CN102539207A - Method for preparing standard sample for testing content of hard-alloy components and method for testing content of hard-alloy components - Google Patents

Abstract

The invention discloses a preparation method and a measurement method of a standard sample for determining the composition of cemented carbide by X-ray fluorescence spectrometry. The standard sample preparation method includes the following steps: firstly, a variety of high Pure single oxide glass frit; then grind multiple single oxide glass frits and bottle them separately; weigh a variety of single oxide glass frit powders containing multiple analyte elements in the sample to be tested to prepare standard samples , and make the content range of each element in the standard sample cover the content of each element in the sample to be tested; finally prepare the standard sample glass frit according to the above method. The working curve is prepared by using the standard sample glass frit, and then the content of each element of the cemented carbide sample to be tested is determined by X-ray fluorescence spectroscopy. By adopting the standard sample prepared by the invention, the restriction on the cemented carbide detection means caused by the standard sample can be removed, the accuracy of the result can be improved and the application range of the X-ray fluorescence spectrum detection can be extended.

Description

Preparation method and determination method of standard sample for determination of cemented carbide composition

technical field

The invention belongs to the technical field of X-ray fluorescence spectrometry analysis, in particular, it relates to a method for measuring samples by X-ray fluorescence spectrometry and a method for preparing standard samples used therein, and more specifically, relates to a method for measuring X-ray fluorescence spectrometry Methods of cemented carbide compositions and the preparation of standard samples for their use. the

Background technique

There are many grades of cemented carbide, and the range of element content of various product grades varies greatly, and the content of each component directly affects the performance of the finished cemented carbide. Therefore, it is necessary to quickly and accurately determine The content of each metal element in the pre-sintering mixture of cemented carbide and cemented carbide products is particularly important. X-ray fluorescence spectrometry is widely used because of its fast analysis speed, high precision, simple sample preparation, simultaneous detection of multiple elements, avoiding wet analysis of cemented carbide, and strong corrosive acids such as hydrofluoric acid for sample digestion. However, since X-ray fluorescence spectroscopic analysis is a relative method, that is, the analysis is performed by comparing the intensity of the analyte elements in the analyte sample and the standard sample, so the preparation of the standard sample directly affects the accuracy of the analysis results. At present, the lack of standard samples of tungsten-based cemented carbide limits the application of X-ray fluorescence spectroscopy. the

In the prior art, X-ray fluorescence spectrometry is used to measure the composition of cemented carbide calcined mixtures and cemented carbide products, and it involves the preparation of standard samples for X-ray fluorescence spectrometry, such as the document "X-ray fluorescence spectrometry determination of iron in high-density tungsten alloys". and Nickel", "Cemented Carbide-X-ray Fluorescence Spectrometry Determination of Metal Element Content-Melting Method", "Progress in the Preparation of Ferroalloy Samples for X-ray Fluorescence Spectrometry Analysis", "Melt Sample Preparation X-ray Fluorescence Spectrometry Determination of Ferro-Niobium Niobium, aluminum, titanium", etc., and the latest implementation of "GB/T 26050-2010 X-ray fluorescence determination of metal element content of cemented carbide-melting method" adopts the same production method in the absence of standard samples The process prepares artificial standard samples, and then carries out chemical determination. the

In a word, at present, the following methods are mainly used for the preparation of standard samples of working curves for X-ray fluorescence spectrometry: a. There are standard samples, and when the number of samples to be tested is large, each standard sample is weighed to cross-preparate the required standard samples; b. For standard samples, artificial standard samples are generally prepared by the same process as the production method, and then chemically determined; c. The major elements are added with corresponding high-purity oxides, and the trace elements are added with corresponding standard solutions. the

However, the above method still has the following deficiencies for the detection of cemented carbide, especially tungsten-based cemented carbide:

① Since most elements of tungsten-based cemented carbide are extremely difficult to dissolve, it is necessary to use highly corrosive hydrofluoric acid and it is extremely difficult to digest at room temperature, and adding unnecessary impurity elements to the standard solution will introduce unnecessary impurity elements, and it must be dried to test As such, the operation requirements are high. the

②Chemical methods must be used to determine the value after the artificial standard samples are prepared according to the same process as the production method, and the workload is relatively large. When the content range of the product changes, artificial standard samples must be prepared again according to the same process as the production method, and then the chemical method must still be used to determine the value, which is costly and time-consuming. the

③The method of directly weighing high-purity oxides to prepare standard samples, the sample size is too small, resulting in large errors; but if the sample size is increased for preparation, it is necessary to grind the high-purity oxides to uniformity, and the high-purity The oxide is not uniform, takes too long to grind and stains easily. the

So far, the existing standard sample preparation technology still cannot solve the above problems. the

Contents of the invention

The object of the present invention is to provide a method for preparing a standard sample for determination of cemented carbide components by X-ray fluorescence spectrometry that is easy to operate and can be freely combined and prepared, and a method for using the prepared standard sample to carry out X-ray fluorescence spectrometry for cemented carbide components. method. the

In order to achieve the above object, one aspect of the present invention provides a method for preparing a standard sample for determining the composition of cemented carbide by X-ray fluorescence spectroscopy. Add flux at a dilution ratio of 1:10 to 1:100, and at the same time add flux with a mass of 0.1 to 1 times the mass of the flux and 0.1 to 2g of release agent, mix well and put it into a muffle furnace or a high-frequency automatic melting machine Inside, heat to 700°C-1200°C to melt for 5-40 minutes, then place it to cool and automatically release the mold to obtain a single oxide glass frit, and prepare a variety of single oxide glass frits as required, wherein the single oxide glass frit is controlled The preparation conditions of the sheet are the same as the preparation conditions of the sample glass frit to be tested; b) weighing various single oxide glass frits, calculating the mass of the single oxide contained in the single oxide glass frit per unit mass, Simultaneously use the tungsten carbide vibrating mortar to grind the single oxide glass frit into powder, and bottle the single oxide glass frit powder respectively according to the type of single oxide; A variety of single oxide glass fusing powders are used to prepare standard samples. When weighing, the weighing quality of the sample to be tested must be satisfied = the weighing quality of each single oxide = the single oxide in multiple single oxide glass fusing powders Add the mass of the substance, and make the content range of each element of the standard sample cover the content of each element in the sample to be tested; d) in the above-mentioned weighed multiple single oxide glass frit powders containing each element of the sample to be tested Mix in 0.1-2 g of release agent, mix evenly, and prepare a standard sample glass frit according to the above heating conditions for preparing a single oxide glass frit. the

According to the preparation method of a standard sample for determining the composition of cemented carbide by X-ray fluorescence spectrometry of the present invention, the cemented carbide is tungsten-based cemented carbide. the

According to the preparation method of standard samples for determination of cemented carbide components by X-ray fluorescence spectrometry of the present invention, the single oxide is at least one of high-purity oxides of cobalt, nickel, iron, chromium, tantalum, niobium and tungsten. the

According to the preparation method of the standard sample for determination of cemented carbide composition by X-ray fluorescence spectrometry of the present invention, the purity of each single oxide can reach 4N or 3N. the

According to the preparation method of standard samples for determination of cemented carbide components by X-ray fluorescence spectrometry of the present invention, the flux is lithium tetraborate, the flux is lithium carbonate, and the release agent is ammonium iodide. the

According to the preparation method of the standard sample used for determining the cemented carbide composition by X-ray fluorescence spectrometry of the present invention, before grinding each single oxide glass frit, the same single oxide glass frit prepared in advance is used to clean the Vibrate the tungsten carbide mortar and wipe it with alcohol, then put the single oxide glass frit to be ground, control the same grinding time for each grinding, the grinding time is 5-60s, put the single oxide glass frit after bottling Store the powder in a desiccator. the

Another aspect of the present invention provides a method for X-ray fluorescence spectrometry determination of cemented carbide components, comprising the following steps: a) preparing a standard sample according to the aforementioned preparation method, making and quantitatively analyzing the work curve with an X-ray fluorescence spectrometer; b ) Weigh a certain mass of the sample to be tested, add the flux according to the dilution ratio of 1:10 to 1:100, and at the same time add the flux with a mass of 0.1 to 1 times the mass of the flux and 0.1 to 2g of the release agent, after mixing evenly Put it into a muffle furnace or a high-frequency automatic melting machine, heat it to 700 ° C ~ 1200 ° C for 5 ~ 40 minutes, and then place it to cool and automatically demould to obtain a glass fusion sheet of the sample to be tested; c) combine the working curve obtained by the standard sample, use The X-ray fluorescence spectrometer measures the glass frit of the sample to be tested. the

According to the method for determining the composition of cemented carbide by X-ray fluorescence spectroscopy of the present invention, the cemented carbide is tungsten-based cemented carbide, the flux is lithium tetraborate, the flux is lithium carbonate, and the release agent is ammonium iodide. the

The present invention adopts a brand-new idea and proposes a method based on high-purity oxide molten salt fine powder, which is prepared by secondary melting for standard samples used for determining cemented carbide components by X-ray fluorescence spectroscopy. Compared with the prior art, the method of the present invention is simple and convenient to operate, greatly shortens the process and time for preparing standard samples, and avoids the cumbersome value determination of existing standard sample preparation methods, the introduction of unnecessary impurity elements, and the preparation of The amount of oxide weighed is too small to bring defects such as errors. Since the high-purity oxide molten salt fine powder is easy to prepare and can be stored for a long time, when preparing subsequent standard samples, the ratio can be changed arbitrarily to obtain standard samples that meet the requirements of the analysis and detection product content range, which makes the preparation of standard samples simple and fast. Using the standard sample finally prepared by the present invention can remove the limitation on the detection means of cemented carbide caused by the inability to obtain the standard sample for X-ray fluorescence spectrum analysis, improve the accuracy of the analysis results and greatly expand the X-ray fluorescence spectrum analysis The scope of application of the test. the

Detailed ways

The method for determining the composition of cemented carbide by X-ray fluorescence spectrometry of the present invention and the preparation method of the standard sample used therein will be described in detail below. the

The idea of the present invention is to use a variety of high-purity single oxide glass fusing powder, prepare according to the content of each element of the sample to be tested, and then undergo secondary melting to prepare a standard sample for X-ray fluorescence spectrum determination of cemented carbide. Then, use the standard sample prepared by this preparation method to measure the content of each metal element such as Co, Ni, Fe, Cr, Ta, Nb, W, etc. in cemented carbide pre-sintered materials and cemented carbide products by X-ray fluorescence spectrometry. content, and make the measurement traceable to the value transfer idea of the reference material, to achieve the purpose of accurately determining the content of primary and secondary elements in cemented carbide by wavelength dispersive X-ray fluorescence spectrometry. the

According to one aspect of the present invention, the preparation method of the standard sample for determining the composition of cemented carbide by X-ray fluorescence spectrometry includes the following steps. the

Step 1: Weigh a certain mass of single oxide, add flux according to the dilution ratio of 1:10~1:100, add flux 0.1~1 times the mass of flux and 0.1~2g release agent at the same time, mix well Then put it into a muffle furnace or a high-frequency automatic melting machine, heat it to 700 ° C ~ 1200 ° C for 5 ~ 40 minutes, and then place it to cool and automatically demould to obtain a single oxide glass fusion sheet, and prepare a variety of single oxide glass fusion sheets as required. piece. Preferably, the mixture of a single oxide, a flux, a co-solvent, and a release agent is melted at a temperature of 1150° C. for 25 minutes. If it is heated in a muffle furnace, it needs to be taken out and shaken once during the period; if it is heated in a high-frequency automatic fusion machine, it does not need to be taken out, and the machine can complete the shaking automatically. Among them, it should be noted that it is necessary to control the preparation conditions of the single oxide glass frit to be the same as the preparation conditions of the sample glass frit to be tested. The dilution ratio of the glass fusing sheet should also be 20, and parameters such as heating time and heating temperature should also be consistent, but not limited thereto. the

The dilution ratio is the mass ratio of the sample to be melted to the flux. The purpose of adding flux is to increase the fluidity of the sample to be melted and reduce the melting temperature. The flux is generally carbonate and the amount added is small. Most of the flux is decomposed at high temperature and is generally not included in the dilution ratio. The amount of flux added is generally flux: flux = 0.1 to 1, and the addition method is to weigh it directly before melting the sample and then add it to the crucible and mix it evenly with the sample to be melted. The release agent was added to facilitate the release of the glass samples. Specifically, the flux can be a mixture of boron trioxide and lithium oxide in any ratio. Flux, metaborate (such as sodium metaborate, lithium metaborate), tetraborate (such as sodium tetraborate, lithium tetraborate) , metaphosphate (such as sodium metaphosphate, lithium metaphosphate), etc.; the flux can be any carbonate that does not affect the determination of the element to be analyzed, such as lithium carbonate; the release agent can be any halide (such as bromide, iodide, chloride, etc.), such as ammonium iodide. the

According to the present invention, the single oxide can be high-purity oxides of cobalt, nickel, iron, chromium, tantalum, niobium and tungsten such as dicobalt oxide, nickel oxide, iron oxide, chromium oxide, pentoxide One of ditantalum, niobium pentoxide and tungsten trioxide, and the purity of the single oxide must reach 4N or 3N. the

Step 2: Weigh various single oxide glass frits, calculate the mass of single oxide contained in the single oxide glass frit per unit mass, and use a tungsten carbide vibrating mortar to shake the single oxide glass frit Grinding, bottling the single oxide glass frit powder according to the type of single oxide. the

In the second step, each single oxide glass frit is accurately weighed with a weighing accuracy of ±0.0001g. The mass of the single oxide contained in the single oxide glass frit per unit mass is calculated according to the weighed mass of the single oxide/the weighed mass of the single oxide glass frit. Preferably, before grinding each single oxide glass frit, clean the tungsten carbide vibrating mortar with the same single oxide frit prepared in advance and wipe it with alcohol, then put the single oxide to be ground For glass frits, control the same grinding time each time, the grinding time is 5-60s, and then bottle the single oxide glass fusing powders separately according to the type of single oxide, and then bottle the single oxide glass The melt powder is stored in a desiccator. the

Step 3: Weigh a variety of single oxide glass fusing powders containing multiple elements to be tested in the sample to be tested to prepare a standard sample. Weighing mass = the sum of the mass of single oxides in multiple single oxide glass frit powders, and make the content range of each element in the standard sample cover the content of each element in the sample to be tested. the

The purpose of this step is to prepare the mixed powder of the standard sample and ensure that the prepared standard sample has the same burning loss and tablet weight as the sample to be tested. The weight difference of this method accounts for about 0.01-0.3% of the tablet weight. the

Step 4: Add 0.1 to 2 g of release agent to the weighed various single oxide glass fusing powders containing each element of the sample to be tested, mix well and prepare according to the above heating conditions for preparing single oxide glass fusing Obtain the standard sample glass frit. the

So far, the preparation of the standard sample for determining the cemented carbide composition by X-ray fluorescence spectrometry has been completed. Specifically, the cemented carbide may be tungsten-based cemented carbide, which includes tungsten-based cemented carbide pre-sintered material and tungsten-based cemented carbide product. The standard sample prepared in the present invention can be used for the determination of the metal elements of the above-mentioned products, but is not limited thereto. the

According to another aspect of the present invention, the method for determining the composition of cemented carbide by X-ray fluorescence spectrometry includes the following steps. the

Firstly, prepare a standard sample according to the method for preparing a standard sample for determination of cemented carbide composition by X-ray fluorescence spectrometry, and use an X-ray fluorescence spectrometer to make and quantitatively analyze the working curve. the

Then, weigh a certain mass of the sample to be tested, add flux according to the dilution ratio of 1:10 to 1:100, and add flux 0.1 to 1 times the mass of flux and 0.1 to 2 g of release agent at the same time, mix well and put Put it into a muffle furnace or a high-frequency automatic melting machine, heat it to 700 ° C ~ 1200 ° C for 5 ~ 40 minutes, and then leave it to cool and automatically demould to obtain a glass fusion piece of the sample to be tested. Similarly, if it is heated in a muffle furnace, it needs to be taken out and shaken once during the period; if it is heated in a high-frequency automatic fusion machine, it does not need to be taken out, and the machine can automatically complete the shaking. Moreover, it is necessary to control the preparation conditions of the single oxide glass frit to be the same as the preparation conditions of the sample glass frit to be tested, and details will not be repeated here. the

Finally, combined with the working curve obtained from the standard sample, the X-ray fluorescence spectrometer is used to measure the glass frit of the sample to be tested, and the content of the primary and secondary elements Co, Ni, Fe, Cr, Nb, Ta, W, etc. can be obtained. the

The specific implementation of the present invention will be further described below in conjunction with the examples. the

Spectrally pure high-purity oxides are used in the embodiments of the present invention: dicobalt oxide, nickel oxide, iron oxide, chromium oxide, tantalum pentoxide, niobium pentoxide, tungsten trioxide, The purity is 3N. And, used in the embodiment of the present invention: analytically pure lithium tetraborate, analytically pure lithium carbonate, analytically pure ammonium iodide; 20mL Pt-Au crucible, tungsten carbide mortar. In addition, the ZSX100e wavelength dispersive X-ray fluorescence spectrometer from Rigaku Corporation, the vibration mill prototype from Rigaku Corporation, and the temperature-controllable muffle furnace from Rigaku Corporation were also used. the

Example 1

Preparation of single oxide tantalum trioxide glass fusing powder

Taking the single oxide tantalum trioxide as an example to illustrate the preparation process and advantages of the single oxide glass frit powder in the standard sample preparation method of the present invention. the

A. Weigh 0.2000g of high-purity tantalum trioxide, add 4.000g of lithium tetraborate at a dilution ratio of 1:20, and add 0.400g of lithium carbonate 0.1 times the mass of lithium tetraborate flux as a flux and 0.5g of lithium tetraborate at the same time. Ammonium iodide was used as a mold release agent, mixed evenly, put into a muffle furnace, heated to 1150°C and melted for 25 minutes, taken out and shaken once during the period, and then left to cool and automatically released from the mold to obtain a tantalum trioxide glass frit. Weigh the tantalum trioxide glass frit, calculate the mass of tantalum trioxide contained in the tantalum trioxide glass frit per unit mass, and grind the tantalum trioxide glass frit for 15 seconds with a tungsten carbide vibrating mortar. The tantalum trioxide glass fusing powder was bottled and sealed for use, and the tantalum trioxide glass fusing powder was called No. 1 sample. the

B. Weigh 0.4000g of high-purity tantalum trioxide, add 8.000g of lithium tetraborate at a dilution ratio of 1:20, and simultaneously add 0.800g of lithium carbonate 0.1 times the quality of lithium tetraborate flux as flux and 0.5g Ammonium iodide was used as a mold release agent, mixed evenly, put into a muffle furnace, heated to 1150°C and melted for 25 minutes, taken out and shaken once during the period, and then left to cool and automatically released from the mold to obtain a tantalum trioxide glass frit. Weigh the tantalum trioxide glass frit, calculate the mass of tantalum trioxide contained in the tantalum trioxide glass frit per unit mass, and grind the tantalum trioxide glass frit for 15 seconds with a tungsten carbide vibrating mortar. The tantalum trioxide glass fusing powder was bottled and sealed for use, and the tantalum trioxide glass fusing powder was called sample No. 2. the

C. Weigh 0.4000g of high-purity tantalum trioxide, add 4.000g of lithium tetraborate at a dilution ratio of 1:10, and simultaneously add 0.400g of lithium carbonate that is 0.1 times the quality of lithium tetraborate flux as a flux and 2g of lithium tetraborate. Ammonium iodide is used as a mold release agent, mixed evenly, put into a muffle furnace, heated to 1150°C for 25 minutes, taken out and shaken once during the period, and then left to cool and automatically released from the mold to obtain a tantalum trioxide glass frit. Weigh the tantalum trioxide glass frit, calculate the mass of tantalum trioxide contained in the tantalum trioxide glass frit per unit mass, and grind the tantalum trioxide glass frit for 15 seconds with a tungsten carbide vibrating mortar. The tantalum trioxide glass fusing powder was bottled and sealed for use, and the tantalum trioxide glass fusing powder was called No. 3 sample. the

D. Weigh 0.1000g of high-purity tantalum trioxide, add 10.000g of lithium tetraborate at a dilution ratio of 1:100, and simultaneously add 1.000g of lithium carbonate which is 0.1 times the mass of lithium tetraborate flux as a flux and 0.1g Ammonium iodide was used as a mold release agent, mixed evenly, put into a muffle furnace, heated to 1150°C and melted for 25 minutes, taken out and shaken once during the period, and then left to cool and automatically released from the mold to obtain a tantalum trioxide glass frit. Weigh the tantalum trioxide glass frit, calculate the mass of tantalum trioxide contained in the unit mass tantalum trioxide glass frit, and grind the tantalum trioxide glass frit with a tungsten carbide vibrating mortar for 60 seconds at the same time, The tantalum trioxide glass fusing powder is bottled and sealed for use, and the tantalum trioxide glass fusing powder is called sample No. 4. the

The test results of the above-mentioned samples No. 1-4 all obtained easy-to-release and transparent glass frits that meet the requirements, as shown in Table 1. the

Table 1 Test results of preparation of tantalum trioxide glass frit powder

From the test results in Example 1 and Table 1, it can be seen that the preparation method of the standard sample of the present invention is simple and easy, and the dilution ratio can be changed, and the mass of the glass frit is enlarged in proportion to the dilution ratio to prepare a single oxide glass frit pink. As can be seen from the last four items in the table, the secondary melting preparation of the standard sample of the present invention contains 25 times of the original pure oxide sample weight, which makes the preparation of low concentration possible, and Weighing errors can be reduced. the

Example 2

Preparation of standard samples

Prepare two grades of tungsten-based cemented carbide standard samples to illustrate the preparation steps in the standard sample preparation method of the present invention. the

Weigh 0.2000g of a single oxide, add 4.000g of lithium tetraborate at a dilution ratio of 1:20, and simultaneously add 0.400g of lithium carbonate that is 0.1 times the mass of lithium tetraborate flux as a flux and 0.5g of ammonium iodide as a flux. Release agent, mixed evenly, put into muffle furnace, heated to 1150°C and melted for 25 minutes, took out and shaked once during the period, then left to cool and automatically released from the mold to obtain a single oxide glass frit. In this example, cobalt trioxide glass frits, nickel sesquioxide glass frits, ferric oxide glass frits, chromium oxide glass frits, tantalum pentoxide glass frits, pentoxide glass frits, Niobium glass frit, tungsten trioxide glass frit. the

Weigh each of the above-mentioned single oxide glass fusion pieces, calculate the mass of the single oxide contained in the unit mass single oxide glass fusion piece, and simultaneously use a tungsten carbide vibrating mortar to grind the single oxide glass fusion piece, according to the unit Varieties of oxides Bottle the single oxide glass fusing powder separately, and, after calculation, the mass of oxide contained in each oxide glass fusing per unit mass is 0.04590mg/mg. the

Weigh various oxide glass frit powders according to the element content of the sample to be tested. What needs to be satisfied is that the weighed mass of the sample to be tested = the weighed mass of each single oxide = the sum of the mass of the single oxides in the multiple single oxide glass frit powders = 0.2000 g = 200 mg. Taking Co element as an example, if the Co content in the sample to be tested is 8wt%, then the required formula can be calculated according to _{the mass of glass frit powder of dicobalt trioxide} × 0.04590 × M _{Co atomic percentage} = 200mg × 8%. The quality of cobalt trioxide glass fusing powder, by analogy, can calculate respectively required nickel sesquioxide glass fusing powder, ferric oxide glass fusing powder, dichromium trioxide glass fusing powder, five The quality of tantalum oxide glass fusing powder, niobium pentoxide glass fusing powder and tungsten trioxide glass fusing powder.

Finally, mix 0.5 g of ammonium iodide into the above-mentioned weighed various single oxide glass frit powders containing each element of the sample to be tested, and after mixing evenly, prepare two groups according to the above conditions for preparing single oxide glass frit Standard sample glass frit. the

Specifically, the two grades of cemented carbide to be tested are WC-Co and WC-Ni, the content of each element and the corresponding amount of each oxide glass fusing powder are shown in Table 2, and the corresponding two standard The samples are referred to as sample No. 5 and sample No. 6. the

The preparation dosage of table 2 standard sample

The test results in Example 2 and Table 2 show that the loss on ignition of each standard glass frit can be artificially controlled to be consistent, and the content range of each element can be changed arbitrarily to meet the requirements of each element in the sample to be tested. content range, the preparation of the standard sample of the present invention is simple and feasible. the

Example 3

Describe the method for X-ray fluorescence spectrometry of the present invention to measure cemented carbide composition and the preparation method of its used standard sample by complete embodiment below. the

Weigh 0.2000g of high-purity single oxide into a platinum crucible, add 4.000g±0.001g of flux lithium tetraborate, 0.400g±0.001g of flux lithium carbonate and 0.5g of release agent according to the dilution ratio of 1:20 Ammonium iodide, mixed evenly, put into the muffle furnace, melted at a temperature of 1150°C for 25 minutes, took it out and shook it once during the period, and then left it to cool and automatically demolded to obtain a single oxide glass frit. Prepare 6 pieces of cobalt oxide, nickel oxide, iron oxide, chromium oxide, and tantalum pentoxide glass frits, and 10 tungsten trioxide glass frits. Each oxide glass frit is weighed separately, and the mass of the single oxide contained in the single oxide glass frit per unit mass is calculated. the

Grind each oxide glass frit with a vibrating mill for 15 s, and then immediately bottle them according to different types of oxide glass frit powder and store them in a desiccator. The mortar must be cleaned before grinding each oxide glass frit, i.e. first use the same pre-prepared oxide glass frit to be ground to grind and clean the mortar, then wipe it with alcohol, discard the powder, and then carry out the For the grinding of the oxide glass fusing powder, the oxide glass fusing powder containing 0.04590 mg of oxide is prepared sequentially according to the above process. Take each oxide glass fusing powder, and prepare 14 standard samples according to the principle that the total amount of each oxide in the oxide glass fusing powder is 0.2000g, and the content range of each element in each standard sample 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%) ), samples with high uniformity requirements can be independently prepared 11 times. Afterwards, the powdered standard sample was mixed evenly with 0.5 g of release agent ammonium iodide and placed in a muffle furnace, heated and melted under the same conditions as before and cooled to obtain a standard sample glass frit. Select one of the standard sample glass frits containing 7 kinds of prepared oxide glass frit powders to carry out specific tests, measure its X-ray intensity and count the standard deviation, this sample is called No. 7 sample, and its test results are shown in the table 3 shown. the

Table 3 Precision of Standard Samples

It can be seen from Table 3 that the preparation precision of the standard sample is good, which can fully meet the requirements for preparing the working curve; the X-ray fluorescence spectrometer comes with the software for matrix calibration, and the calibration factor of the working curve of each element is greater than 0.9999, and the accuracy is less than 0.01. Fully meet the determination requirements of the sample. the

Then, four WC-Co cemented carbide grades were selected: CMS032 produced by Sichuan Keliite Cemented Carbide Company, and 11YG15, 11YG6A, YT5 produced by Sichuan Zigong Cemented Carbide Factory. Pre-oxidize the above four kinds of cemented carbide samples to be tested (pre-oxidize according to GB/T 26050-2010, oxidize at 800°C for 1h), then weigh 0.2000g of the pre-oxidized samples to be tested and place them in a platinum crucible, add 4.000g±0.001g of lithium tetraborate as a flux, 0.400g±0.001g of lithium carbonate as a flux and 0.5g of ammonium iodide as a release agent, mix well and put them in a muffle furnace, heat to 1150°C and melt for 25 minutes , take it out and shake it once during the period, and automatically release the mold after cooling to obtain the sample glass frit to be tested. According to the above preparation conditions, two pieces of glass frits to be tested were prepared for each grade of cemented carbide. Then the working curve obtained by the standard sample prepared by the present invention is measured for the sample to be tested, and the test results are as shown in table 4. the

Table 4 actual measured sample composition to be measured and the data contrast (wt%) of given value

As can be seen from Table 4, the working curve prepared according to the standard sample prepared by the present invention has an error between the measurement result and the contrast result of the hard alloy sample to be tested in GB/T 26050-2010 "Carbide X-ray Fluorescence Determination of Metal Elements". Content-melting method "in the allowable error scope, show that the analysis result of the standard sample prepared by the present invention has higher accuracy and reliability. the

In summary, the method for preparing the standard sample of cemented carbide composition by X-ray fluorescence spectrometry of the present invention prepares the standard sample by using a variety of high-purity single oxide glass fusing powders, not only the sample preparation of the standard sample has good reproducibility , and the oxide glass frit powder is easy to store, and various standard samples can be flexibly configured. The standard sample glass frit prepared according to the present invention is used in various wavelength dispersive X-ray fluorescence spectrometers to measure hard alloys to make quantitative analysis work curves, which can realize the analysis of tungsten-based hard alloys such as hard alloy pre-sintered materials and hard alloys. Efficient and reliable determination of metal element content in alloy products. the

The present invention is not limited to the above-mentioned embodiments, and various variations and modifications can be made without departing from the protection scope of the claims of the present invention. the

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.