JPH06109722A - Heat resistance testing device - Google Patents

Abstract

PURPOSE:To improve the work efficiency, accuracy, and reliability by automating the heat resistance testing method of a sample containing the nitric ester group. CONSTITUTION:Multiple test tubes 5a-5d filled with nitrocellulose as a sample containing the nitric ester group are set on heating containers 10a-10d fed with the hot water of a heating section 1, the test tubes 5a-5d are heated for a preset time, then the gas containing NO and NO2 generated in the test tubes 5a-5d is guided in sequence to a trace nitrogen analyzer 3 employing the chemiluminescence method by a gas conveying device 2. The photoelectric transfer signal indicating the NO2 quantity is obtained by the trace nitrogen analyzer 3, and it is outputted to a data processing section 4 for data processing and recording. When the analysis of one sample is completed, the analysis of the next sample is automatically made in sequence.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat resistance test device for a sample containing a nitrate ester group. Specifically, it relates to a heat resistance test device for nitrocellulose, nitroglycerin, and mixtures thereof.

[0002]

2. Description of the Related Art Conventionally, for example, JIS-K4812 is used for the heat resistance test of nitrocellulose for explosives, and NDS-K4013 is used for the heat resistance test of nitrocellulose for ammunition.
For the heat resistance test of industrial nitrocellulose, JI
The test method is specified in each of S-K6703. That is, in the heat resistance test of nitrocellulose, a sample and a potash starch iodide test paper, the upper one third of which was moistened with a glycerin solution, were put in a test tube, and the test tube was heated in warm water. This is a method of comparing the color appearing in the dry and wet areas of the test paper with a standard color paper and judging the heat resistance by the time when the color tone is the same. Also, if it is a heat resistance test at high temperature,
A method of using methyl violet test paper instead of potassium iodide starch test paper is described.

[0003]

However, in any of the above-mentioned conventional heat resistance test methods, the slight difference between the color of the test paper and the standard color of the standard colored paper is determined by the naked eye's colorimetric comparison. Therefore, there is an unsolved problem that a large error is caused by an individual, and considerable skill is required before an accurate determination can be made. Further, most of the steps of the heat resistance test are manual work, and there is an unsolved problem that work efficiency is poor.

Therefore, the present invention has been made by paying attention to the unsolved problems of the above-mentioned conventional examples.
An object of the present invention is to provide a heat resistance test apparatus capable of accurately, easily and automatically performing a heat resistance test on a sample containing a nitrate ester group such as nitroglycerin and a mixture thereof.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the unsolved problems of the above-mentioned conventional examples, the present inventors have found that
The inventors have found that NO and NO ₂ gas generated by heating a sample are detected by a chemiluminescence method instead of being detected by a potassium iodide starch test paper or a methyl violet test paper, and have reached the present invention.

That is, as shown in the basic configuration diagram of FIG. 1, the heat resistance test apparatus according to the present invention is used to test the heat resistance of a sample containing a nitrate ester group. A heating unit for heating the container, and NO and N in the gas generated from the sample heated by the heating unit
A trace nitrogen analyzer that detects O ₂ using a chemiluminescence method and outputs an analysis value as an electric signal, and a gas carrier that conveys the gas generated in each container individually to the trace nitrogen analyzer together with a carrier gas. Means, a data processing part for data processing the analysis value of the trace nitrogen analyzer, and a control means for sequentially sequence-controlling the heating part, the gas transfer means and the data processing part for each test container. I am trying.

[0007]

In the present invention, a plurality of samples to be subjected to the heat resistance test are individually housed in the test containers, and these test containers are arranged in the heating section, so that the heating section heats them for a predetermined time under the control of the control means. To be done. Then, the gas generated in each test container by heating is individually introduced to the trace nitrogen analyzer together with the carrier gas by the gas conveying means. The gas led to the trace nitrogen analyzer is oxidized to NO ₂ by ozone and NO
Light generated when ₂ returns to NO is received by, for example, a photomultiplier tube, the photoelectric conversion output is electrically amplified and output as a nitrogen content. This signal output is recorded by performing necessary processing such as integration processing in the data processing unit. Thus, when the test of one sample is completed, the control means automatically starts the measurement of the next sample. As described above, once a plurality of test containers into which the sample has been injected are set in the apparatus, the subsequent measurement is automatically performed without any labor.

[0008]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 2 is a block diagram showing an embodiment of the present invention, in which 1 is a plurality of test containers, for example, 4 as a test container into which a sample containing a nitrate ester group such as nitrocellulose, nitroglycerin, and a mixture thereof is injected. Book test tubes 5a-5
This is a heating unit for heating d, and the gas heated in the heating unit 1 and generated in the test tubes 5a to 5d is supplied to the trace nitrogen analyzer 3 by the gas transfer device 2 as gas transfer means. An analytical value representing the nitrogen content output from the analyzer 3 is supplied to the data processing unit 4. Then, the heating unit 1, the gas transfer device 2, and the data processing unit 4 are sequence-controlled by a sequencer 6 as a control means.

The heating unit 1 has narrow-necked heating containers 6a to 6d for individually mounting and holding the test tubes 5a to 5d, and a hot water tank 7 for storing hot water to be supplied to the heating containers 6a to 6d.
The hot water in the hot water tank 7 is pumped up through the introduction pipes 8a to 8d, and the heating containers 6a to 6d through the supply pipes 9a to 9d.
Water supply pumps 10a to 10d which are individually supplied to the bottom of the
And one end communicates with the upper side of each heating container 6a to 6d,
The drain pipes 11a to 11 having the other end opened to the upper surface of the warm water tank 8
and d. Here, the hot water tank 7 is provided with a heater 12 for heating at the bottom thereof, and a temperature sensor 13 is provided from the upper surface side, and the temperature detection value of the temperature sensor 13 is fed back to the temperature controller 14. It is supplied as a signal and compared with a preset temperature set in the temperature controller 14, and the energization amount of the heater 12 is controlled so that the two match. Further, the hot water tank 7 is provided with a circulation pump 15 that circulates the hot water at the bottom of the hot water tank 7, and the circulation pump 15 makes the temperature distribution of the hot water in the hot water tank 7 uniform. Further, the hot water supply pumps 10a to 10d are rotationally driven and controlled by the sequencer 6, and the heating container 6a
The heating time of the test tubes 5a to 5d by ~ 6d is controlled.

The gas transfer device 2 is connected to the rubber cap CP of each of the test tubes 5a to 5d and has one end of NO and N.
Carrier gas not containing O ₂ Carrier gas, for example, introducing pipes 17 a to 17 d connected to a supply source (not shown) for supplying air and having introducing valves 16 a to 16 d, which are electromagnetic shut-off valves, and the like. A discharge pipe 19a in which discharge valves 18a to 18d composed of electromagnetic opening / closing valves are inserted in the middle
˜19d, a distribution pipe 20 to which the ends of these discharge pipes 19a to 19d are connected, and a vacuum pump 21 connected to this distribution pipe 20 via a trace nitrogen analyzer 3, and is a test object 1 By opening the inlet valve 16i and the discharge valve 18i connected to the test tube 5i (i = a to d) of the book and driving the vacuum pump 21, the test tube 5i
The gas in i, together with the carrier gas, is a trace nitrogen analyzer 3
Be transported to.

The trace nitrogen analyzer 3 is, as shown in FIG.
N from the test tube 5i conveyed through the distribution pipe 20
A gas containing O and NO ₂ is supplied, the nitrogen content is analyzed using a chemiluminescence method, and an NO analysis unit 22 that outputs an electric signal corresponding to this is provided, and an oxidation gas is supplied to the NO analysis unit 22. As a result, an ozone generator 23 that supplies air containing ozone and an electric signal output from the NO analysis unit 22 are input and amplified by the electric control unit 24 that adjusts the sensitivity and analyzed by the NO analysis unit 22. And an ozone decomposing unit 25 for decomposing residual ozone in the gas that has finished
The ozone decomposing unit 25 is connected to the vacuum pump 21 described above. Here, the NO analysis unit 22 uses the gas containing NO and NO ₂ introduced from the test tube 5i and the ozone generator 23.
Is mixed with the air supplied through the gas to oxidize all NO contained in the gas from the test tube 5i into unstable NO ₂ .
590 to 2500 emitted when this NO ₂ returns to NO
Light having a wavelength of nm is received by the photomultiplier tube, and the photoelectric conversion output corresponding to the NO ₂ concentration is output from the photomultiplier tube to the electric control unit 24 as an electric signal.

The data processing section 4 performs data processing such as averaging processing by integration of the electric signal corresponding to the nitrogen content output from the electric control section 24 of the trace nitrogen analyzer 3 and NO.
_The analysis data that accurately represents the _two densities is obtained, and this analysis data is output to the output device 26 including a display, a printer, etc., and stored in the storage device 27. When the test start switch 30 is pressed down, the sequencer 6 executes a preset sequence process shown in FIG. 4 and sets a predetermined heating time for each of the test tubes 5a to 5d to the hot water supply pumps 10a to 10d. Is controlled by driving and controlling, and after a lapse of a predetermined time, the introduction valves 16a to 16d and the discharge valves 18a to 18d are simultaneously opened and the vacuum pump 21 is driven to remove NO and NO ₂ generated in the test tubes 5a to 5d. The contained gas is conveyed to the trace nitrogen analyzer 3 and the data processing unit 4 is operated to output N as the analysis result of the trace nitrogen analyzer 3.
It controls the data processing and recording of the output signal representing the O ₂ concentration.

In the present embodiment, the trace nitrogen analyzer 3 is the analyzer portion (ECL-77A) of the Yanamoto Corporation trace nitrogen analyzer TN-7, and the data processor 4 is the Shimadzu chromatopack ( Product name), Sequencer 6
As an example, PR015 made by OMRON is applied. Next, the operation of the above embodiment will be described with reference to the flowchart of FIG. 4 showing an example of the processing procedure of the sequencer 6.

The sequencer 6 includes a test start switch 31.
When is pressed, execution of the process of FIG. 4 is started. That is, first, in step S1, the test tube code C is set to, for example, "1", and the test tube to be tested first is, for example, 5a.
Is set, then the process proceeds to step S2, the hot water supply pump 10a corresponding to the test tube code is rotationally driven, and then the process proceeds to step S3 to determine whether or not a preset heating time has elapsed. If the heating time has not elapsed, the process returns to step S2 to continue driving the hot water supply pump 10a, and if the heating time has elapsed, step S2.
Go to 4.

In step S4, the introduction valve 16a and the discharge valve 18a for the test tube 5a corresponding to the test tube code C are provided.
Are simultaneously opened, and the vacuum pump 16 is driven to convey the gas containing NO and NO ₂ generated in the test tube 5a to the trace nitrogen analyzer 3. Next, in step S5, a data processing command is sent to the data processing unit 4, and an output signal representing the NO ₂ concentration output from the trace oxygen analyzer 3 is read and predetermined data processing is executed.

Next, in step S6, it is determined whether or not a predetermined time required for analysis has elapsed. If the predetermined time has not elapsed, the process waits until the predetermined time elapses, and the predetermined time elapses. If so, the process proceeds to step S7. In step S7, it is determined whether or not the test tube code C has reached the preset number N of test tubes. If the test tube code has not reached the number of test tubes, a heat resistance test is performed on all the test tubes. When it is judged that there is an untested test tube that has not been completed, the process proceeds to step S8 and the value obtained by adding "1" to the current test tube code C is added to the new test tube code C.
Then, the process returns to step S2, and when the test tube code C has reached the number N of test tubes, it is determined that the heat resistance test has been completed for all the test tubes, and the process is ended.

Therefore, each of the test tubes 5a to 5d, into which the sample containing a nitrate ester group such as nitrocellulose, nitroglycerin, and a mixture thereof is injected in advance, is introduced into each of the introduction tubes 17a to 17d and the discharge tubes 19a to 19a.
The cap CP to which d is connected is capped and installed in the heating containers 6a to 6d. In this state, by pressing the test start switch 30 of the sequencer 6, the sequencer 6 is brought into an operating state, and under the control of the sequencer 6, the test tubes 5a are sequentially heated by the heating unit 1 for a predetermined time, NO and N generated in the test tube 5a
The gas containing O ₂ is introduced into the test tube 5a while the introduction valve 16a and the discharge valve 18a are opened, and the vacuum pump 21 is operated to trace the gas containing NO and NO ₂ in the test tube 5a.
To introduce. Then, the N introduced into the trace nitrogen analyzer 3
The gas containing O and NO ₂ is mixed with the air that has passed through the ozone generator 23 in the NO analysis unit 22 and is all oxidized to NO ₂ , and the luminescence generated when unstable NO ₂ returns to NO is NO.
The photomultiplier tube of the analysis unit 22 receives the light and converts it into an electric signal. This photoelectric conversion signal is amplified and adjusted in sensitivity by the electric control unit 24 and output to the data processing unit 4. In the data processing unit 4, this electric signal is subjected to data processing such as integration processing and the processed data is heat-resistant. The data is stored in the storage device as the sex test data and is output to the output device to be printed or displayed.
The gas for which analysis has been completed decomposes residual ozone in the ozone decomposing unit 25 and is then exhausted to the outside of the system through the vacuum pump 21.
In this way, when the analysis of the first sample is completed, the test tube code C becomes "2", the switch of the second hot water supply pump 10b is turned on, and heating for a predetermined time starts. Hereinafter, the analysis of the test tube 5b is started by the same processing procedure as that of the test tube 5a. Thus, if the samples are first set in the four test tubes, then the analysis automatically advances to the fourth sample, and when the analysis of the last sample is completed, the heat resistance test process is terminated.

Next, the results of an actual heat resistance test of nitrocellulose using the above heat resistance test apparatus will be described below. 1.3 g of nitrocellulose of the same lot was weighed 4 times, placed in test tubes 5a to 5d, and heated in a heating container 6a.
Set to ~ 6d. N was generated when the heat resistance was tested by a sequence of heating this at 65.5 ° C. for 35 minutes.
The measured O ₂ concentration was as shown in Table 1 below.

[0019]

[Table 1]

On the other hand, the same sample as above was used for NDS-K401.
When tested by the conventional potash starch iodide test paper method based on 3, the coloring of the potash starch iodide test paper was not observed as much as the standard colored paper after heating for 35 minutes.
When the heat resistance of another lot of nitrocellulose was tested with this apparatus, it was 14 ppm. The coloring degree of the potassium iodide starch test paper of this lot was about the same as that of the standard colored paper, and the heat resistance was unacceptable with the conventional method. As a result, NO ₂ generated by heating using this test device
It has been proved that the heat resistance can be accurately judged if the amount is grasped.

In the above embodiment, the case where the test tubes 5a to 5d are applied as the test container has been described, but the present invention is not limited to this, and other containers may be applied. Further, the number of test containers is not limited to four and can be set to any number. Further, in the above-mentioned embodiment, the case where the hot water tank 7 that stores hot water as a heating medium is applied as the heating unit 1 has been described, but the present invention is not limited to this, and heat resistance at a temperature decrease of 100 ° C. or more is used. Including cases such as when conducting a test, a heating medium such as glycerin or silicone oil may be applied instead of hot water, and the heating method is not limited to the solvent circulation method and may be a direct heating method using a metal block. .

Further, the trace nitrogen analyzer 3, the data processing unit 4, and the sequencer 6 are not limited to the configurations of the above-mentioned embodiments, and any type can be applied as long as they have equivalent functions. Furthermore, in the above embodiment, the case where the sequencer 6 is applied as the control means has been described, but the present invention is not limited to this, and other control means such as a microcomputer may be applied.

[0023]

As described above, according to the heat resistance test apparatus of the present invention, NO and NO ₂ gas generated by heating a sample having a nitrate ester group is traced by the chemiluminescence method. since then analyzed by nitrogen analyzer is adapted to measure the NO ₂ concentration, the heat resistance of the sample NO ₂
It is possible to quantitatively grasp the concentration, and there is no need for skilled testing work because there is a large individual difference by visual observation as in the conventional example, and even a non-expert can accurately determine whether heat resistance is acceptable or not. At the same time, the heating unit, the trace nitrogen analyzer, and the data processing unit can be applied to existing devices. In addition, once multiple test vessels filled with a sample are set in the heating section, the measurement is automatically performed under the control of the control means without any human intervention. There is also an effect that work efficiency can be significantly improved as compared with the law.

[Brief description of drawings]

FIG. 1 is a block diagram showing a basic configuration of the present invention.

FIG. 2 is a configuration diagram showing an embodiment of the present invention.

FIG. 3 is a configuration diagram showing a trace nitrogen analyzer and a data processing unit applicable to the present invention.

FIG. 4 is a flowchart showing an example of a processing procedure of a sequencer applicable to the present invention.

[Explanation of Codes] 1 heating unit 2 gas transfer device 3 trace nitrogen analyzer 4 data processing unit 5a to 5d test tube 6a to 6d heating container 7 hot water tank 10a to 10d hot water supply pump 16a to 16d introduction valve 18a to 18d discharge valve 21 vacuum pump 22 NO analysis unit 23 ozone generator 24 electric control unit 25 ozone decomposition unit

Claims (1)

[Claims] 1. A heating unit for heating a plurality of test vessels into which a sample containing a nitrate ester group is injected, and NO and NO in the gas generated from the sample heated by the heating unit.
A trace nitrogen analyzer that detects ₂ using a chemiluminescence method and outputs an analysis value as an electric signal, and a gas transfer means that individually conveys the gas generated in each container together with a carrier gas to the trace nitrogen analyzer. And a data processing unit that processes the analysis value of the trace nitrogen analyzer, and a control unit that sequentially controls the heating unit, the gas transfer unit, and the data processing unit for each test container. Heat resistance test equipment.