CN117517388A - Method for measuring crystallization temperature of high-level waste liquid glass solidified body - Google Patents
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- 238000002425 crystallisation Methods 0.000 title claims abstract description 162
- 230000008025 crystallization Effects 0.000 title claims abstract description 162
- 238000000034 method Methods 0.000 title claims abstract description 85
- 239000002927 high level radioactive waste Substances 0.000 title claims abstract description 20
- 235000019353 potassium silicate Nutrition 0.000 title claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 92
- 238000012360 testing method Methods 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 230000000630 rising effect Effects 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001938 differential scanning calorimetry curve Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 102000004169 proteins and genes Human genes 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims 4
- 239000007787 solid Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 2
- 238000004031 devitrification Methods 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
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- G01N25/12—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering of critical point; of other phase change
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- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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Abstract
The invention discloses a method for measuring crystallization temperature of a high-level waste liquid glass solidified body, and belongs to the technical field of glass detection. The method comprises the following steps: measuring the crystallization temperature of the calibration sample by a gradient furnace method; respectively crushing, sieving and grinding the glass solidified body calibration sample into powder to obtain a sample with the particle size of more than 150 meshes; the temperature rising rate of the DTA/DSC is more than 30 ℃/min, and the sample is respectively tested to obtain the extrapolated crystallization starting temperature of the calibration sample; drawing a relation curve by taking the extrapolated crystallization starting temperature measured by a DTA/DSC as an abscissa and the crystallization temperature measured by a gradient furnace method as an ordinate; and selecting a glass solidified body sample to be analyzed, measuring the extrapolated crystallization starting temperature of the sample in the same way, and substituting the extrapolated crystallization starting temperature into a relation curve to obtain the crystallization temperature of the sample. According to the invention, the devitrification initial temperature of the actual glass solidified body is brought into the correlation curve to calculate and obtain the devitrification temperature of the actual glass solidified body, the measuring method is quick and simple, and the accuracy of the test result is high.
Description
Technical Field
The invention relates to the technical field of glass detection, in particular to a method for measuring crystallization temperature of a high-level waste liquid glass solidified body.
Background
At present, nuclear energy application is changed into a power stack from a production stack, and the power stack adopts a nitric acid-based high-level waste liquid process, unlike the previous high-level waste liquid process of production stack, so that the problem that yellow phase crystallization is easy to occur in the early-stage high-level waste liquid glass solidification process of production stack sulfuric acid is solved. In order to avoid crystallization of the glass solidified body caused by nuclide decay and overall temperature rise in a short-term placement time and damage to the performance of a finished product of the glass solidified body, the quality control of the high-level waste liquid glass solidified body heat treatment process is realized by adopting an index of evaluating the crystallization temperature of the glass solidified body.
The existing glass solidified body crystallization temperature test mode is as follows: the DTA/DSC method adopts the crystallization exothermic peak temperature in a calorimetric curve measured at a heating rate of 10 ℃/min as the crystallization temperature. The method is used for evaluating the glass solidified body easy to crystallize, belongs to a mature and accepted testing method, but along with the scene change generated by high-level waste liquid, the crystallization behavior of the existing glass solidified body is weak, the crystallization peak temperature is difficult to obtain on a calorimetric curve, and the method is not suitable for evaluating the crystallization temperature.
In the prior art, when the crystallization temperature of glass is measured, a gradient furnace method is generally adopted, firstly, crushed glass is put into a gradient furnace to be heated and kept for a period of time, and then is observed by a microscope after being cooled, so as to determine the crystallization temperature, for example, patent CN108663393A, CN116068012A, CN110455798A and the like. However, in the prior art, the crystallization temperature is measured by a gradient furnace method, the crystallization temperature of the high-level waste liquid glass solidified body is not measured by the gradient furnace method, the measurement result of the method allows errors within +/-10 ℃, the time consumption is long in the measurement process of the gradient furnace method, and the energy consumption is increased.
Compared with the crystallization temperature value measured by the DTA/DSC method, the crystallization temperature measured by the gradient furnace method is generally considered to be higher in accuracy in the industry, but is relatively less in application due to longer time consumption, complicated testing method and high energy consumption.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a method for measuring the crystallization temperature of a high-level waste liquid glass solidified body.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a method for measuring crystallization temperature of a high-level waste liquid glass solidified body, which comprises the following steps:
step S1: selecting multiple glass solidified body calibration samples with different crystallization temperatures, and respectively measuring the crystallization temperatures of the calibration samples by using a gradient furnace method;
step S2: respectively crushing, sieving and grinding the glass solidified body calibration sample into powder, and obtaining a sample with the particle size of more than 150 meshes through sieving; the obtained powder sample is not subjected to other treatment, and is not polluted in the preparation process
Step S3: setting test conditions, respectively testing the samples in the step S2 to obtain DTA/DSC curves, analyzing the DTA/DSC curves, and obtaining the extrapolated crystallization starting temperature of the calibration sample;
step S4: drawing a relation curve by taking the extrapolated crystallization starting temperature measured by a DTA/DSC as an abscissa and the crystallization temperature measured by a gradient furnace method as an ordinate;
step S5: and selecting a glass solidified body sample to be analyzed, carrying out sample treatment in the same crushing mode as in the step S2, measuring the extrapolated crystallization starting temperature of the sample under the same test condition as in the step S3, substituting the extrapolated crystallization starting temperature into a relation curve, and calculating to obtain the crystallization temperature of the sample.
Preferably, before the step S1, the method further includes: crushing a glass solidified body sample to be analyzed, wherein the general crushing mesh is less than 30 meshes, performing a DTA/DSC test, and obtaining the crystallization range of the glass solidified body sample to be analyzed through analyzing a DTA/DSC curve. Through the step, the crystallization temperature of the glass solidified body to be measured can be roughly measured, a calibration sample can be selected according to the numerical value, and the crystallization temperature of the glass solidified body to be measured is covered by the temperature range of the calibration sample, so that a reliable calibration relation is obtained, and further an accurate test result is obtained.
Alternatively, since the crystallization temperature of a general glass solidified body is in the range of 600 ℃ to 750 ℃, the crystallization temperature span of a glass solidified body calibration sample can be selected according to practical experience to be 600 ℃ to 750 ℃, and the number of the glass solidified body calibration samples is more than 3.
Preferably, the number of the glass solidification calibration samples is 5, and the crystallization temperature range comprises a conventional glass solidification extraction crystallization temperature range, or according to the crystallization temperature of the glass solidification to be measured, several calibration samples corresponding to crystallization temperature points are respectively selected above and below the crystallization temperature.
Preferably, in the step S1, glass solidification body calibration samples with different crystallization temperatures are obtained by the following methods:
firstly, collecting different glass solidified body samples, determining crystallization temperatures of the samples through a gradient path method, establishing a crystallization temperature database of the different samples, and then selecting different glass solidified bodies as standard samples according to the glass solidified body samples to be analyzed, wherein the crystallization temperatures of the glass solidified bodies to be analyzed are covered by a crystallization temperature range of a calibration sample.
The glass solidification body calibration sample can be selected according to the crystallization temperature marked by a commercial product (gradient furnace method), or the sample can be prepared according to the crystallization temperature recorded in the literature, so long as the crystallization temperature of the marked calibration sample meets the requirement. Further, in the step S3, DTA/DSC test conditions are as follows: the temperature is raised to 1000 ℃ at the temperature rising speed of 30 ℃/min-45 ℃/min, nitrogen is purged, the nitrogen flow rate is 20mL/min-40mL/min, and the sample weighing is 20mg-30mg.
Preferably, in the step S3, DTA/DSC test conditions are as follows: the temperature is raised to 1000 ℃ at the temperature rising speed of 30 ℃/min-35 ℃/min, nitrogen is purged, the nitrogen flow rate is 40mL/min, and the sample is weighed to be 25mg.
Further, the DTA/DSC curve was analyzed using NETZSCH protein software. Analysis software that is typically self-contained with the test instrument may be used for analysis or drawing software (origin) may be used.
Further, the relationship curve drawn in the step S4 is a linear relationship: t (T) c ＝AT eic +B；
Wherein T is c : crystallization temperature by a gradient furnace method, wherein the crystallization temperature is in units of ℃;
T eic : extrapolating crystallization starting temperature in units of ℃;
a is the slope of the relationship curve;
b is the intercept of the relationship curve.
Preferably, the gradient furnace method is used for respectively measuring the crystallization temperature of the calibration sample, and specifically comprises the following steps: respectively crushing the glass solidified body calibration samples, then putting the glass solidified body calibration samples into a temperature gradient furnace through a platinum boat, and preserving heat for 24 hours or more; after the heat preservation is completed, taking out and cooling the glass solidified body calibration sample; and (5) observing the cooled glass solidified body calibration sample by using a microscope, and determining the crystallization temperature.
Compared with the prior art, the invention has the following beneficial effects:
the method provided by the invention is based on a relation curve method, the crystallization temperature of the glass solidified body is determined by a gradient furnace method, the relation between the crystallization temperature and the crystallization extrapolation initial temperature measured by a DTA/DSC method is established, and the crystallization temperature of the glass solidified body is quantitatively measured. Compared with a gradient furnace method, the method provided by the invention has the advantages that the sampling amount is small, the analysis speed is high after the curve is established, the problem of peak temperature drift caused by analysis condition change of a thermal analyzer can be solved, and the crystallization temperature of the glass solidified body can be accurately and efficiently tested. The method provided by the invention uses the powder with high heating rate, high sample weighing and small particle size as the test condition to improve the response of DTA/DSC to the crystallization behavior of the test glass solidified body, and solves the problem that the peak-out characteristic of the thermal analysis curve of the difficult crystallization glass solidified body is not obvious.
Drawings
FIG. 1 is a graph of a DTA calorimetric curve obtained in step S3 of example 1 of the present invention, corresponding to a calorimetric curve of sample 1# to be measured;
FIG. 2 is a graph showing the relationship between the extrapolated crystallization onset temperature and the crystallization temperature obtained in step S4 of example 1 of the present invention;
FIG. 3 is a graph of DSC calorimetric curve obtained in step S3 of example 2 of the present invention, corresponding to the calorimetric curve of sample No. 2 to be measured;
FIG. 4 is a graph showing the relationship between the extrapolated crystallization onset temperature and the crystallization temperature obtained in step S4 of example 2 of the present invention;
FIG. 5 is a DSC calorimetric curve of the comparative example 1 of the present invention obtained in step S3;
FIG. 6 is a DSC calorimetric curve of the comparative example 2 obtained in step S3 of the present invention;
FIG. 7 is a DSC calorimetric curve of the sample obtained in step S3 of comparative example 3;
FIG. 8 is a DSC calorimetric curve of the sample obtained in step S3 of comparative example 4.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
The materials and reagents used in the present invention are not specifically described and are commercially available.
The invention provides a method for measuring crystallization temperature of a high-level waste liquid glass solidified body, and specific examples are as follows.
In the invention, firstly, different glass solidified body samples are collected, and the crystallization temperature of the samples is determined by a gradient furnace method, specifically: respectively crushing the glass solidified body calibration samples, screening to obtain glass solidified bodies with the particle size smaller than 30 meshes, and then placing the glass solidified bodies into a gradient furnace through a platinum boat, and preserving heat for 72 hours; after the heat preservation is completed, rapidly taking out the glass solidified body calibration sample and cooling at room temperature; observing the cooled glass solidified body calibration sample by utilizing a microscope, marking the crystallization starting position, embedding a temperature fitting formula reflecting the relation between the temperature and the position of the gradient furnace in the adopted gradient furnace software, calculating the crystallization temperature, and establishing a liquidus temperature database of different samples.
Among them, a glass-cured body calibration sample can be purchased commercially or prepared by a literature formulation.
Example 1
A method for measuring crystallization temperature of high-level waste liquid glass solidified body comprises the following steps:
step S1: selecting calibration samples of five crystallization temperature points at 642 ℃, 650 ℃, 660 ℃, 680 ℃ and 710 ℃ from an established database, numbering the calibration samples 1#, the calibration samples 2#, the calibration samples 3#, the calibration samples 4#, and the calibration samples 5#, and carrying out value setting on the calibration samples by using a gradient furnace method, wherein the specific steps are as follows:
respectively crushing the glass solidified body calibration samples, screening to obtain glass solidified bodies with the particle size smaller than 30 meshes, and then placing the glass solidified bodies into a gradient furnace through a platinum boat, and preserving heat for 72 hours; after the heat preservation is completed, rapidly taking out the glass solidified body calibration sample and cooling at room temperature; observing the crystallization position of the cooled glass solidified body calibration sample by using a microscope, and determining the crystallization temperature, wherein the specific test result is shown in table 1;
step S2: respectively crushing the glass solidified body calibration sample, sieving the crushed sample to obtain glass solidified body calibration sample powder with the particle size of more than 150 meshes, and ensuring that the obtained sample in the powder form is not polluted in the preparation process;
step S3: respectively testing the prepared calibration sample powder samples by using DTA; setting a test program: the temperature was raised from room temperature to 1000℃at a rate of 35℃per minute, purged with nitrogen, and the flow rate was 40mL/min, and 25mg of the sample was weighed.
Analysis of the measured DTA calorimetric curves using NETZSCH protein software, for example, calibration sample 1# is shown in fig. 1, obtaining extrapolated crystallization onset temperatures for different calibration samples 647.9 ℃, and extrapolated crystallization onset temperatures for other calibration samples are shown in table 1;
TABLE 1
| Sequence number | Crystallization temperature/DEGC | Crystallization temperature/DEGC of gradient furnace | DTA extrapolated crystallization onset temperature/. Degree.C |
| Calibration sample 1# | 642 | 642.3 | 647.9 |
| Calibration sample 2# | 650 | 653.2 | 657.9 |
| Calibration sample 3# | 660 | 665.7 | 673.2 |
| Calibration sample 4# | 680 | 680.4 | 685.3 |
| Calibration sample 5# | 710 | 708.9 | 713.6 |
Step S4: drawing a relation curve of the extrapolated crystallization starting temperature obtained by the DTA method and the crystallization temperature of the fixed value of the gradient furnace method, performing curve fitting by taking the extrapolated crystallization starting temperature as an abscissa and the crystallization temperature as an ordinate, and establishing the relation curve as shown in figure 2 as follows:
T c ＝1.3544T eic -197.42；R 2 ＝0.9948；
wherein T is c : crystallization temperature by a gradient furnace method, wherein the crystallization temperature is in units of ℃;
T eic : extrapolating crystallization starting temperature in units of ℃;
step S5: selecting 4 glass solidified body samples as samples to be tested, processing the samples to be tested in the same crushing mode as the step S2, measuring the initial temperature of extrapolated crystallization of the samples under the same test conditions as the step S3, and thenThen substituting the obtained product into the relation curve of the step S4, and respectively calculating crystallization temperatures T of 4 samples c . Without verifying the accuracy of the results, the inventors tested these 4 glass solidified body samples by using a gradient furnace method to obtain corresponding crystallization temperatures, and the results are shown in table 2.
TABLE 2
As is clear from Table 2, the crystallization temperature obtained by the method of the present invention has a front-back error of + -2.8deg.C or less, and the error is smaller than the crystallization temperature measured by the gradient furnace method, thereby satisfying the requirements of the art. In addition, the method only needs to draw a working curve once, and when the crystallization temperature is measured subsequently, the crystallization temperature data which is not much different from the gradient furnace method can be obtained by measuring the extrapolated crystallization starting temperature of the quantitative thermal curve, so that the method is short in use time and convenient and quick.
Example 2
A method for measuring crystallization temperature of high-level waste liquid glass solidified body comprises the following steps:
step S1: selecting calibration samples of five crystallization temperature points at 642 ℃, 650 ℃, 660 ℃, 680 ℃ and 710 ℃ from an established database, numbering the calibration samples 1#, the calibration samples 2#, the calibration samples 3#, the calibration samples 4#, and the calibration samples 5#, and carrying out value setting on the calibration samples by using a gradient furnace method, wherein the specific steps are as follows:
respectively crushing the glass solidified body calibration samples, screening to obtain glass solidified bodies with the particle size smaller than 30 meshes, and then placing the glass solidified bodies into a gradient furnace through a platinum boat, and preserving heat for 72 hours; after the heat preservation is completed, rapidly taking out the glass solidified body calibration sample and cooling at room temperature; observing the crystallization position of the cooled glass solidified body calibration sample by using a microscope, and determining the crystallization temperature, wherein the specific test result is shown in Table 3;
step S2: respectively crushing the glass solidified body calibration sample, sieving the crushed sample to obtain glass solidified body calibration sample powder with the particle size more than 325 meshes, and ensuring that the obtained sample in the powder form is not polluted in the preparation process;
step S3: testing the prepared calibration sample powder samples by DSC respectively; setting a test program: the temperature was raised from room temperature to 1000℃at a rate of 35℃per minute, purged with nitrogen, and the flow rate was 40mL/min, and 25mg of the sample was weighed.
Analysis of the measured DSC calorimetric curve using NETZSCH protein software, for example, calibration sample No. 2 is shown in fig. 3, to obtain extrapolated crystallization onset temperatures for different calibration samples 663.8 ℃, and extrapolated crystallization onset temperatures for other calibration samples are shown in table 3;
TABLE 3 Table 3
| Sequence number | Crystallization temperature/DEGC | Crystallization temperature/DEGC of gradient furnace | DSC extrapolated crystallization onset temperature/DEGC |
| Calibration sample 1# | 642 | 642.3 | 652.3 |
| Calibration sample 2# | 650 | 653.2 | 663.8 |
| Calibration sample 3# | 660 | 665.7 | 672.3 |
| Calibration sample 4# | 680 | 680.4 | 685.8 |
| Calibration sample 5# | 710 | 708.9 | 711.3 |
Step S4: drawing a relation curve of the extrapolated crystallization starting temperature obtained by a DSC method and the crystallization temperature of a gradient furnace method fixed value, performing curve fitting by taking the extrapolated crystallization starting temperature as an abscissa and the crystallization temperature as an ordinate, and establishing the relation curve as shown in fig. 4 as follows:
T c ＝0.9044T eic +82.106；R 2 ＝0.9974；
wherein T is c : crystallization temperature by a gradient furnace method, wherein the crystallization temperature is in units of ℃;
T eic : extrapolating crystallization starting temperature in units of ℃;
step S5: selecting 4 glass solidified body samples as samples to be tested, processing the samples to be tested in the same crushing mode as the step S2, measuring the initial temperature of extrapolated crystallization of the samples under the same test condition as the step S3, substituting the initial temperature into the relation curve of the step S4, and respectively calculating the crystallization temperatures T of the 4 samples c . Without verifying the accuracy of the results, the inventors tested these 4 glass solidified body samples by using a gradient furnace method to obtain corresponding crystallization temperatures, and the results are shown in table 4.
TABLE 4 Table 4
| Sequence number | Crystallization temperature/DEGC of gradient furnace | Crystallization temperature/°c measured by the method of the invention |
| Sample 1# to be tested | 642.6 | 643.6 |
| Sample 2# to be measured | 658.3 | 658.0 |
| Sample 3# to be tested | 659.9 | 659.6 |
| Sample to be measured 4# | 665.3 | 666.1 |
As is clear from Table 4, the crystallization temperature obtained by the method of the present invention has a front-back error of + -1.9deg.C or less, and the error is smaller than the crystallization temperature measured by the gradient furnace method, thereby satisfying the requirements of the art.
Example 3
In this embodiment: firstly, DSC test is carried out on a sample No. 2 to be tested, and a test program is set: the temperature was raised from room temperature to 1000℃at a rate of 35℃per minute, purged with nitrogen, and the flow rate was 40mL/min, and 25mg of the sample was weighed. Analyzing the measured DSC calorimetric curve by using NETZSCH protein software, wherein the crystallization range is 652-670 ℃;
selecting five calibration samples at 642 ℃, 650 ℃, 660 ℃, 680 ℃ and 710 ℃ from the established database according to the crystallization range;
the subsequent procedure is as in example 2.
And finally, the crystallization temperature is calculated to be 660.2 ℃, and the test accuracy is higher.
Example 4
In the embodiment, the test program is set to be heated from room temperature to 1000 ℃, the heating rate is 30 ℃/min, nitrogen is purged, the flow rate is 30mL/min, and the sample weighing is about 20mg; the other conditions were the same as in example 2.
Example 5
In the embodiment, the test program is set to be heated from room temperature to 1000 ℃, the heating rate is 40 ℃/min, nitrogen is purged, the flow rate is 20mL/min, and the sample weighing is about 30mg; the other conditions were the same as in example 2.
The crystallization temperatures obtained by the method have little difference from the crystallization temperatures measured by the gradient furnace method, namely, the crystallization temperatures detected by the method have higher accuracy, simple operation and shorter time consumption.
To further illustrate the beneficial effects of the present invention, the following comparative examples were constructed.
Comparative example 1
The test procedure is set in this comparative example to heat from room temperature to 1000 ℃, the heating rate is 10 ℃/min, nitrogen is purged, the flow rate is 40mL/min, and the sample is weighed to be about 25mg; the other conditions were the same as in example 2.
Comparative example 2
The test procedure is set in this comparative example to heat from room temperature to 1000 ℃, heat rate 20 ℃/min, nitrogen purge, flow rate 40mL/min, and sample weighing about 25mg; the other conditions were the same as in example 2.
Comparative example 3
In this comparative example, the glass-cured product calibration sample was subjected to crushing treatment, and sieved to obtain a sample having a particle size of 50 mesh to 100 mesh, and the other conditions were the same as in example 2.
Comparative example 4
In this comparative example, the glass-cured product calibration sample was subjected to crushing treatment, and the sample was sieved to obtain a 100-150 mesh particle size sample, and the other conditions were the same as in example 2.
As is clear from the calorimetric curves 5 to 8 of comparative examples 1 to 4, the curves in the figures have no distinct turns, and the extrapolated onset temperatures cannot be recognized. The comparative examples 1-2 are poor in crystallization peak effect due to the fact that the temperature rising rate is low, and are not easy to observe; comparative examples 3-4 are due to the larger particle size of the sample and weaker peak development.
In summary, the invention quantitatively measures the crystallization temperature of the glass solidified body by establishing a relation curve between the crystallization temperature by a gradient furnace method and the crystallization extrapolated initial temperature measured by a DTA/DSC method. Compared with a gradient furnace method, the method provided by the invention has the advantages of small sampling amount and high analysis speed after curve establishment, and realizes high-efficiency measurement of the crystallization temperature of the glass solidified body.
While the foregoing is directed to the preferred embodiments of the present invention, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the principles of the invention.
Claims (9)
1. The method for measuring the crystallization temperature of the high-level waste liquid glass solidified body is characterized by comprising the following steps of:
step S1: selecting multiple glass solidified body calibration samples with different crystallization temperatures, and respectively measuring the crystallization temperatures of the calibration samples by using a gradient furnace method;
step S2: respectively crushing, sieving and grinding the glass solidified body calibration sample into powder, and obtaining a sample with the particle size of more than 150 meshes through sieving;
step S3: setting test conditions, respectively testing the samples in the step S2 to obtain DTA/DSC curves, analyzing the DTA/DSC curves, and obtaining the extrapolated crystallization starting temperature of the calibration sample;
step S4: drawing a relation curve by taking the extrapolated crystallization starting temperature measured by a DTA/DSC as an abscissa and the crystallization temperature measured by a gradient furnace method as an ordinate;
step S5: and selecting a glass solidified body sample to be analyzed, carrying out sample treatment in the same crushing mode as in the step S2, measuring the extrapolated crystallization starting temperature of the sample under the same test condition as in the step S3, substituting the extrapolated crystallization starting temperature into a relation curve, and calculating to obtain the crystallization temperature of the sample.
2. The method for measuring the crystallization temperature of a glass solidified body with high level of waste liquid according to claim 1, wherein the step S1 further comprises: crushing a glass solidified body sample to be analyzed, performing a DTA/DSC test, analyzing a DTA/DSC curve to obtain a crystallization range of the glass solidified body sample to be analyzed, and then selecting a plurality of glass solidified body calibration samples containing the crystallization temperature range.
3. The method for measuring the crystallization temperature of a glass solidified body with high level of waste liquid according to claim 1, wherein in the step S1, the crystallization temperature of the glass solidified body calibration sample is 600 ℃ to 750 ℃, and the number of the glass solidified body calibration samples is 3 or more.
4. The method for measuring the crystallization temperature of the glass solidified body with high level of waste liquid according to claim 1, wherein in the step S1, glass solidified body calibration samples with different crystallization temperatures are obtained by the following methods:
firstly, collecting different glass solidified body samples, determining crystallization temperatures of the samples through a gradient furnace method, establishing a crystallization temperature database of the different samples, and then selecting different glass solidified bodies as standard samples according to the glass solidified body samples to be analyzed, wherein the crystallization temperatures of the glass solidified bodies to be analyzed are covered by a crystallization temperature range of a calibration sample.
5. The method for measuring crystallization temperature of high level waste glass solidified body according to claim 1, wherein in the step S3, DTA/DSC test conditions are as follows: the temperature is raised to 1000 ℃ at the temperature rising speed of 30 ℃/min-45 ℃/min, nitrogen is purged, the nitrogen flow rate is 20mL/min-40mL/min, and the sample weighing is 20mg-30mg.
6. The method for measuring crystallization temperature of high level waste glass solid according to claim 5, wherein in the step S3, DTA/DSC test conditions are as follows: the temperature is raised to 1000 ℃ at the temperature rising speed of 30 ℃/min-35 ℃/min, nitrogen is purged, the nitrogen flow rate is 40mL/min, and the sample is weighed to be 25mg.
7. The method for measuring the crystallization temperature of a glass solidified body of high level waste liquid according to claim 1, wherein the DTA/DSC curve is analyzed by NETZSCH protein software.
8. The method for measuring the crystallization temperature of the glass solidified body with high level of waste liquid according to claim 1, wherein the relationship curve drawn in the step S4 is a linear relationship: t (T) c ＝AT eic +B；
Wherein T is c : crystallization temperature by a gradient furnace method, wherein the crystallization temperature is in units of ℃;
T eic : extrapolating crystallization starting temperature in units of ℃;
a is the slope of the relationship curve;
b is the intercept of the relationship curve.
9. The method for measuring the crystallization temperature of a high-level waste liquid glass solidified body according to claim 1, wherein the gradient furnace method is characterized in that the crystallization temperature of the calibration sample is measured by: respectively crushing the glass solidified body calibration samples, then putting the glass solidified body calibration samples into a temperature gradient furnace through a platinum boat, and preserving heat for 24 hours or more; after the heat preservation is completed, taking out and cooling the glass solidified body calibration sample; and (5) observing the cooled glass solidified body calibration sample by using a microscope, and determining the crystallization temperature.
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