CN113702411A - Method for measuring molar ratio of calcium to zirconium in calcium zirconate - Google Patents

Method for measuring molar ratio of calcium to zirconium in calcium zirconate Download PDF

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CN113702411A
CN113702411A CN202111086291.7A CN202111086291A CN113702411A CN 113702411 A CN113702411 A CN 113702411A CN 202111086291 A CN202111086291 A CN 202111086291A CN 113702411 A CN113702411 A CN 113702411A
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zirconium
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CN113702411B (en
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邓贵仁
林文标
梁火生
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Fujian Basic Electronic Materials Co ltd
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    • G01—MEASURING; TESTING
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    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/2202—Preparing specimens therefor

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Abstract

The invention provides a method for measuring the molar ratio of calcium to zirconium in calcium zirconate, which comprises the steps of firstly setting a series of different molar ratios of calcium to zirconium, and mixing zirconium dioxide and calcium carbonate according to the set values to obtain a series of standard products with different molar ratios of calcium to zirconium; and then preparing a fuse piece, placing the fuse piece into XRF for testing, establishing a standard curve of the signal intensity ratio of calcium and zirconium elements and the molar ratio of calcium and zirconium, and then testing a sample to be tested to obtain the molar ratio of calcium and zirconium of the sample to be tested. The method directly fits the signal intensity ratio and the molar ratio of calcium and zirconium to establish a standard curve, defaults the Zr molar weight to 1, and outputs the Ca molar weight as the result of the Ca/Zr molar ratio, thereby directly obtaining the Ca/Zr molar ratio of the calcium zirconate; or the relationship between Ca and Zr is replaced, thereby obtaining the Zr/Ca molar ratio of the calcium zirconate. Compared with the traditional detection method, the method provided by the invention omits complicated steps, can quickly and intuitively obtain the molar ratio of calcium to zirconium, and has high accuracy and good stability.

Description

Method for measuring molar ratio of calcium to zirconium in calcium zirconate
Technical Field
The invention relates to the field of element testing, in particular to a method for determining the molar ratio of calcium to zirconium in calcium zirconate.
Background
Calcium zirconate (CaZrO)3) Is a relatively stable compound and has wide application in high-temperature ceramics and refractory materials. Theoretically, calcium zirconate (CaZrO)3) The Ca/Zr molar ratio of (1: 1), but in practice, the purity of the raw material is not 100%, impurities, ignition loss, moisture and errors in the weighing process cause the theoretical value of the charge andthe difference exists between the actual values of the products, and whether the calcium-zirconium ratio reaches the target range needs to be determined through detection. Calcium zirconate belongs to electronic ceramic powder and is a raw material of an MLCC (multilayer ceramic capacitor), the Ca/Zr molar ratio has obvious influence on the sintering temperature of a client, and further has great influence on the electrical property of the MLCC, so that the determination of the molar ratio of calcium to zirconium in a calcium zirconate product is very important.
At present, there is no method in the prior art for directly determining the Ca/Zr molar ratio in calcium zirconate. Generally, the element content is firstly measured and then converted, and the steps are complicated, time-consuming and labor-consuming.
Disclosure of Invention
In view of the above, the present invention is directed to a method for determining the molar ratio of calcium to zirconium in calcium zirconate. The determination method provided by the invention can directly and quickly obtain the molar ratio of calcium to zirconium in the calcium zirconate through detection, omits fussy test operation and conversion, and has high accuracy and good stability.
The invention provides a method for determining the molar ratio of calcium to zirconium in calcium zirconate, which comprises the following steps:
a) setting a series of different calcium-zirconium molar ratios, and mixing zirconium dioxide and calcium carbonate according to the set calcium-zirconium molar ratios to obtain a series of standard products with different calcium-zirconium molar ratios;
b) mixing the standard substance with a fluxing agent and a release agent, and preparing a sample by a high-frequency sample melting machine to obtain a series of standard fuse pieces;
c) building a standard:
respectively putting the series of standard fuse pieces into XRF (X-ray fluorescence), measuring the X-ray signal intensity ratio of a series of calcium-zirconium elements, and fitting the signal intensity ratio with the corresponding calcium-zirconium molar ratio by XRF analysis software to obtain an XRF standard curve;
d) testing a sample to be tested:
placing the calcium zirconate to-be-tested fuse piece into XRF for testing, and automatically obtaining the molar ratio of calcium to zirconium by XRF analysis software;
the calcium zirconate to-be-detected fuse piece is prepared by the following preparation method:
and mixing the calcium zirconate sample to be tested with a fluxing agent and a release agent, and preparing the sample by using a high-frequency melting machine to obtain the calcium zirconate melting sheet to be tested.
Preferably, the first and second liquid crystal materials are,
in the standard establishing process of the step c), in XRF analysis software, defaulting the molar weight of Zr element as 1 and inputting the molar weight of Ca element according to the Ca/Zr molar ratio; selecting the X-ray signal intensity ratio of the corresponding Ca/Zr element, and fitting the X-ray signal intensity ratio with the molar weight of the input Ca element to obtain an XRF standard curve; the XRF standard curve actually represents a standard curve of an X-ray signal intensity ratio of Ca/Zr element and a Ca/Zr molar ratio;
in the step d), in XRF analysis software, the Zr molar weight is defaulted to 1, and the Ca molar weight is output as the Ca/Zr molar ratio result to directly obtain the Ca/Zr molar ratio of the calcium zirconate;
or
In the standard establishing process of the step c), defaulting the molar weight of Ca element as 1 and inputting the molar weight of Zr/Ca element as the molar weight input of Zr element in XRF analysis software; selecting the corresponding X-ray signal intensity ratio of Zr/Ca element, and fitting the X-ray signal intensity ratio with the input molar weight of the Zr element to obtain an XRF standard curve, wherein the XRF standard curve actually represents the standard curve of the X-ray signal intensity ratio of the Zr/Ca element and the Zr/Ca molar ratio;
in step d), in the XRF analysis software, the Ca molar quantity is defaulted to 1, and the Zr molar quantity is output as the Zr/Ca molar ratio result to directly obtain the Zr/Ca molar ratio of the calcium zirconate.
Preferably, in the XRF, the test conditions for the X-ray signal intensity of the Ca element are set as follows:
using the K.alpha.1-HS-MIN line;
voltage: 50 Kv; current: 60 mA;
a collimator: 0.46 dg;
crystal: LiF 200;
a detector: flow Counter;
in the XRF, the test conditions of the X-ray signal intensity of the Zr element are set as follows: using the L alpha 1-HS line;
voltage: 30 Kv; current: 100 mA;
a collimator: 0.46 dg;
crystal: PET;
a detector: flow Counter.
Preferably, the sample preparation conditions for preparing the standard substance into the standard fuse block are as follows:
the sample melting temperature is: 1100-1200 ℃,
the front standing time is as follows: the time of the reaction is 200 to 300s,
the swinging time is as follows: 550-650 s;
the standard substance is pretreated before being mixed with fluxing agent and release agent;
the pretreatment of the standard substance comprises the following steps: heat treatment is carried out for 30-60 min at 105-150 ℃;
the sample preparation conditions for preparing the calcium zirconate sample to be detected into the calcium zirconate melt sheet to be detected are as follows:
the sample melting temperature is: 1100-1200 ℃,
the front standing time is as follows: the time of the reaction is 200 to 300s,
the swinging time is as follows: 550-650 s;
the calcium zirconate sample to be tested is pretreated before being mixed with a fluxing agent and a release agent;
the pretreatment of the calcium zirconate sample to be tested comprises the following steps: heat treatment is carried out for 30-60 min at 200-400 ℃.
Preferably, the sample preparation conditions for preparing the standard substance into the standard fuse block are as follows:
the sample melting temperature is: at 1170 c,
the front standing time is as follows: 240s of the number of the first and second groups,
the swinging time is as follows: 600 s;
the pretreatment of the standard substance comprises the following steps: heat treating at 150 deg.C for 30 min;
the sample preparation conditions for preparing the calcium zirconate sample to be detected into the calcium zirconate melt sheet to be detected are as follows:
the sample melting temperature is: at 1170 c,
the front standing time is as follows: 240s of the number of the first and second groups,
the swinging time is as follows: 600 s;
the pretreatment of the calcium zirconate sample to be tested comprises the following steps: heat treatment at 400 deg.C for 30 min.
Preferably, in step c), the formula of the XRF standard curve is formula (1):
i-2.251 × (C-0.0581) formula (1);
wherein:
i is the X-ray signal intensity ratio of calcium and zirconium elements;
c is the molar ratio of calcium to zirconium.
Preferably, the fluxing agent is a mixture of lithium tetraborate and lithium metaborate; the release agent is an aqueous solution of anhydrous lithium bromide.
Preferably, the mass ratio of the lithium tetraborate in the fluxing agent is 67%; the concentration of anhydrous lithium bromide in the anhydrous lithium bromide aqueous solution is 30.5g/50 mL.
Preferably, in the preparation of the standard melt sheet:
the mass ratio of the standard substance to the fluxing agent is (0.4-0.8) to (4-8);
the mass ratio of the release agent to the standard substance is (0.45-0.55) to (0.4-0.8);
in the preparation of the calcium carbonate to-be-detected fuse piece:
the mass ratio of the calcium zirconate sample to be detected to the fluxing agent is (0.4-0.8) to (4-8);
the mass ratio of the release agent to the calcium zirconate sample to be detected is (0.45-0.55) to (0.4-0.8).
Preferably, in the step a), the molar ratio of calcium to zirconium is set to a decimal place; the set different calcium-zirconium molar ratios are selected from 0.9650-1.0000.
The invention provides a method for determining the molar ratio of calcium to zirconium in calcium zirconate, which comprises the steps of establishing a standard curve by directly fitting the signal intensity ratio of calcium to zirconium to the molar ratio, defaulting the molar amount of Zr to 1, and outputting the molar amount of Ca as the result of the molar ratio of Ca to Zr, so as to directly obtain the molar ratio of Ca to Zr of the calcium zirconate; or by replacing the relationship between Ca and Zr according to the above process, the Zr/Ca molar ratio of the calcium zirconate is obtained. Compared with the traditional detection method (respectively measuring the contents of calcium and zirconium in a sample and then calculating the molar ratio), the method provided by the invention omits complicated steps, can quickly and intuitively measure the molar ratio of calcium to zirconium, and has high accuracy and good stability.
The test result shows that the calcium-zirconium molar ratio result can be directly obtained by the test method of the invention through an instrument, the instrument continuously tests the same sample for 10 times, the relative standard deviation RSD% is below 0.051%, and the instrument stability is higher; the method of the invention is repeated to prepare 7 groups, the relative standard deviation RSD% of the test result is below 0.068%, and the whole test process shows higher stability. In addition, the relative error of the test value and the actual value is below 0.15%, and the accuracy is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a graph showing the relationship between the heat loss of a flux and the temperature of a molten sample;
FIG. 2 is a graph showing the relationship between flux weight and calcium-zirconium ratio;
FIG. 3 is a schematic diagram of the operation of selecting the intensity ratio of two elements;
FIG. 4 is a graph showing the inputs of Ca and Zr to the software during fitting.
Detailed Description
The invention provides a method for determining the molar ratio of calcium to zirconium in calcium zirconate, which comprises the following steps:
a) setting a series of different calcium-zirconium molar ratios, and mixing zirconium dioxide and calcium carbonate according to the set calcium-zirconium molar ratios to obtain a series of standard products with different calcium-zirconium molar ratios;
b) mixing the standard substance with a fluxing agent and a release agent, and preparing a sample by a high-frequency sample melting machine to obtain a series of standard fuse pieces;
c) building a standard:
respectively putting the series of standard fuse pieces into XRF (X-ray fluorescence), measuring the X-ray signal intensity ratio of a series of calcium-zirconium elements, and fitting the signal intensity ratio with the corresponding calcium-zirconium molar ratio by XRF analysis software to obtain an XRF standard curve;
d) testing a sample to be tested:
placing the calcium zirconate to-be-tested fuse piece into XRF for testing, and automatically obtaining the molar ratio of calcium to zirconium by XRF analysis software;
the calcium zirconate to-be-detected fuse piece is prepared by the following preparation method:
and mixing the calcium zirconate sample to be tested with a fluxing agent and a release agent, and preparing the sample by using a high-frequency melting machine to obtain the calcium zirconate melting sheet to be tested.
According to the method for determining the molar ratio of calcium to zirconium in calcium zirconate provided by the invention, a standard curve is established by directly fitting the signal intensity ratio of calcium to zirconium to the molar ratio, the molar weight of Zr is defaulted to 1, and the molar weight of Ca is output as the result of the molar ratio of Ca to Zr, so that the molar ratio of Ca to Zr of calcium zirconate is directly obtained; or by replacing the relationship between Ca and Zr according to the above process, the Zr/Ca molar ratio of the calcium zirconate is obtained. Compared with the traditional detection method (respectively measuring the contents of calcium and zirconium in a sample and then calculating the molar ratio), the method provided by the invention omits complicated steps, can quickly and intuitively measure the molar ratio of calcium to zirconium, and has high accuracy and good stability.
Concerning step a): setting a series of different calcium-zirconium molar ratios, and mixing zirconium dioxide and calcium carbonate according to the set calcium-zirconium molar ratios to obtain a series of standard products with different calcium-zirconium molar ratios.
Step a) of the invention is selection and preparation of standard substances before establishing standards (establishing standard curves). In the invention, zirconium dioxide and calcium carbonate are selected as raw materials of the standard product. According to the invention, a series of different calcium-zirconium molar ratios are set firstly, and zirconium dioxide and calcium carbonate are mixed according to the set values respectively to obtain a series of standard products corresponding to the calcium-zirconium molar ratios. The method for mixing zirconium dioxide and calcium carbonate is not particularly limited, and the zirconium dioxide and the calcium carbonate can be uniformly mixed.
In the present invention, the calcium-zirconium molar ratio may be a Ca/Zr molar ratio (i.e., a Ca/Zr molar ratio) or a Zr/Ca molar ratio (i.e., a Zr/Ca molar ratio). In some embodiments of the invention, the calcium zirconium molar ratio is a Ca/Zr molar ratio (i.e., a Ca: Zr molar ratio).
In the present invention, the set series of calcium-zirconium molar ratios are preferably decimal fractions of ten thousands of bits, i.e. four digits after decimal fraction. In the present invention, the set series of different calcium-zirconium molar ratios is preferably selected from 0.9650 to 1.0000. In some embodiments of the invention, 8 different calcium zirconium mole ratios were set, 0.9650, 0.9699, 0.9752, 0.9802, 0.9851, 0.9902, 0.9950, 0.9998, respectively.
Concerning step b): and mixing the standard substance with a fluxing agent and a release agent, and preparing a sample by using a high-frequency melting machine to obtain a series of standard fuse pieces.
In the present invention, the standard substance is preferably subjected to a pretreatment before being mixed with other materials. The pretreatment is heat treatment, and the treatment temperature is 105-150 ℃, more preferably 150 ℃; the treatment time is 30-60 min, and more preferably 30 min.
In the present invention, the flux is preferably a mixture of lithium tetraborate and lithium metaborate. Wherein the mass ratio of the lithium tetraborate in the flux is preferably 67%. In the invention, the mass ratio of the standard substance to the fluxing agent is preferably (0.4-0.8) to (4-8); the mass ratio is more preferably 1: 10, wherein the dosage of the standard substance is 0.4-0.8 g.
In the present invention, the release agent is preferably an aqueous solution of anhydrous lithium bromide. In the present invention, the concentration of anhydrous lithium bromide in the aqueous solution of anhydrous lithium bromide is preferably 30.5g/50 mL. In the invention, the mass ratio of the release agent to the standard substance is preferably (0.45-0.55) to (0.4-0.8), and more preferably (0.45-0.55) to 0.6.
In the present invention, the mixing process is preferably: and (3) putting the standard substance and the fluxing agent into a crucible, uniformly stirring, and dripping a release agent. Wherein the crucible is preferably a platinum crucible.
According to the invention, after the materials are mixed, the mixture is put into a high-frequency melting machine for sample preparation, so that the standard melting piece is obtained. In some embodiments of the invention, the high frequency fusion model used is analymate-V4D +. In the invention, the sample preparation conditions for preparing the standard substance into the standard fuse piece by using the high-frequency fusion machine are preferably as follows: the sample melting temperature is 1100-1200 ℃, and 1170 ℃ is more preferable; the front standing time is 200-300 s, and more preferably 240 s; the swing time is 550-650 s, and more preferably 600 s. In the invention, a system adopted by sample preparation of sample melting equipment is as follows: first heat → second heat → melting, wherein, in the first heat and the second heat, only heating is carried out, but the melting crucible keeps still, when entering the melting process, the crucible can automatically rotate and swing back and forth according to the set degree, so that the melted sample wafer is more uniform. The sample melting process set in the invention is as follows: the first heating time is 0, the second heating is directly carried out, the time corresponding to the second heating is the previous standing time, then the melting is carried out, and the time corresponding to the melting stage is the swing time.
The determination of the temperature of the molten sample is obtained through a series of gradient tests, the temperature is the optimal melting temperature, if the temperature of the molten sample is too low, the sample is not completely melted, unpredictable fluctuation can occur in the result, and if the temperature of the molten sample is too high, the final test result is smaller, and the accuracy of the test method is influenced.
Preparing a series of standard products with different calcium-zirconium molar ratios obtained in the step a) according to the process, thereby obtaining a series of standard fusion pieces.
Concerning step c): building a standard: and respectively putting the series of standard fuse pieces into XRF (X-ray fluorescence), measuring the X-ray signal intensity ratio of a series of calcium-zirconium elements, and fitting the signal intensity ratio with the corresponding calcium-zirconium molar ratio by XRF analysis software to obtain an XRF standard curve.
In the invention, the XRF is an X-ray fluorescence spectrometer. The X-ray fluorescence spectrometer mainly comprises: the X-ray detector comprises an X-ray generator (an X-ray tube, a high-voltage power supply and a stable current stabilizer), a light splitting detection system (an analysis crystal, a collimator and a detector) and a counting and recording system. The XRF is equipped with a computer (containing analysis software) connected with the XRF, and is a data processing and instrument state parameter display device of the fluorescence spectrometer, and the display and analysis of the sample scanning pattern are mainly completed through the computer.
In some embodiments of the invention, an XRF (X-ray fluorescence spectrometer) model S8TIGER is used. The XRF was equipped with analytical software model SPECTRAplus (3.0).
In the present invention, the standard fuse pieces are separately placed in the XRF, and the XRF detects the X-ray signal intensity of Ca element and the X-ray signal intensity of Zr element.
Wherein:
the test conditions for the intensity of the X-ray signal of Ca element are preferably as follows:
using the K.alpha.1-HS-MIN line;
voltage: 50 Kv; current: 60 mA;
a collimator: 0.46 dg;
crystal: LiF 200;
a detector: flow Counter.
The test conditions for the X-ray signal intensity of Zr element are preferably as follows:
using the L alpha 1-HS line;
voltage: 30 Kv; current: 100 mA;
a collimator: 0.46 dg;
crystal: PET;
a detector: flow Counter.
In the invention, after XRF detection is finished, a sample scanning map is displayed on a computer, and analysis software can obtain the X-ray signal intensity (I) of Ca elementCa) And the X-ray signal intensity (I) of Zr elementZr) And calculating the X-ray signal intensity ratio (I) of Ca/Zr elementCa/IZr). After a series of standard fuse tests, a series of X-ray signal intensity ratios ((I) of Ca/Zr elements are obtained on analysis softwareCa/IZr)1、(ICa/IZr)2、(ICa/IZr)3、(ICa/IZr)4、……、(ICa/IZr)n)。
Meanwhile, the Ca/Zr molar ratio of each sample is correspondingly recorded on the analysis software, and the software fits the X-ray signal intensity ratios of the series of Ca/Zr elements with the corresponding Ca/Zr molar ratios to obtain an XRF standard curve.
Specifically, the method comprises the following steps: when the molar ratio of calcium to zirconium of the sample is recorded on the software, the molar amount of the Zr element is defaulted to 1 input, and the molar ratio of Ca/Zr is used as the molar amount input of the Ca element (shown in the following table 1); the resulting curve is fitted and formally viewed as the X-ray signal intensity ratio (I) of the Ca/Zr elementCa/IZr) Standard curve between the molar amounts of Ca element (signal intensity ratio is plotted on the ordinate and the molar amount of Ca element is plotted on the ordinate), which actually represents the X-ray signal intensity ratio (I) of Ca/Zr elementCa/IZr) Standard curve between Ca/Zr molar ratios.
Table 1 shows the form of the molar amount of the elements ca and zr in the XRF software simulation
Figure BDA0003265676970000091
In the present invention, the same applies to the case where the Ca element and the Zr element are reversed, that is, the relationship between the Ca element and the Zr element is substituted. That is, the X-ray signal intensity ratio (I) of Zr/Ca element was obtainedZr/ICa) When the molar ratio of calcium to zirconium of the sample is recorded on the software, the molar amount of Ca element is input as 1 by default, and the Zr/Ca molar ratio is input as the molar amount of Zr element; the resulting curve is fitted and formally viewed as the X-ray signal intensity ratio (I) of the Zr/Ca elementZr/ICa) Standard curve between the molar amounts of Zr element (signal intensity ratio is plotted on the ordinate and the molar amount of Zr element is plotted on the ordinate), actually representing the X-ray signal intensity ratio (I) of Zr/Ca elementZr/ICa) -standard curve between Zr/Ca molar ratios. That is, the method can fit a standard curve of the Ca/Zr molar ratio, and obtain the Ca/Zr molar ratio of a sample when an unknown sample to be tested is tested subsequently; and fitting a standard curve of the Zr/Ca molar ratio, and obtaining the Zr/Ca molar ratio of the sample when the unknown sample to be tested is tested subsequently.
In the invention, the formula of the XRF standard curve obtained by fitting is shown as formula (1):
i-2.251 × (C-0.0581) formula (1);
wherein:
i is the X-ray signal intensity ratio of calcium and zirconium elements;
c is the molar ratio of calcium to zirconium.
The I can be the X-ray signal intensity ratio I of Ca/Zr elementCa/IZrThe X-ray signal intensity ratio I of Zr/Ca element may be setZr/ICa(ii) a C may be a molar ratio of Ca/Zr element or a molar ratio of Zr/Ca element; the relationship between Ca and Zr is only required to be matched.
The standard deviation of the standard curve is 0.0011%, and the square R of the correlation coefficient2Is 0.993.
Concerning step d): testing a sample to be tested: and (3) placing the to-be-tested calcium zirconate melting piece into XRF for testing, and automatically obtaining the molar ratio of calcium to zirconium by XRF analysis software.
In the invention, the calcium zirconate to-be-detected fuse piece is prepared by the following preparation method: and mixing the calcium zirconate sample to be tested with a fluxing agent and a release agent, and preparing the sample by using a high-frequency melting machine to obtain the calcium zirconate melting sheet to be tested.
In the invention, the calcium zirconate sample to be tested is preferably pretreated before being mixed with other materials. The pretreatment is heat treatment, and the treatment temperature is 200-400 ℃, and more preferably 400 ℃; the treatment time is 30-60 min, and more preferably 30 min. The invention pretreats the standard substance and the sample to be tested, pretreats the standard substance and the sample to be tested under different conditions, removes some additives or organic matters added or introduced in the production process through the pretreatment, and the substances are not contained in the melting of the standard sample, so that the difference between the weight of the sample measured in the actual detection and the weight measured in the melting of the standard sample is caused.
In the invention, the types of the fluxing agent and the release agent, the dosage of the calcium zirconate sample to be tested, the fluxing agent and the release agent, sample preparation conditions and the like are consistent with those of the standard substance melt piece preparation. The method comprises the following specific steps:
the fluxing agent is preferably a mixture of lithium tetraborate and lithium metaborate. Wherein the mass ratio of the lithium tetraborate in the flux is preferably 67%. In the invention, the mass ratio of the calcium zirconate sample to be detected to the fluxing agent is preferably (0.4-0.8) to (4-8); the mass ratio is more preferably 1: 10, wherein the dosage of the calcium zirconate sample to be measured is 0.4-0.8 g.
The release agent is preferably an aqueous solution of anhydrous lithium bromide. In the present invention, the concentration of anhydrous lithium bromide in the aqueous solution of anhydrous lithium bromide is preferably 30.5g/50 mL. In the invention, the mass ratio of the release agent to the sample to be detected of the calcium zirconate is preferably (0.45-0.55) to (0.4-0.8), and more preferably (0.45-0.55) to 0.6.
The sample preparation conditions are preferably as follows: the sample melting temperature is 1100-1200 ℃, and 1170 ℃ is more preferable; the front standing time is 200-300 s, and more preferably 240 s; the swing time is 550-650 s, and more preferably 600 s.
In the invention, the to-be-tested calcium zirconate melting piece is placed into XRF for testing, and the XRF analysis software automatically obtains the molar ratio of calcium to zirconium. Specifically, the XRF test and analysis obtains the X-ray signal intensity ratio of calcium and zirconium elements in a sample to be tested, and the X-ray signal intensity ratio can be automatically substituted into the established XRF standard curve, so that the molar ratio of calcium and zirconium can be automatically obtained.
Specifically, in the XRF analysis software, the molar amount of Zr is defaulted to 1, and the molar amount of Ca is output as a result of the molar ratio of Ca to Zr, and the obtained output result is the molar ratio of Ca to Zr, that is, the molar ratio of Ca to Zr of calcium zirconate is directly output through the software. Similarly, in the present invention, the same applies to the case where the Ca element and the Zr element are reversed, that is, when the molar amount of Ca is assumed to be 1 and the molar amount of Zr is outputted as a result of the Zr/Ca molar ratio in the XRF analysis software, the Zr/Ca molar ratio of calcium zirconate is directly obtained.
In the prior art, the molar ratios of the elements are generally not directly obtainable, and are generally as follows: respectively obtaining a standard curve of Ca element signal intensity and molar mass and a standard curve of Zr element signal intensity and molar mass by software, then respectively testing the molar mass of Ca element and the molar mass of Zr element of an unknown sample to be tested, and finally obtaining the molar ratio by manual calculation. The method is complex, time-consuming and labor-consuming, and the testing method provided by the invention can directly obtain the Ca/Zr molar ratio result, so that the step of converting the molar ratio after the molar weight result is measured is omitted.
In the above-described measuring method of the present invention, the temperature is controlled by monitoring the heat loss before and after the flux is burned (i.e., before and after the sample is melted) when the sample is prepared by the high-frequency sample melting machine. The high-frequency sample melting machine adopted by the invention heats the platinum crucible in an induction heating mode, and the working temperature of the platinum crucible cannot be accurately obtained in a better mode at present, and the effect of the traditional temperature measuring ring or the infrared thermometer is not good. Whether the set temperature is consistent with the actual working temperature or not and whether the left and right temperatures of the sample melting equipment are consistent or not are initially unclear. Moreover, the longer the platinum crucible is used, the more serious the loss is, and certain influence can be caused on the working temperature. Therefore, the loss amount of the fluxing agent before and after ignition after the platinum crucible is heated is adopted to replace the temperature during the representation work. The present invention determines the above-described manner of controlling the temperature through experimentation and exploration. The method comprises the following specific steps: the applicant finds that the most intuitive influence caused by different sample melting temperatures of the high-frequency sample melting machine is different in heat loss of the fluxing agent, and the influence of the different sample melting temperatures of the high-frequency sample melting machine on the heat loss of the fluxing agent is monitored by the invention, so that the result is shown in fig. 1, and fig. 1 is a graph showing the relation of the heat loss of the fluxing agent with the change of the sample melting temperature. It can be seen that the higher the temperature, the greater the heat loss. Meanwhile, the method simulates the difference of heat loss by changing the flux weight so as to judge whether the heat loss of the flux has influence on the result, the result shows that the heat loss of the flux has influence on the calcium-zirconium ratio detection result, and the result is shown in fig. 2, and fig. 2 is a relation graph of the flux weight and the calcium-zirconium ratio. The above studies show that the relationship between the three is roughly: the temperature rises, the heat loss of the fluxing agent is increased, and the final detection result is reduced. Therefore, as long as the heat loss of the fluxing agent is controlled to be consistent with the heat loss when the standard sample wafer is established (the heat loss value of the fluxing agent can be adjusted by directly adjusting the set temperature and the relative position of the platinum crucible and the heating copper tube, namely the working temperature is controlled), the stability of the detection result can be basically ensured.
The invention provides a method for determining the molar ratio of calcium to zirconium in calcium zirconate, which comprises the steps of establishing a standard curve by directly fitting the signal intensity ratio of calcium to zirconium to the molar ratio, defaulting the molar amount of Zr to 1, and outputting the molar amount of Ca as the result of the molar ratio of Ca to Zr, so as to directly obtain the molar ratio of Ca to Zr of the calcium zirconate; or by replacing the relationship between Ca and Zr according to the above process, the Zr/Ca molar ratio of the calcium zirconate is obtained. Compared with the traditional detection method (respectively measuring the contents of calcium and zirconium in a sample and then calculating the molar ratio), the method provided by the invention omits complicated steps, can quickly and intuitively measure the molar ratio of calcium to zirconium, and has high accuracy and good stability.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In the following examples, the main instruments and reagents used are as follows: x-ray fluorescence spectrometer: model S8TIGER, supplied by Bruker AXS, Inc., Germany. High-frequency melting machine: model analymate-V4D +, available from Sci Tech, Inc., Beijing, of the quiet remote century. Lithium tetraborate (analytically pure), lithium metaborate (analytically pure).
Example 1
1. Test procedure
S1, setting a series of different Ca/Zr molar ratios, and mixing zirconium dioxide and calcium carbonate according to the set ratio to obtain a series of standard products with different Ca/Zr molar ratios.
The set values are as follows: 0.9650, 0.9699, 0.9752, 0.9802, 0.9851, 0.9902, 0.9950, 0.9998.
S2, treating the standard substance at 150 ℃ for 30min to obtain a pretreatment standard substance.
0.6000g +/-0.0001 g of the pretreatment standard and 6.0000g +/-0.0001 g of the fluxing agent (67 percent of lithium tetraborate and 33 percent of lithium metaborate) are weighed and put into a platinum crucible and stirred uniformly. Then, 0.5. + -. 0.05g of a mold release agent (an anhydrous lithium bromide solution, concentration: 30.5g/50mL) was added dropwise. Then, putting the sample into a high-frequency melt machine for sample preparation under the conditions as follows: the temperature of the molten sample is 1170 ℃, the pre-standing time is 240s, and the swinging time is 600 s. Obtaining the standard fuse block.
S3, establishing a standard:
and (4) respectively putting the series of standard fuse pieces obtained in the step S2 into XRF, measuring a series of X-ray signal intensity ratios of Ca/Zr elements, and fitting the signal intensity ratios with corresponding Ca/Zr molar ratios by analysis software of the XRF to obtain an XRF standard curve. Specifically, the method comprises the following steps: inputting the molar weight of the Zr element as 1 by default and inputting the Ca/Zr molar ratio as the molar weight of the Ca element (see figure 4); and selecting the corresponding X-ray signal intensity ratio of Ca/Zr element, and fitting with the molar weight of the input Ca element to obtain an XRF standard curve.
The operation of selecting the intensity ratio of the two elements and the input display effect of calcium and zirconium are respectively shown in fig. 3 and fig. 4, fig. 3 is a schematic diagram of the operation of selecting the intensity ratio of the two elements, and fig. 4 is a display diagram of the input of calcium and zirconium on software during fitting. As can be seen from fig. 4, for each of the 8 standards, the molar amount of Zr was regarded as 1 by default, and the molar amount of Ca element was input as the molar amount of Ca element, which corresponds to the Ca/Zr molar ratio.
The formula of the obtained standard curve is shown as formula (1):
i-2.251 × (C-0.0581) formula (1);
wherein:
i is the X-ray signal intensity ratio of Ca/Zr element;
c is the molar ratio of Ca/Zr elements.
S4, testing the sample to be tested:
and (3) treating the calcium zirconate sample to be tested with the target calcium-zirconium ratio of 0.9725 at 400 ℃ for 30min to obtain a pretreatment sample to be tested. And according to the operation process of the step S2, preparing the pre-treated sample to be tested into the calcium zirconate melt to be tested.
And preparing the pre-treated sample to be tested into a calcium zirconate to be tested fuse piece, putting the calcium zirconate to be tested fuse piece into XRF for testing, wherein the molar weight of Zr is defaulted to 1, and the XRF analysis software directly outputs the Ca/Zr molar ratio to obtain 0.9726.
2. Detection device stability verification
The above calcium zirconate test sample was continuously measured repeatedly for 10 times by the step S4, and the results are shown in table 2:
table 2 example 1 test results of 10 consecutive measurements of the sample
Sample (I) Test sequence Molar ratio of calcium to zirconium
Sample 1 1 0.9731
Sample 1 2 0.9725
Sample 1 3 0.9720
Sample 1 4 0.9729
Sample 1 5 0.9727
Sample 1 6 0.9725
Sample 1 7 0.9720
Sample 1 8 0.9722
Sample 1 9 0.9724
Sample 1 10 0.9726
Mean value 0.9725
Standard deviation of 0.0004
RSD％ 0.037％
As can be seen from the test results in Table 2 above, the relative standard deviation (RSD%) of the continuous measurement using the same sample is low, which proves that the device of the present invention has good stability.
3. Test method stability verification
In the invention, the sample melting equipment can melt two samples at one time, the samples are divided into a left side and a right side, the positions of the left and the right samples have certain temperature difference, the two samples on the left and the right sides are independently tested in the testing process, the average value of the two samples is taken as the testing result, and the testing result in the table 3 is also the average value of the testing results of the two samples on the left and the right sides.
According to the procedure, 7 sets of samples were repeated for each sample, and the left and right parallel samples of each set were measured. The test results are shown in Table 3.
Test results for the set of samples in Table 37
Sample (I) Ca/Zr molar ratio for the left hand sample Ca/Zr molar ratio for the right sample Ca/Zr molar ratio (mean)
Group 1 0.9726 0.9715 0.9721
2 groups of 0.9710 0.9732 0.9721
Group 3 0.9734 0.9733 0.9734
4 groups of 0.9721 0.9731 0.9726
5 groups of 0.9708 0.9718 0.9713
6 groups of 0.9734 0.9723 0.9729
7 groups of 0.9731 0.9713 0.9722
Mean value 0.9723 0.9724 0.9724
Standard deviation of 0.0011 0.0008 0.0007
RSD％ 0.112％ 0.087％ 0.068％
As can be seen from the test results in Table 3, the relative standard deviation (RSD%) of the Ca/Zr molar ratio test results is lower after the sample preparation is continuously repeated for 7 times, which proves that the stability of the whole detection process of the invention is better.
4. Accuracy verification
The values tested in test 3 were compared with the target Ca/Zr molar ratio, the results are shown in Table 4.
TABLE 47 comparison of sample test results with actual target Ca/Zr molar ratios
Figure BDA0003265676970000151
As can be seen from the test results in Table 4, the absolute value of the relative error between the test value and the actual target value of the 7 groups of samples is below 0.10%, and the accuracy is better.
Example 2
1. Test procedure
S1, setting a series of different Ca/Zr molar ratios, and mixing zirconium dioxide and calcium carbonate according to the set ratio to obtain a series of standard products with different Ca/Zr molar ratios.
The set values are as follows: 0.9650, 0.9699, 0.9752, 0.9802, 0.9851, 0.9902, 0.9950, 0.999.
S2, treating the standard substance at 150 ℃ for 30min to obtain a pretreatment standard substance.
0.6000g +/-0.0001 g of the pretreatment standard and 6.0000g +/-0.0001 g of the fluxing agent (67 percent of lithium tetraborate and 33 percent of lithium metaborate) are weighed and put into a platinum crucible and stirred uniformly. Then, 0.5. + -. 0.05g of a mold release agent (an anhydrous lithium bromide solution, concentration: 30.5g/50mL) was added dropwise. Then, putting the sample into a high-frequency melt machine for sample preparation under the conditions as follows: the temperature of the molten sample is 1170 ℃, the pre-standing time is 240s, and the swinging time is 600 s. Obtaining the standard fuse block.
S3, establishing a standard:
and (4) respectively putting the series of standard fuse pieces obtained in the step S2 into XRF, measuring a series of X-ray signal intensity ratios of Ca/Zr elements, and fitting the signal intensity ratios with corresponding Ca/Zr molar ratios by analysis software of the XRF to obtain an XRF standard curve. Specifically, the method comprises the following steps: inputting the molar weight of the Zr element as 1 by default, and inputting the Ca/Zr molar ratio as the molar weight of the Ca element; and selecting the corresponding X-ray signal intensity ratio of Ca/Zr element, and fitting with the molar weight of the input Ca element to obtain an XRF standard curve.
The formula of the obtained standard curve is shown in formula (1):
i-2.251 × (C-0.0581) formula (1);
wherein:
i is the X-ray signal intensity ratio of Ca/Zr element;
c is the molar ratio of Ca/Zr elements.
S4, testing the sample to be tested:
and (3) treating the calcium zirconate sample to be tested with the target calcium-zirconium ratio of 0.9950 at 400 ℃ for 30min to obtain a pretreatment sample to be tested. And according to the operation process of the step S2, preparing the pre-treated sample to be tested into the calcium zirconate melt to be tested.
And preparing the pre-treated sample into a calcium zirconate to-be-tested fuse piece, placing the calcium zirconate to-be-tested fuse piece into XRF for testing, wherein the molar weight of Zr is defaulted to 1, and the XRF analysis software directly outputs the Ca/Zr molar ratio to obtain the Ca/Zr molar ratio of 0.9961.
2. Detection device stability verification
The above calcium zirconate test sample was continuously measured repeatedly 10 times through step S4, and the results are shown in table 5:
table 5 test results of example 2 samples measured 10 times in succession
Sample (I) Test sequence Molar ratio of calcium to zirconium
Sample 2 1 0.9951
Sample 2 2 0.9957
Sample 2 3 0.9959
Sample 2 4 0.9944
Sample 2 5 0.9946
Sample 2 6 0.9947
Sample 2 7 0.9953
Sample 2 8 0.9950
Sample 2 9 0.9956
Sample 2 10 0.9950
Mean value 0.9951
Standard deviation of 0.0005
RSD％ 0.051％
As can be seen from the test results of Table 5 above, the relative standard deviation (RSD%) of the continuous measurement using the same sample is low, which proves that the device of the present invention has good stability.
3. Test method stability verification
According to the procedure, 7 sets of samples were repeated for each sample, and the left and right parallel samples of each set were measured. The test results are shown in Table 6.
Test results for the group of samples in Table 67
Sample (I) Ca/Zr molar ratio for the left hand sample Ca/Zr molar ratio for the right sample Ca/Zr molar ratio (mean)
Group 1 0.9961 0.9966 0.9964
2 groups of 0.9943 0.9954 0.9949
Group 3 0.9955 0.9959 0.9957
4 groups of 0.9956 0.9947 0.9952
5 groups of 0.9951 0.9944 0.9948
6 groups of 0.9946 0.9949 0.9948
7 groups of 0.9949 0.9955 0.9952
Mean value 0.9952 0.9953 0.9953
Standard deviation of 0.0006 0.0008 0.0006
RSD％ 0.062％ 0.076％ 0.059％
As can be seen from the test results in Table 6, the relative standard deviation (RSD%) of the Ca/Zr molar ratio test results is lower after the sample preparation is continuously repeated for 7 times, which proves that the stability of the whole detection process of the invention is better.
4. Accuracy verification
The values tested in test 3 were compared with the target Ca/Zr molar ratio, the results are shown in Table 7.
TABLE 77 comparison of sample test results with actual target Ca/Zr molar ratios
Figure BDA0003265676970000171
As can be seen from the test results in Table 4, the relative error between the test value and the actual target value of 7 groups of samples is below 0.15%, and the accuracy is better.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (10)

1. A method for determining the molar ratio of calcium to zirconium in calcium zirconate is characterized by comprising the following steps:
a) setting a series of different calcium-zirconium molar ratios, and mixing zirconium dioxide and calcium carbonate according to the set calcium-zirconium molar ratios to obtain a series of standard products with different calcium-zirconium molar ratios;
b) mixing the standard substance with a fluxing agent and a release agent, and preparing a sample by a high-frequency sample melting machine to obtain a series of standard fuse pieces;
c) building a standard:
respectively putting the series of standard fuse pieces into XRF (X-ray fluorescence), measuring the X-ray signal intensity ratio of a series of calcium-zirconium elements, and fitting the signal intensity ratio with the corresponding calcium-zirconium molar ratio by XRF analysis software to obtain an XRF standard curve;
d) testing a sample to be tested:
placing the calcium zirconate to-be-tested fuse piece into XRF for testing, and automatically obtaining the molar ratio of calcium to zirconium by XRF analysis software;
the calcium zirconate to-be-detected fuse piece is prepared by the following preparation method:
and mixing the calcium zirconate sample to be tested with a fluxing agent and a release agent, and preparing the sample by using a high-frequency melting machine to obtain the calcium zirconate melting sheet to be tested.
2. The method of claim 1,
in the standard establishing process of the step c), in XRF analysis software, defaulting the molar weight of Zr element as 1 and inputting the molar weight of Ca element according to the Ca/Zr molar ratio; selecting the X-ray signal intensity ratio of the corresponding Ca/Zr element, and fitting the X-ray signal intensity ratio with the molar weight of the input Ca element to obtain an XRF standard curve; the XRF standard curve actually represents a standard curve of an X-ray signal intensity ratio of Ca/Zr element and a Ca/Zr molar ratio;
in the step d), in XRF analysis software, the Zr molar weight is defaulted to 1, and the Ca molar weight is output as the Ca/Zr molar ratio result to directly obtain the Ca/Zr molar ratio of the calcium zirconate;
or
In the standard establishing process of the step c), defaulting the molar weight of Ca element as 1 and inputting the molar weight of Zr/Ca element as the molar weight input of Zr element in XRF analysis software; selecting the corresponding X-ray signal intensity ratio of Zr/Ca element, and fitting the X-ray signal intensity ratio with the input molar weight of the Zr element to obtain an XRF standard curve, wherein the XRF standard curve actually represents the standard curve of the X-ray signal intensity ratio of the Zr/Ca element and the Zr/Ca molar ratio;
in step d), in the XRF analysis software, the Ca molar quantity is defaulted to 1, and the Zr molar quantity is output as the Zr/Ca molar ratio result to directly obtain the Zr/Ca molar ratio of the calcium zirconate.
3. The method according to claim 1, wherein the test conditions for the X-ray signal intensity of Ca element in XRF are set as follows:
using the K.alpha.1-HS-MIN line;
voltage: 50 Kv; current: 60 mA;
a collimator: 0.46 dg;
crystal: LiF 200;
a detector: flow Counter;
in the XRF, the test conditions of the X-ray signal intensity of the Zr element are set as follows:
using the L alpha 1-HS line;
voltage: 30 Kv; current: 100 mA;
a collimator: 0.46 dg;
crystal: PET;
a detector: flow Counter.
4. The method of claim 1, wherein the standard is prepared into the standard fuse block under the following sample preparation conditions:
the sample melting temperature is: 1100-1200 ℃,
the front standing time is as follows: the time of the reaction is 200 to 300s,
the swinging time is as follows: 550-650 s;
the standard substance is pretreated before being mixed with fluxing agent and release agent;
the pretreatment of the standard substance comprises the following steps: heat treatment is carried out for 30-60 min at 105-150 ℃;
the sample preparation conditions for preparing the calcium zirconate sample to be detected into the calcium zirconate melt sheet to be detected are as follows:
the sample melting temperature is: 1100-1200 ℃,
the front standing time is as follows: the time of the reaction is 200 to 300s,
the swinging time is as follows: 550-650 s;
the calcium zirconate sample to be tested is pretreated before being mixed with a fluxing agent and a release agent;
the pretreatment of the calcium zirconate sample to be tested comprises the following steps: heat treatment is carried out for 30-60 min at 200-400 ℃.
5. The method according to claim 1 or 4, wherein the standard is prepared into the standard fuse piece under the following sample preparation conditions:
the sample melting temperature is: at 1170 c,
the front standing time is as follows: 240s of the number of the first and second groups,
the swinging time is as follows: 600 s;
the pretreatment of the standard substance comprises the following steps: heat treating at 150 deg.C for 30 min;
the sample preparation conditions for preparing the calcium zirconate sample to be detected into the calcium zirconate melt sheet to be detected are as follows:
the sample melting temperature is: at 1170 c,
the front standing time is as follows: 240s of the number of the first and second groups,
the swinging time is as follows: 600 s;
the pretreatment of the calcium zirconate sample to be tested comprises the following steps: heat treatment at 400 deg.C for 30 min.
6. The method according to claim 1, wherein in step c), the XRF standard curve is formulated as formula (1):
i-2.251 × (C-0.0581) formula (1);
wherein:
i is the X-ray signal intensity ratio of calcium and zirconium elements;
c is the molar ratio of calcium to zirconium.
7. The method of claim 1, wherein the fluxing agent is a mixture of lithium tetraborate and lithium metaborate;
the release agent is an aqueous solution of anhydrous lithium bromide.
8. The method of claim 7, wherein the lithium tetraborate is present in the flux in a mass ratio of 67%;
the concentration of anhydrous lithium bromide in the anhydrous lithium bromide aqueous solution is 30.5g/50 mL.
9. The method of claim 1 or 7, wherein in the preparation of the standard melt sheet:
the mass ratio of the standard substance to the fluxing agent is (0.4-0.8) to (4-8);
the mass ratio of the release agent to the standard substance is (0.45-0.55) to (0.4-0.8);
in the preparation of the calcium carbonate to-be-detected fuse piece:
the mass ratio of the calcium zirconate sample to be detected to the fluxing agent is (0.4-0.8) to (4-8);
the mass ratio of the release agent to the calcium zirconate sample to be detected is (0.45-0.55) to (0.4-0.8).
10. The method according to claim 1, wherein in step a), the molar ratio of calcium to zirconium is set to a decimal fraction of ten thousand;
the set different calcium-zirconium molar ratios are selected from 0.9650-1.0000.
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