation method's preparation standard of any one claim sample to the claim 6 according to claim 1, with Xray fluorescence spectrometer make, the quantitative test working curve;
B) take the testing sample of certain mass, dilution ratio according to 1:10～1:100 adds flux, adding simultaneously quality is the flux of 0.1～1 times of flux quality and the release agent of 0.1～2g, put into muffle furnace or high frequency molten model machine automatically after mixing, be heated to 700 ℃～1200 ℃ melting 5～40min, place afterwards cooling automatic demoulding and obtain the testing sample bead;
C) working curve that obtains of combined standard sample, measure described testing sample bead 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, described wimet is the tungsten base cemented carbide, and described flux is lithium tetraborate, and described flux is lithium carbonate, and described release agent is ammonium iodide.
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