CN113466364B - Device and method for evaluating influence of nitramine azide on storage stability of nitrocotton and nitroglycerin gunpowder - Google Patents
Device and method for evaluating influence of nitramine azide on storage stability of nitrocotton and nitroglycerin gunpowder Download PDFInfo
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- CN113466364B CN113466364B CN202110689918.1A CN202110689918A CN113466364B CN 113466364 B CN113466364 B CN 113466364B CN 202110689918 A CN202110689918 A CN 202110689918A CN 113466364 B CN113466364 B CN 113466364B
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Abstract
The invention discloses an evaluation device and an evaluation method for the influence of nitramine azide on the storage stability of nitrocotton and nitroglyceryl gunpowder. The device comprises a cup body, a cap, an extraction opening, a heating furnace, a gas production device and a gas chromatograph. The method comprises the steps of filling nitrocotton containing azido nitramine and nitroglycerin based gunpowder samples into a reactor consisting of a cup body and a cap, filling nitrocotton containing no azido nitramine and nitroglycerin based gunpowder into another reactor, heating for 8 hours at 100 ℃, cooling to room temperature, and detecting gas production. By comparing the CO2 content in the decomposed gas of the two samples, the influence of the nitro-amine azide on the storage stability of the nitrocotton and the nitroglycerin base gunpowder can be known. The invention is designed according to the fact that the decomposition mechanism of the nitramine azide is different from that of nitroglycerin, and can avoid misjudgment that the storage stability of nitrocotton and nitroglycerin gunpowder is deteriorated by the nitramine azide in a vacuum stability test.
Description
Technical Field
The invention belongs to the field of gunpowder detection, mainly relates to a device and a method for evaluating stability of NC (nitrocotton) and NG (nitroglycerin) based gunpowder, and particularly relates to a method for determining the influence of DIANP (azido nitramine) on storage stability of NC and NG based gunpowder.
Background
In the patent, NC and NG base gunpowder refer to traditional double-base gunpowder and triple-base gunpowder, and the gunpowder contains NC and NG.
NC used as energy and adhesive is rigid linear macromolecule, the plasticity is poor, and the processing and mechanical properties can be improved by adding the plasticizer. NG is a mature energetic plasticizer for NC, but has high sensitivity, a high freezing point and poor thermal stability. For NC and NG-based gunpowder, a insensitive energetic plasticizer is adopted to replace NG, the sensitivity of the NC and NG-based gunpowder is reduced as much as possible on the basis of ensuring the energy level, and the method is one of the main directions of the technical development of the gunpowder. Wherein DIANP (1, 5-diazide-3-nitryl aza pentane) is a novel energetic plasticizer, the impact sensitivity, the friction sensitivity and the heat sensitivity of the plasticizer are all less than those of NG, and the dissolubility of NC with high nitrogen content is better than that of NG. The nitroamine group, azide group and NC in the DIANP form hydrogen bonds to improve the interfacial adhesion between NC and plasticizer, and the low-temperature impact strength of NC and NG base powder can be improved by replacing part of NG with DIANP and increasing the DIANP content when the total amount of plasticizer is not changed. The DIANP shows good application prospect in NC and NG base powder.
The explosive has the characteristics of long-term storage and one-time use, so the explosive not only has good functional characteristics, but also has better storage stability. The storage stability of NC and NG-based gunpowder is mainly chemical stability, which means the ability to retard decomposition and prevent automatic chemical changes during storage. If the DIANP will reduce the storage stability of NC and NG-based gunpowder and increase the automatic chemical change of the NC and NG-based gunpowder, the popularization and the application of the DIANP will be influenced. Therefore, it is necessary to determine the effect of DIANP on the storage stability of NC and NG-based gunpowder.
There are many methods for evaluating the storage stability of explosives and powders, including vacuum stability method (VST), microcalorimetry and Differential Scanning Calorimetry (DSC). The VST has the advantages of large sample amount and approximate test temperature to the working condition temperature of the explosive production process, has an evaluation standard, is one of the commonly used important evaluation methods, is established in China in the 20 th century and 70 th century by referring to the American military Standard (MIL-STD-286B), supports the development and production of various formulas and types of products in the first generation and the second generation of explosives in China, is widely used, and is the most widely applied method for researching and testing the stability of explosives at home and abroad at present. The microcalorimetry and DSC method have small sample amount and are only used in the scientific research stage of explosive products.
VST theory of operation: placing 5g of a quantitative sample in a special glass reaction tube, and vacuumizing; the stability of the explosive sample was characterized by continuously heating the sample at a constant temperature (the temperature of NC/NG base powder is 90 ℃) to decompose the sample, measuring the pressure of the gas released from the sample within 48 hours, and converting the pressure into the volume of the gas in a standard state.
After part of NG in NC and NG base fire drugs is replaced by DIANP, the outgassing amount of a VST test is increased, and the increase of the outgassing amount represents that more NC is decomposed according to the judgment of the original evaluation standard, which indicates that the DIANP reduces the storage stability of the NC and NG base fire drugs. However, when part of NG in NC-and NG-based explosives was replaced with DIANP as measured by DSC, the peak temperature of thermal decomposition increased, indicating that DIANP increased the storage stability of NC-and NG-based explosives.
Through a thermal accelerated ageing test, the safe storage life of NC-based gunpowder and NG-based gunpowder is estimated, after part of NG in the NC-based gunpowder and NG-based gunpowder is replaced by DIANP, the safe storage life is prolonged by 0.34 times, the safe storage life of the gunpowder with good stability is long, although the test period of estimating the safe storage life of the NC-based gunpowder and NG-based gunpowder by the thermal accelerated ageing test is overlong (after part of NG in the NC-based gunpowder and the NG-based gunpowder is replaced by DIANP, the test time at 65 ℃ is nearly 300 days), the DIANP is enough to prove that the storage stability of the NC-based gunpowder and NG-based gunpowder is increased.
It can be seen that the results of the DSC method and the safe storage life estimation method are consistent, whereas the results of the VST method are opposite to them.
It was analyzed that this is due to the different decomposition mechanism of DIANP from nitrate: both NC and NG belong to nitrate compounds, with O-NO in the molecule after heating 2 Decompose to give NO 2 ，NO 2 Has catalytic effect on decomposition of nitrate compound, and 1.5% stabilizer (C) is added into NC and NG based pyrotechnic composition to reduce the autocatalysis 2 )，C 2 Absorption of NO 2 Prevent NO 2 Catalytic decomposition of nitrate ester compounds; after heating of DIANP, -N in the molecule 3 Decompose to release N 2 ，N 2 Cannot be absorbed (a component cannot be added to NC and NG base powder to absorb N 2 Since even one can find a substance to absorb N 2 Also, the NC and NG base powder contact N in the air during the production and assembly process 2 The substance is quickly depleted of light, losing its absorptive capacity).
The modified gunpowder formed by replacing NG in NC and NG base gunpowder with DIANP part has less nitrate compound compared with original NC and NG base gunpowder, and under the same thermal stress, the NO decomposed by the new gunpowder is not only 2 Less gas and becauseNew gunpowder generates N 2 Decrease NO 2 Such that: one is C in the new gunpowder 2 The consumption speed is reduced, and NO can be performed in a longer time 2 The absorption of (2); second, NO in the new gunpowder 2 Is lower in concentration at C 2 After the absorption capacity has disappeared, NO 2 The catalytic action on the new gunpowder is weaker than that of the original gunpowder. Therefore, although the DIANP improves the storage stability of NC-and NG-based gunpowder, the gas yield is slightly increased, and the VST method detection result shows that the DIANP reduces the storage stability of NC-and NG-based gunpowder, which is a misjudgment.
In addition, some conventional gunpowder is in a negative oxygen balance state (such as a conventional propellant system), the VST test dosage is large (5 g), a sample is in a vacuum state, and the vacuum state is not consistent with the actual charging condition (such as the conventional propellant is loaded in a projectile body in a certain regular manner, and the gaps among the propellant are filled with air). For compounds with negative oxygen balance, the oxygen in the air affects the extent of the reaction. Therefore, it is considered that NC and NG-based gunpowder samples should be decomposed by heating in an air atmosphere, and thus the obtained test results can more accurately characterize the storage stability.
Moreover, VST needs to heat the sample for 48h continuously, and then detects the amount of outgas, and the whole test period is too long, and is not suitable for the requirement of the current rapid detection.
In summary, when VST was used to evaluate the effect of dinp on NC and NG-based propellant storage stability, the following problems were found:
(1) The incorrect belief that DIANP leads to a deterioration in the storage stability of NC-and NG-based gunpowders
The VST detection method is suitable for detecting the stability of the nitrate-containing compound explosive, aims at solving the problem that nitrogen oxide and carbon oxide gas are generated by decomposing the nitrate compound, and shows that the more decomposed gas, the larger the decomposition degree of the nitrate compound is, and the worse the stability of a sample is. However, the decomposition gas of the DIANP as the novel energetic plasticizer in the initial stage of heating is N 2 Since it is not absorbed, the gas production of NC and NG-based powder containing dinp increases, and storage stability of NC and NG-based powder is deteriorated due to incorrect recognition of dinp.
(2) The sample is in a vacuum environment in the test process and is not in accordance with the actual charging environment
Some conventional gunpowder is in a negative oxygen balance state, has different reaction capacities in an air environment and an oxygen-deficient environment, and has a great influence on the reaction degree due to the existence of oxygen in the environment during slow oxidative decomposition over a long storage period. The propellant charge is in air atmosphere, so the stability test result in vacuum environment cannot better reflect the actual storage stability.
(3) The test time is too long
VST needs to heat the sample for 48h continuously, then the pressure (about 5 minutes) is detected, the air release amount is converted, the whole test period is too long, and the requirement of gradually increased rapid detection cannot be met.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides an evaluation device for the influence of DIANP on the storage stability of NC and NG-based gunpowder, which comprises a cup body 1, a cap 2, an air extraction opening 3, a heating furnace 4, an air production device 5 and a gas chromatograph 6;
the cup body 1 is a barrel, the wall thickness of the cup body 1 is 2.5mm, the inner diameter is 25mm, the outer height is 80mm, the bottom thickness is 3mm, the upper end part of the outer surface of the cup body 1 is a first external thread area, the height of the first external thread area is 10mm, and the cup body 1 is made of 316 stainless steel;
the outer diameter of the cap 2 is 36mm, the outer height of the cap is 15mm, the inner depth of the cap 2 is 10.5mm, a second internal thread area with the height of 8mm is arranged from the bottom end to the top of the cap 2, the second internal thread area is matched with the thread of the first external thread area of the cup body 1, and an air hole with the diameter of 1mm is formed in the center of the circle on the upper surface of the cap 2; the uppermost end in the cap 2 is provided with a second sealing ring, and the outer diameter, the inner diameter and the thickness of the second sealing ring are 30mm, 26mm and 3mm respectively; the second sealing gasket is made of silicon rubber, and the rest materials are 316 stainless steel;
the cap 2 is positioned right above the cup body 1;
the air pumping port 3 consists of an upper part and a lower part, the lower part of the air pumping port 3 is an air pumping pipe, and the upper part of the air pumping port 3 is a Shiviaoke quick connector A part; the material of the air extraction opening 3 is 316 stainless steel; the length of the exhaust pipe is 100mm, the upper end of the exhaust pipe is connected with the Shiviaoke quick connector A part, and the Shiviaoke quick connector A part plays a role in sealing the exhaust pipe;
the air exhaust port 3 is positioned right above the cap 2, the lower end of the air exhaust pipe is welded at the center of the upper surface of the cap 2, and the inside of the air exhaust pipe is communicated with an air hole of the cap 2;
1 cup body 1, 1 cap 2 and 1 extraction opening 3 form 1 reactor;
the heating furnace 4 consists of an upper part, a middle part and a lower part, the lower part of the heating furnace 4 is a heating body, the middle part of the heating furnace 4 is a protection plate, and the upper part of the heating furnace 4 is a heat-insulating cover; the heating body is a cylinder, sample placing holes are uniformly distributed on the upper plane of the heating body, the depth of each sample placing hole is 90mm, the diameter of each sample placing hole is 38mm, and the upper left end and the upper right end of the side surface of the heating body are respectively provided with 1 hinge quick lock A part; the protection plate is a curved surface and is consistent with the curvature of the outer side surface of the heating body, and the protection plate is welded on the outer ring of the upper surface of the heating body; the width of the protection plate is 200mm, the thickness of the protection plate is 5mm, the protection plate is 200mm higher than the upper plane of the heating body, and the protection plate is made of 316 stainless steel; the heat preservation cover is a flat cylinder, and the diameter of the heat preservation cover is consistent with that of the heating body; the heat preservation cover is not connected with the heating body and the protection plate; the left end point and the right end point of the side surface of the heat preservation cover are respectively provided with 1 hinge quick lock catch B part, and the hinge quick lock catch B part is matched with the hinge quick lock catch A part of the heating body;
the cup body 1 is positioned right above the sample placing hole of the heating furnace 4;
the gas production device 5 consists of a left part, a middle part and a right part, the left part of the gas production device 5 is a gas production pipe, the middle part of the gas production device 5 is a quantitative pipe, and the right part of the gas production device 5 is an air pump; the gas production pipe consists of a polytetrafluoroethylene pipeline and a Shiviaoke quick joint B part; the left end of the polytetrafluoroethylene pipeline is connected with a Shiweioke quick joint B part, and the Shiweioke quick joint B part is matched with the Shiweioke quick joint A part of the air extraction opening 3; the right end of the polytetrafluoroethylene pipeline is connected with an air pump through a quantitative pipe, and the volume of the quantitative pipe is 0.5mL;
a quantitative tube and an air pump in the gas production device 5 are arranged inside the gas chromatograph 6, and a gas production tube is positioned outside the gas chromatograph 6; the gas production device 5 is not connected with the cup body 1, the cap 2, the extraction opening 3 and the heating furnace 4;
the gas chromatograph 6 comprises a chromatographic column, a thermal conductivity detector and a workstation; the work of the workstation comprises the steps of controlling the starting of an air pump, feeding sample by a quantitative tube, adjusting the temperature of a chromatographic column, adjusting the temperature of a thermal conductivity detector and recording the area of a chromatographic peak;
the gas chromatograph 6 is not connected with the cup body 1, the cap 2, the extraction opening 3 and the heating furnace 4;
the evaluation device for the influence of DIANP on the storage stability of NC and NG-based fire drugs comprises the following steps:
step 4, starting the gas chromatograph 6, and setting the temperature of the detector to be 250 ℃ and the temperature of the chromatographic column to be 80 ℃; after the instrument is stabilized, pumping air to detect 2 unheated empty reactors; inserting the Shiweiroc quick joint B part of the gas production device 5 into the Shiweiroc quick joint A part of the extraction opening 3, and communicating a gas production pipe of the gas production device 5 with the interior of the reactor; the gas chromatograph 6 workstation controls the air pump, the gas in the reactor is pumped into the quantitative tube of the gas production device 5 from the air pumping port 3, and then the gas is injected into the chromatographic column for separation, the thermal conductivity detector detects, and the chromatographic peak areas of oxygen and nitrogen are recorded; comparing the chromatographic peak areas of oxygen and nitrogen of the 2 empty reactors, judging that the state of the instrument is stable when the difference of the 2 peak areas is not more than 5%, and detecting the heated reactor;
step 7, decomposing CO in the gas by using the original sample 2 Content = CO in the reactor gas as received 2 Volume content-CO in heated empty reactor gas 2 Volume content; CO in 2 original decomposed gases 2 The average value of the contents is used as the CO in the raw decomposed gas 2 Content omega 0 (ii) a CO in 2 original decomposed gases 2 The absolute value of the content difference is recorded as sigma;
step 8, modifying CO in the sample decomposed gas 2 Content omega 1 = CO in reactor gas containing modified sample 2 Volume content-CO in heated empty reactor gas 2 Volume content;
step 9, let ω be 0 Minus omega 1 Is equal to Δ; when-3 sigma is less than or equal to delta and less than or equal to 3 sigma, the DIANP with the content has no influence on the storage stability of NC and NG-based fire drugs; when Δ > 3 σ, it was evaluated that the content of DIANP could improve the storage stability of NC and NG base powder; when Δ < -3 σ, the evaluation is thatThe content of DIANP decreases the storage stability of NC and NG-based gunpowder.
The invention relates to a device and a method for evaluating the influence of DIANP on the storage stability of NC and NG-based gunpowder, which are characterized in that the NC and NG-based gunpowder is double-base gunpowder or triple-base gunpowder containing NC and NG, and the NC and NG-based gunpowder containing DIANP is modified gunpowder formed by replacing part of NG in the NC and NG-based gunpowder with DIANP.
The invention mainly focuses on the following problems and carries out corresponding technical design when overcoming the defects of the prior method:
(1) By increasing the amount of sample and the heating temperature, the detection time is shortened
VST is a method in which a 5-g sample is heated at 90 ℃ for 48 hours to measure the amount of gas generated from the sample. Under the condition that the gas production rate is unchanged, the heating time can be shortened in two ways: the first is to increase the amount of the sample, and the larger the amount of the sample, the more the gas production amount under the same heating condition; the second method is based on the "time-temperature equivalence" principle, that is, for a physicochemical reaction with a certain reaction depth, increasing the reaction temperature is equivalent to shortening the reaction time, and can be calculated by using a temperature coefficient method, wherein the calculation formula is as follows:
in the formula: tau is the heating time under the newly set heating temperature T; tau. 90 Heating at 90 deg.C for 48 hr; t is a new set heating temperature; gamma is the temperature coefficient, i.e. the time tau to reach the same reaction depth shortens by a factor of 10 deg.c for each increase in temperature, and gamma for NC and NG based charges is typically taken to be 3.
When the detection time is shortened by increasing the sample amount, attention is paid to: the heating gunpowder sample has higher safety risk, in order to ensure safety, the gunpowder and explosive laboratory has sample quantitative requirements, if the sample amount is too large, more rooms and more heating equipment are needed, the cost performance is lower, and finally the sample amount is determined to be 10 g.
When the time for sample decomposition is shortened by increasing the reaction temperature (heating temperature), and the detection time is shortened accordingly, it is noted that: the reaction temperature cannot be increased too high because the reaction mechanism of NC and NG based fire drugs is changed at the too high reaction temperature (heating temperature), the detection result at the high temperature cannot represent the safe storage life at the lower temperature, and the higher the heating temperature is, the greater the danger is (especially when the drug amount is large), the reaction temperature (heating temperature) is finally determined to be 100 ℃.
In order to be consistent with the reaction depth (gas production) of 5g of NC and NG-based fire drugs in a VST test, the heating method established by the patent comprises the following steps: a10 g aliquot was heated at 100 ℃ for 8 hours.
(2) Detecting items
The VST test measures the total volume of gas produced by decomposition, and since the dinp decomposition mechanism is not the same as that of NC and NG based explosives, the degree of decomposition cannot be expressed in terms of gas volume. Gaseous decomposition products of nitrate compounds in NC and NG base gunpowder except NO 2 And also CO 2 ，CO 2 Does not have catalytic action on the decomposition of nitrate ester, and does not have NO-like effect 2 Is absorbed, so that the modified NC and NG-based powder with part of NG replaced by DIANP or the original NC and NG-based powder can pass through CO 2 The degree of decomposition of the nitrate ester compound was characterized. NC-based and NG-based fire drugs with large decomposition degree have poor stability, and under the same heating condition, the NC-based and NG-based fire drugs decompose CO in the fire drugs 2 The high content indicates poor storage stability, and the influence of DIANP on the storage stability of NC-and NG-based explosives can be determined accordingly.
(3) Reactor designed to heat a sample
In the VST test, 5g of a sample is placed in a glass reactor, a vacuum piston and a heating test tube of the reactor are ground, high-vacuum sealing grease is respectively coated on the vacuum piston and the heating test tube, and then the mixture is heated at 90 ℃ for 48 hours. When the NC and NG-based gunpowder used in the patent is heated, the sealing effect is not ideal, the air leakage probability is high, and therefore a new reactor for heating a sample needs to be designed, and the air leakage in the whole test process is ensured.
In addition to ensuring the tightness, when designing the reactor, attention is also paid to: the actual charging process of NC and NG base gunpowder is to charge the propellant into the bullet, the bullet is not strictly sealed during long-term storage, so the oxygen in the air in the bullet is not completely consumed, when the stability of gunpowder is detected by raising the temperature, if the space of the reactor is too small, the oxygen is less, at this moment, the decomposition degree of NC and NG base gunpowder is increased by heating, if the oxygen is less than the oxygen demand (the reactor has good sealing performance, the oxygen outside the reactor cannot seep into the inside of the reactor), the decomposition product of the reaction is different from the decomposition product when the oxygen is sufficient, namely, the reaction mechanism after heating is different from the reaction mechanism during actual storage, so the size of the reactor cannot be too small. Of course, the size of the reactor must not be too large either, since an excessively large reactor means an excessively large heating device and an excessively large area of the laboratory.
Considering comprehensively, the reactor is designed as follows: the reactor consists of a cup body, a cap and an air extraction opening; the cup body is a cylindrical barrel, the wall thickness of the cup body is 2.5mm, the inner diameter is 25mm, the outer height is 80mm, the bottom thickness is 3mm, the upper end part of the outer surface of the cup body is a first external thread area, the height of the first external thread area is 10mm, and the cup body is made of 316 stainless steel; the outer diameter of the cap is 36mm, the outer height of the cap is 15mm, the inner depth of the cap is 10.5mm, a second internal thread area with the height of 8mm is arranged on the cap from the bottom end to the top, the second internal thread area is matched with the threads of the first external thread area of the cup body, and an air hole with the diameter of 1mm is formed in the center of the circle on the upper surface of the cap; the uppermost end in the cap is provided with a second sealing ring, and the outer diameter, the inner diameter and the thickness of the second sealing ring are 30mm, 26mm and 3mm respectively; the second sealing gasket is made of silicon rubber, and the rest materials are 316 stainless steel; the cap is positioned right above the cup body; the air pumping port consists of an upper part and a lower part, the lower part of the air pumping port is provided with an air pumping pipe, and the upper part of the air pumping port is provided with a Shiviaoke quick coupling A part; the material of the air extraction opening is 316 stainless steel; the length of the air exhaust pipe is 100mm, the upper end of the air exhaust pipe is connected with the Shivaloke quick connector A part, and the Shivaloke quick connector A part plays a role in sealing the air exhaust pipe; the air exhaust opening is positioned right above the cap (2), the lower end of the air exhaust pipe is welded at the center of the upper surface of the cap, and the inside of the air exhaust pipe is communicated with the air hole of the cap.
(4) Size requirement for sample handling
The VST test requires large-particle powder and powder columns to be crushed, and samples are taken through a test sieve (the sieve is SSW1.40/0.71GB 6004-1985), and the sizes of the samples are very small.
For some insensitive NC and NG-based gunpowder with a slightly large size (for example, the last process of producing the insensitive NC-based propellant is to passivate the surface of the propellant in a soaking mode, a layer of passivation film is formed on the surface of the propellant, and the passivation film is beneficial to improving the storage stability of the propellant), if the propellant is crushed during stability detection, the passivation film is damaged, the higher the crushing degree is, the more serious the damage is, and the stability detection result deviates from the actual storage condition.
Moreover, the sample in VST is in vacuum state, mainly is self-reaction under anaerobic condition, and the influence of particle size on reaction result is relatively small; in the patent, the sample is in the air, and the different sizes of the sample mean that the contact surfaces of the sample and the air are different in size, and the influence on the chemical reaction of the sample is also different, namely the small-size reaction is obviously different from the actual large-size storage condition, and the small-size detection result is obviously different from the actual storage condition.
Therefore, this patent does not adopt a method of crushing the sample.
On the other hand, an oversize sample corresponds to an oversized reactor volume and heating means, so the size of the sample cannot be oversized either. In order to avoid the influence of the size of the drug form, it should be ensured that the new drug added with DIANP and the original drug without DIANP are processed to the same size.
Finally, the sample is determined to be processed into the shape of 'length, width and height not more than 10 mm'.
(5) Ensuring the safety of the test process
Compared with a VST test, the method has the advantages that the added medicine amount is 10g, the size of a sample is large, the heating temperature is 100 ℃, in addition, most of NC and NG base powder are poor thermal conductors, heat accumulation at a certain position in the sample can occur, the reaction speed is accelerated, the gas yield is increased rapidly, if threads between a cap and a cup body slide, the cap can jump out to hurt people, and therefore some safety measures need to be taken when a heating furnace is designed.
Therefore, a protective plate is added on the heating furnace, and a using method is specified, and in case of cap jumping out, the protective plate can prevent the cap from hurting people, and the specific measures are as follows: the protection plate is a curved surface and is consistent with the curvature of the outer side surface of the heating body, and the protection plate is welded on the outer ring of the upper surface of the heating body; the width of the protection plate is 200mm, the thickness of the protection plate is 5mm, the protection plate is 200mm higher than the upper plane of the heating body, the material is 316 stainless steel \8230, the material is 8230, in the sample taking and placing operation process, an operator stands vertically right opposite to the protection plate, and the distance between the body and the protection plate of the heating furnace (4) is 100-200 mm.
(6) Ensuring the accuracy of the detection result
The patent judges the storage stability by detecting the thermally generated decomposed gas of NC and NG-based gunpowder, and determines 5 links for analysis according to the heating gas production, gas production injection chromatograph, chromatograph detection data processing and judgment basis, and the following control measures are required to be taken to improve the accuracy of the evaluation result:
I. heating gas production link
The sample is uniformly heated, the sealing performance of the reactor is good, and the gas production rate of the sample subjected to thermal decomposition can not be obviously different even if the sample is placed into different reactors. The control measures adopted by the patent are as follows: the reactor is made of 316 stainless steel and has good heat conductivity; the depth of a lofting hole of the heating furnace is 90mm, the diameter of the lofting hole is 38mm, and the whole reactor can be placed into the lofting hole; the heating furnace is provided with a heat preservation cover for heat preservation.
II, gas production injection chromatograph link
The decomposed gas generated by collecting the sample is injected into the gas chromatograph, and automatic sample injection rather than manual sample injection is used, so that the gas leakage rate during air extraction from the reactor can be reduced.
The automatic sample introduction is realized by a Shiviaroc quick connector. The Shiviaroc quick connector is divided into a part A and a part B. The Shiviaroc quick coupling A is fixed on the reactor, and the Shiviaroc quick coupling B is fixed on the gas chromatograph. The Shiviaroc quick connector A is matched with the Shiviaroc quick connector B, when the Shiviaroc quick connector A is not connected with the Shiviaroc quick connector B, the A has sealing performance and seals a port of an exhaust pipe, so that after the cup body 1 and the cap 2 are screwed, the cup body 1, the cap 2 and the exhaust port 3 form a closed space, and gas in the space is not communicated with the atmosphere. Only after the Shiviaroc quick coupling B part is inserted into the Shiviaroc quick coupling A part, the Shiviaroc quick coupling A part does not have the sealing function any more and becomes a passage. At the moment, the air pump works, gas in the reactor enters the quantitative pipe through the gas production pipe, and then is automatically injected into the chromatographic column for separation and detected by the thermal conductivity detector.
The air pump is arranged in the gas chromatograph, the gas chromatograph workstation controls the air pump to pump air, the gas in the reactor enters the gas production pipe and the air pump, the gas in the initial section can only be taken as the gas in the middle section and sent into the quantitative pipe because the gas is not equal to the gas in the reactor and cannot be used for quantitative detection because the gas is mixed with the original air in the gas production pipe, and then the gas is automatically injected into the chromatograph to be detected. In addition, the gas production pipe in the device also needs to waste certain gas, so the gas quantity extracted from the reactor by the air extraction pump is far larger than the gas quantity entering the chromatogram.
Because of decomposition of CO in the gas 2 The content is low, the chromatograph is provided with a thermal conductivity detector TCD, and the sensitivity of the TCD is low, so that the gas amount detected by the chromatograph cannot be too little, otherwise, CO cannot be detected 2 The situation (detection limit is too high). However, the gas flow detected is too large, the reactor may have a strong negative pressure, and accurate quantification is not facilitated. Thus, the appropriate amount of gas to be chromatographed is determined. And comprehensively considering, and finally determining the detection gas amount to be 0.5mL.
Detecting link of chromatograph
Generally, when gas content is detected by using gas chromatography, the effective method for determining the result is 'repeating air extraction test for 2 times for each sample, and when the difference between the areas of two peaks is not more than 5%, the determination result is effective'. When the method is adopted for automatic air extraction and sample injection, the 'effective criterion of the measurement result' is required to be reestablished most probably because the air quantity in the reaction tank is not enough to be detected for 2 times.
A testing cap is designed, the testing cap is provided with a ventilation hole more than the cap of the invention, the inner diameter of the ventilation hole is 0.1mm, and the ventilation hole is positioned at the position 5mm from the center of the testing cap (the ventilation hole is plugged by Vaseline). The reactor is assembled by replacing the cap with a testing cap, and the gas in the empty reactor is continuously detected by the invention for 6 times in total, wherein CO is detected 2 The chromatographic peak areas are 65207, 64867, 65195 and 65535 respectively65681 and 66191, the oxygen and air chromatographic peak areas are 84485027, 83299734, 83292731, 83856192, 83662190 and 83461735 respectively, and the calculated CO can be obtained 2 The content is 0.059%, 0.060%, 0.061%. It is stated that when the composition of the gas to be measured is unchanged, the detection data is stable as long as the apparatus reaches a stable state. Similarly, as long as the device reaches a stable state, even if the detection gas amount is 0.5mL, the gas in each reactor can be only subjected to sample introduction detection for 1 time.
In the above empty reactor test: CO2 2 In the chromatographic peak area detection results, the minimum area of 6 chromatographic peaks is 64867, the maximum area is 66191, and the difference between the two peak areas is 2.0%; the minimum peak area of oxygen and nitrogen chromatographic spectra is 83292731, the maximum peak area is 84485027, and the difference of the two peak areas is 1.4%. CO2 2 The chromatographic peak area difference value and the oxygen and nitrogen chromatographic peak area difference value all meet the requirements that the air extraction test is repeated for 2 times for each sample tank, and when the area difference between the two peaks does not exceed 5 percent, the measurement result is effective, which shows that the method has the advantages of automatic air extraction and sample injection operation, very good repeatability and CO of the gas in the air reactor 2 The chromatographic peak area, the oxygen and nitrogen chromatographic peak areas can all represent the stability of the state of the instrument.
Taking into account some CO in laboratory air 2 May be too low, thus determining the stability of the instrument state characterized by the oxygen and nitrogen chromatographic peak areas, so the new criterion of "effective measurement result" is determined as follows: "2 empty unheated reactor gas is detected, when the difference of chromatographic peak area of oxygen and nitrogen in 2 times of detection is not more than 5%, the state of the apparatus is judged to be stable, and the detection of decomposed gas of the sample can be started.
IV, chromatographic detection data processing link
The detector that this patent gas chromatography was equipped with is thermal conductivity detector TCD, and TCD can produce the response to any gas, obtains response signal according to the thermal conductivity of different gases, but the thermal conductivity of each kind of gas has a little difference, and the chromatographic peak area's of different components ratio is not exactly equal to their volume ratio (volume content).
The specific measures taken in this patent are to consult the resourcesCorrecting the peak area of the chromatographic spectrum to make the calculated result equal to the volume ratio (volume content), and the specific measures are as follows: "CO in gas 2 Volume content = (CO) 2 Chromatographic peak area ÷ 1.3) ÷ nitrogen and oxygen chromatographic peak area × 100% ". In addition, there is a little CO in the air 2 Gases, need to be deducted from the decomposition gases.
The CO in the decomposed gas is obtained by the two measures 2 The content accuracy is higher.
V. judgment basis determination link
The errors are divided into systematic errors, random errors and gross errors, and even if the technical control measures of the 4 links are adopted, the detection result still has certain random errors. In the final evaluation, the misjudgment of the judgment result due to random errors must be avoided.
This patent decomposes CO in the gas through 2 former samples 2 And determining the random error by using the absolute value sigma of the content difference. According to experience, the random error is determined in this way in the detection, and generally a coefficient of 2 to 3 is multiplied, and considering that there is some difference between the modified sample and the original sample, the random error is determined to be 3 σ for the sake of safety, and the specific judgment basis is as follows: "2 original sample decomposed CO in gas 2 The average value of the contents is used as the CO in the original decomposed gas 2 Content omega 0 823060, 823080, decomposing CO in gas by modified sample 2 Content omega 1 823060 \ 8230a primer omega 0 Minus omega 1 Is equal to Δ; when-3 sigma is less than or equal to delta is less than or equal to 3 sigma, the DIANP with the content is evaluated to have no influence on the storage stability of NC and NG-based fire drugs; when Δ > 3 σ, it is evaluated that the content of DIANP can improve the storage stability of NC and NG-based powder; when Delta < -3. Sigma., it was evaluated that the DIANP content decreased the storage stability of NC and NG-based gunpowder "
By paying attention to the problems and carrying out corresponding technical design, the invention obtains the device and the method for evaluating the influence of DIANP on the storage stability of NC and NG-based explosives. The beneficial effects of the invention are shown in the following aspects:
(1) Accurate and objective assessment of the effect of DIANP on storage stability of NC-and NG-based explosives
According to DIANP and nitrateThe decomposition properties of the substances, determined by CO 2 The decomposition degree of NC-based gunpowder and NG-based gunpowder is represented, and the NC-based gunpowder and NG-based gunpowder with large decomposition degree have poor stability. Under the same heating condition, NC and NG based fire drugs decompose CO in the fire drugs 2 The content is high, which indicates that the storage stability is poor, so that the influence of DIANP on the storage stability of NC and NG-based explosives is evaluated, and N is avoided 2 Not absorbed leads to a misjudgment of increased gas production (VST method).
The high accuracy of the evaluation result is ensured by the technical control measures taken in 5 links of heating gas production, gas production injection chromatograph, chromatograph detection data processing and evaluation basis determination.
(2) The sample is in a more sufficient air environment in the test process and conforms to the actual charging environment
Through the design of the reactor, the sample is ensured to be in an abundant air atmosphere in the heating process, and the detection result can reflect the actual storage stability of NC and NG base gunpowder.
The method modifies the requirement of the VST on the sample size, and avoids the deviation of the detection result which is inconsistent with the actual storage condition due to the undersize of the sample in the air environment.
The laboratory detection result is consistent with the actual situation, and the accuracy of the evaluation result is further improved.
(3) Greatly shortening the test time
By the design of increasing the sample amount, heating temperature, safety guarantee and the like, on the premise of ensuring that the reaction mechanism is consistent with the normal-temperature actual storage state and the test process is safe, the continuous heating time of the sample is shortened to 8h from 48h of a VST method, the whole test time is only one sixth of the previous test time (the time for detecting the pressure in the VST and the time for detecting the chromatogram in the VST are both 5 minutes), and the whole test period is greatly shortened.
Drawings
FIG. 1 is a schematic view of the apparatus. 1. The gas production device comprises a cup body, 2 a cap, 3 an air extraction opening, 4 a heating furnace, 5 a gas production device and 6 a gas chromatograph.
FIG. 2 is a chromatogram of a sample decomposition gas and air.
Detailed Description
The invention will be described in more detail with reference to the accompanying drawings and preferred embodiments.
Example 1
The method is characterized in that DIANP is used for replacing 3% by mass of NG in NC-based propellant powder (which belongs to three-base gunpowder, namely NG 16%, NC 29.5%, nitroguanidine 47%, and the balance of 7.5%) to prepare a modified propellant powder, and the influence of DIANP on the storage stability of NC-based and NG-based propellant powders is evaluated by the patent.
As shown in figure 1, a DIANP is to the assessment device of NC and NG basic fire medicine storage stability influence, the said apparatus includes comprising cup body 1, cap 2, air extraction 3, heating furnace 4, gas production device 5 and gas chromatograph 6;
the cup body 1 is a barrel, the wall thickness of the cup body 1 is 2.5mm, the inner diameter is 25mm, the outer height is 80mm, the bottom thickness is 3mm, the upper end part of the outer surface of the cup body 1 is a first external thread area, the height of the first external thread area is 10mm, and the cup body 1 is made of 316 stainless steel;
the outer diameter of the cap 2 is 36mm, the outer height of the cap 2 is 15mm, the inner depth of the cap 2 is 10.5mm, a second internal thread area with the height of 8mm is arranged from the bottom end to the top of the cap 2, the second internal thread area is matched with the thread of the first external thread area of the cup body 1, and an air hole with the diameter of 1mm is formed in the center of the circle on the upper surface of the cap 2; the uppermost end in the cap 2 is provided with a second sealing ring, and the outer diameter, the inner diameter and the thickness of the second sealing ring are 30mm, 26mm and 3mm respectively; the second sealing gasket is made of silicon rubber, and the rest materials are 316 stainless steel;
the cap 2 is positioned right above the cup body 1;
the air pumping port 3 consists of an upper part and a lower part, the lower part of the air pumping port 3 is an air pumping pipe, and the upper part of the air pumping port 3 is a Shiviaoke quick connector A part; the material of the air extraction opening 3 is 316 stainless steel; the length of the exhaust pipe is 100mm, the upper end of the exhaust pipe is connected with the Shiviaoke quick connector A part, and the Shiviaoke quick connector A part plays a role in sealing the exhaust pipe;
the air exhaust port 3 is positioned right above the cap 2, the lower end of the air exhaust pipe is welded at the center of the upper surface of the cap 2, and the inside of the air exhaust pipe is communicated with the air hole of the cap 2;
1 cup body 1, 1 cap 2 and 1 extraction opening 3 form 1 reactor;
the heating furnace 4 consists of an upper part, a middle part and a lower part, the lower part of the heating furnace 4 is a heating body, the middle part of the heating furnace 4 is a protection plate, and the upper part of the heating furnace 4 is a heat-insulating cover; the heating body is a cylinder, sample holes are uniformly distributed on the upper plane of the heating body, the depth of each sample hole is 90mm, the diameter of each sample hole is 38mm, and the upper left end and the upper right end of the side surface of the heating body are respectively provided with 1 hinge quick lock catch part A; the protection plate is a curved surface and is consistent with the curvature of the outer side surface of the heating body, and the protection plate is welded on the outer ring of the upper surface of the heating body; the width of the protection plate is 200mm, the thickness of the protection plate is 5mm, the protection plate is 200mm higher than the upper plane of the heating body, and the protection plate is made of 316 stainless steel; the heat preservation cover is a flat cylinder, and the diameter of the heat preservation cover is consistent with that of the heating body; the heat preservation cover is not connected with the heating body and the protection plate; the left end point and the right end point of the side surface of the heat preservation cover are respectively provided with 1 hinge quick lock catch B part, and the hinge quick lock catch B part is matched with the hinge quick lock catch A part of the heating body;
the cup body 1 is positioned right above the sample placing hole of the heating furnace 4;
the gas production device 5 consists of a left part, a middle part and a right part, the left part of the gas production device 5 is a gas production pipe, the middle part of the gas production device 5 is a quantitative pipe, and the right part of the gas production device 5 is an air pump; the gas production pipe consists of a polytetrafluoroethylene pipeline and a Shiviaoke quick joint B part; the left end of the polytetrafluoroethylene pipeline is connected with a Shiviaoke quick joint B part, and the Shiviaoke quick joint B part is matched with the Shiviaoke quick joint A part of the air suction port 3; the right end of the polytetrafluoroethylene pipeline is connected with an air pump through a quantitative pipe, and the volume of the quantitative pipe is 0.5mL;
a quantitative tube and an air pump in the gas production device 5 are arranged inside the gas chromatograph 6, and a gas production tube is positioned outside the gas chromatograph 6; the gas production device 5 is not connected with the cup body 1, the cap 2, the extraction opening 3 and the heating furnace 4;
the gas chromatograph 6 comprises a chromatographic column, a thermal conductivity detector and a workstation; the work of the workstation comprises the steps of controlling the starting of an air pump, feeding sample by a quantitative tube, adjusting the temperature of a chromatographic column, adjusting the temperature of a thermal conductivity detector and recording the area of a chromatographic peak;
the gas chromatograph 6 is not connected with the cup body 1, the cap 2, the extraction opening 3 and the heating furnace 4;
the evaluation device for the influence of DIANP on the storage stability of NC and NG-based fire drugs comprises the following steps:
step 4, starting the gas chromatograph 6, and setting the temperature of the detector to be 250 ℃ and the temperature of the chromatographic column to be 80 ℃; after the instrument is stabilized, pumping air to detect 2 unheated empty reactors; inserting the Shiweiroc quick joint B part of the gas production device 5 into the Shiweiroc quick joint A part of the extraction opening 3, and communicating a gas production pipe of the gas production device 5 with the interior of the reactor; the gas chromatograph 6 workstation controls the air pump, the gas in the reactor is pumped into the quantitative tube of the gas production device 5 from the air pumping port 3, and then the gas is injected into the chromatographic column for separation, the thermal conductivity detector detects, and the chromatographic peak areas of oxygen and nitrogen are recorded; comparing the chromatographic peak areas of oxygen and nitrogen of 2 empty reactors, judging that the state of the instrument is stable when the difference of the 2 peak areas is not more than 5%, and detecting the heated reactor;
step 7, decomposing CO in the gas by using the original sample 2 Content = CO in the reactor gas as received 2 Volume content-CO in heated empty reactor gas 2 Volume content; CO in 2 original decomposed gases 2 The average value of the contents is used as the CO in the original decomposed gas 2 Content omega 0 (ii) a CO in 2 original decomposed gases 2 The absolute value of the content difference is recorded as sigma;
step 8, modifying CO in the sample decomposed gas 2 Content omega 1 = CO in reactor gas containing modified sample 2 Volume content-CO in heated empty reactor gas 2 Volume content;
step 9, let omega 0 Minus omega 1 Is equal to Δ; when-3 sigma is less than or equal to delta and less than or equal to 3 sigma, the DIANP with the content has no influence on the storage stability of NC and NG-based fire drugs; when Δ > 3 σ, it is evaluated that the content of DIANP can improve the storage stability of NC and NG-based powder; when Δ < -3 σ, it was evaluated that this content of DIANP decreased the storage stability of NC and NG-based gunpowder.
The detection result of this embodiment: CO in original decomposed gas 2 The contents are 0.69% and 0.80% respectively, and the average value is 0.74% of CO in the original decomposed gas 2 Content omega 0 2 original CO in decomposed gas 2 The absolute value of the content difference σ is 0.11%, and 3 σ is0.33 percent; modified sample decomposed CO in gas 2 Content omega 1 0.51%; Δ (ω) 0 Minus omega 1 ) Equal to 0.23% < 0.33%. Therefore, it was confirmed that 3% of DIANP had no effect on the storage stability of NC-based propellant powder (tribasic powder). The detection result is consistent with the detection result of the DSC method.
Example 2
The effect of DIANP on the storage stability of NC-and NG-based propellants was evaluated by this patent by replacing 10% by mass of NG in an NC-based propellant (which is a double-base powder, NG 26.7%, NC 56.0%, and the remaining 17.3%) with DIANP to produce a modified propellant.
As shown in figure 1, a DIANP is to the assessment device of NC and NG basic fire medicine storage stability influence, the said apparatus includes comprising cup body 1, cap 2, air extraction 3, heating furnace 4, gas production device 5 and gas chromatograph 6;
the cup body 1 is a barrel, the wall thickness of the cup body 1 is 2.5mm, the inner diameter is 25mm, the outer height is 80mm, the bottom thickness is 3mm, the upper end part of the outer surface of the cup body 1 is a first external thread area, the height of the first external thread area is 10mm, and the cup body 1 is made of 316 stainless steel;
the outer diameter of the cap 2 is 36mm, the outer height of the cap 2 is 15mm, the inner depth of the cap 2 is 10.5mm, a second internal thread area with the height of 8mm is arranged from the bottom end to the top of the cap 2, the second internal thread area is matched with the thread of the first external thread area of the cup body 1, and an air hole with the diameter of 1mm is formed in the center of the circle on the upper surface of the cap 2; the uppermost end in the cap 2 is provided with a second sealing ring, and the outer diameter, the inner diameter and the thickness of the second sealing ring are 30mm, 26mm and 3mm respectively; the second sealing gasket is made of silicon rubber, and the rest materials are 316 stainless steel;
the cap 2 is positioned right above the cup body 1;
the air pumping port 3 consists of an upper part and a lower part, the lower part of the air pumping port 3 is an air pumping pipe, and the upper part of the air pumping port 3 is a Shiviaoke quick connector A part; the material of the air extraction opening 3 is 316 stainless steel; the length of the exhaust pipe is 100mm, the upper end of the exhaust pipe is connected with the Shiviaoke quick connector A part, and the Shiviaoke quick connector A part plays a role in sealing the exhaust pipe;
the air exhaust port 3 is positioned right above the cap 2, the lower end of the air exhaust pipe is welded at the center of the upper surface of the cap 2, and the inside of the air exhaust pipe is communicated with an air hole of the cap 2;
1 cup body 1, 1 cap 2 and 1 extraction opening 3 form 1 reactor;
the heating furnace 4 consists of an upper part, a middle part and a lower part, the lower part of the heating furnace 4 is a heating body, the middle part of the heating furnace 4 is a protection plate, and the upper part of the heating furnace 4 is a heat-insulating cover; the heating body is a cylinder, sample placing holes are uniformly distributed on the upper plane of the heating body, the depth of each sample placing hole is 90mm, the diameter of each sample placing hole is 38mm, and the upper left end and the upper right end of the side surface of the heating body are respectively provided with 1 hinge quick lock A part; the protection plate is a curved surface and is consistent with the curvature of the outer side surface of the heating body, and the protection plate is welded on the outer ring of the upper surface of the heating body; the width of the protection plate is 200mm, the thickness of the protection plate is 5mm, the protection plate is 200mm higher than the upper plane of the heating body, and the protection plate is made of 316 stainless steel; the heat preservation cover is a flat cylinder, and the diameter of the heat preservation cover is consistent with that of the heating body; the heat preservation cover is not connected with the heating body and the protection plate; the left end point and the right end point of the side surface of the heat preservation cover are respectively provided with 1 hinge quick lock catch B part, and the hinge quick lock catch B part is matched with the hinge quick lock catch A part of the heating body;
the cup body 1 is positioned right above the sample placing hole of the heating furnace 4;
the gas production device 5 consists of a left part, a middle part and a right part, the left part of the gas production device 5 is a gas production pipe, the middle part of the gas production device 5 is a quantitative pipe, and the right part of the gas production device 5 is an air pump; the gas production pipe consists of a polytetrafluoroethylene pipeline and a Shiviaoke quick joint B part; the left end of the polytetrafluoroethylene pipeline is connected with a Shiviaoke quick joint B part, and the Shiviaoke quick joint B part is matched with the Shiviaoke quick joint A part of the air suction port 3; the right end of the polytetrafluoroethylene pipeline is connected with an air pump through a quantitative pipe, and the volume of the quantitative pipe is 0.5mL;
a quantitative tube and an air pump in the gas production device 5 are arranged inside the gas chromatograph 6, and a gas production tube is positioned outside the gas chromatograph 6; the gas production device 5 is not connected with the cup body 1, the cap 2, the extraction opening 3 and the heating furnace 4;
the gas chromatograph 6 comprises a chromatographic column, a thermal conductivity detector and a workstation; the work of the workstation comprises the steps of controlling the starting of an air pump, feeding sample by a quantitative tube, adjusting the temperature of a chromatographic column, adjusting the temperature of a thermal conductivity detector and recording the area of a chromatographic peak;
the gas chromatograph 6 is not connected with the cup body 1, the cap 2, the extraction opening 3 and the heating furnace 4;
the evaluation device for the influence of DIANP on the storage stability of NC and NG-based fire drugs comprises the following steps:
step 4, starting the gas chromatograph 6, and setting the temperature of the detector to be 250 ℃ and the temperature of the chromatographic column to be 80 ℃; after the instrument is stabilized, pumping air to detect 2 unheated empty reactors; inserting the Shiweiroc quick joint B part of the gas production device 5 into the Shiweiroc quick joint A part of the extraction opening 3, and communicating a gas production pipe of the gas production device 5 with the interior of the reactor; the gas chromatograph 6 workstation controls the air pump, the gas in the reactor is pumped into the quantitative tube of the gas production device 5 from the air pumping port 3, and then the gas is injected into the chromatographic column for separation, the thermal conductivity detector detects, and the chromatographic peak areas of oxygen and nitrogen are recorded; comparing the chromatographic peak areas of oxygen and nitrogen of the 2 empty reactors, judging that the state of the instrument is stable when the difference of the 2 peak areas is not more than 5%, and detecting the heated reactor;
step 7, decomposing CO in the gas in the original sample 2 Content = CO in the reactor gas as received 2 Volumetric content-CO in heated empty reactor gas 2 Volume content; CO in 2 original decomposed gases 2 The average value of the contents is used as the CO in the original decomposed gas 2 Content omega 0 (ii) a CO in 2 original decomposed gases 2 The absolute value of the content difference is recorded as sigma;
step 8, modifying CO in the sample decomposed gas 2 Content omega 1 = CO in reactor gas containing modified sample 2 Volume content-CO in heated empty reactor gas 2 Volume content;
step 9, let omega 0 Minus omega 1 Is equal to Δ; when-3 sigma is less than or equal to delta is less than or equal to 3 sigma, the DIANP with the content is evaluated to have no influence on the storage stability of NC and NG-based fire drugs; when Δ > 3 σ, it is evaluated that the content of DIANP can improve the storage stability of NC and NG-based powder; when Δ < -3 σ, it was evaluated that this content of DIANP decreased the storage stability of NC and NG-based gunpowder.
The detection result of this embodiment: CO in original decomposed gas 2 The contents were 1.32% and 1.45%, respectively, and the average value of 1.38% was as-isCO in the decomposed gas 2 Content omega 0 2 original decomposed CO in gas 2 The absolute value sigma of the content difference is 0.13 percent, and the absolute value 3 sigma is 0.39 percent; CO in modified sample decomposed gas 2 Content omega 1 0.75%; Δ (ω) 0 Minus omega 1 ) Equal to 0.63% > 0.39%. Thus, it is believed that 10% DIANP provides the NC-based propellant (as a bis-based powder) with storage stability. The detection result is consistent with the detection result of the DSC method.
Claims (2)
1. A method for evaluating the influence of nitramine azide on the storage stability of nitrocotton and nitroglycerin based gunpowder is characterized in that a device used in the method comprises a cup body (1), a cap (2), an air extraction opening (3), a heating furnace (4), an air extraction device (5) and a gas chromatograph (6);
the cup body (1) is a barrel, the wall thickness of the cup body (1) is 2.5mm, the inner diameter is 25mm, the outer height is 80mm, the bottom thickness is 3mm, the upper end part of the outer surface of the cup body (1) is a first external thread area, the height of the first external thread area is 10mm, and the cup body (1) is made of 316 stainless steel;
the outer diameter of the cap (2) is 36mm, the outer height of the cap is 15mm, the inner depth of the cap is 10.5mm, a second internal thread area with the height of 8mm is arranged from the bottom end of the cap (2) to the top, the second internal thread area is matched with the thread of the first external thread area of the cup body (1), and an air hole with the diameter of 1mm is formed in the center of the circle on the upper surface of the cap (2); the uppermost end in the cap (2) is provided with a second sealing ring, and the outer diameter, the inner diameter and the thickness of the second sealing ring are 30mm, 26mm and 3mm respectively; the second sealing gasket is made of silicon rubber, and the rest materials are 316 stainless steel;
the cap (2) is positioned right above the cup body (1);
the air extraction opening (3) consists of an upper part and a lower part, the lower part of the air extraction opening (3) is provided with an air extraction pipe, and the upper part of the air extraction opening (3) is provided with a Shiviaoke quick connector A part; the material of the air extraction opening (3) is 316 stainless steel; the length of the air exhaust pipe is 100mm, the upper end of the air exhaust pipe is connected with the Shivaloke quick connector A part, and the Shivaloke quick connector A part plays a role in sealing the air exhaust pipe;
the air exhaust port (3) is positioned right above the cap (2), the lower end of the air exhaust pipe is welded at the center of the upper surface of the cap (2), and the inside of the air exhaust pipe is communicated with the air hole of the cap (2);
1 reactor is composed of 1 cup body (1), 1 cap (2) and 1 pumping hole (3);
the heating furnace (4) consists of an upper part, a middle part and a lower part, the lower part of the heating furnace (4) is a heating body, the middle part of the heating furnace (4) is a protection plate, and the upper part of the heating furnace (4) is a heat-insulating cover; the heating body is a cylinder, sample placing holes are uniformly distributed on the upper plane of the heating body, the depth of each sample placing hole is 90mm, the diameter of each sample placing hole is 38mm, and the upper left end and the upper right end of the side surface of the heating body are respectively provided with 1 hinge quick lock A part; the protection plate is a curved surface and is consistent with the curvature of the outer side surface of the heating body, and the protection plate is welded on the outer ring of the upper surface of the heating body; the width of the protection plate is 200mm, the thickness of the protection plate is 5mm, the protection plate is 200mm higher than the upper plane of the heating body, and the protection plate is made of 316 stainless steel; the heat preservation cover is a flat cylinder, and the diameter of the heat preservation cover is consistent with that of the heating body; the heat preservation cover is not connected with the heating body and the protection plate; the left end point and the right end point of the side surface of the heat preservation cover are respectively provided with 1 hinge quick lock catch B part, and the hinge quick lock catch B part is matched with the hinge quick lock catch A part of the heating body;
the cup body (1) is positioned right above the sample placing hole of the heating furnace (4);
the gas production device (5) consists of a left part, a middle part and a right part, the left part of the gas production device (5) is a gas production pipe, the middle part of the gas production device (5) is a quantitative pipe, and the right part of the gas production device (5) is an air extraction pump; the gas production pipe consists of a polytetrafluoroethylene pipeline and a Shiviaoke quick joint B part; the left end of the polytetrafluoroethylene pipeline is connected with a Shiweoke quick coupling B part, and the Shiweoke quick coupling B part is matched with the Shiweoke quick coupling A part of the extraction opening (3); the right end of the polytetrafluoroethylene pipeline is connected with an air pump through a quantitative pipe, and the volume of the quantitative pipe is 0.5mL;
a quantitative pipe and an air pump in the gas production device (5) are arranged in the gas chromatograph (6), and a gas production pipe is positioned outside the gas chromatograph (6); the gas production device (5) is not connected with the cup body (1), the cap (2), the extraction opening (3) and the heating furnace (4);
the gas chromatograph (6) comprises a chromatographic column, a thermal conductivity detector and a workstation; the work of the workstation comprises the steps of controlling the starting of an air pump, feeding sample by a quantitative tube, adjusting the temperature of a chromatographic column, adjusting the temperature of a thermal conductivity detector and recording the area of a chromatographic peak;
the gas chromatograph (6) is not connected with the cup body (1), the cap (2), the extraction opening (3) and the heating furnace (4);
the method specifically comprises the following steps:
step 1, treating 30 g of nitrocotton NC and nitroglycerin NG based propellant without nitrine nitroamine DIANP to ensure that the length, width and height of the nitrocotton NC and the nitroglycerin NG based propellant are not more than 10mm and are marked as original samples; treating 30 g of NC and NG based fire powder containing DIANP to make length, width and height not more than 10mm, and marking as modified sample;
step 2, putting 1 cup body (1) with an upward opening on a workbench, filling 10g of modified sample, and screwing down a cap (2) to assemble the reactor; taking another 2 cup bodies (1) with upward openings, placing the cup bodies on a workbench, respectively filling 10g of original samples, screwing a cap (2) and assembling the reactor to obtain parallel samples; assembling 3 empty reactors without samples;
step 3, heating the heating furnace (4) to 100 ℃, after the temperature is stable, putting the 3 reactors with the samples and 1 empty reactor which are assembled in the step 2 into 4 sample placing holes of the heating furnace (4), and bending the air exhaust pipe of the air exhaust port (3) of each reactor towards the outer side of the heating body so that the part A of the Shiviaoke quick connector is not positioned above the heating body; covering a heat-insulating cover, enabling the 2 hinge quick lock catches B of the heat-insulating cover to correspond to the 2 hinge quick lock catches A of the heating body, and enabling the heat-insulating cover to be connected with the heating body through the upper hinge quick lock catches; recording the heating time after 30min, opening the hinge quick lock catch after heating for 8 hours, and taking the heat preservation cover away; the extraction pipe of the extraction opening (3) of each reactor faces upwards, the reactor is taken out, and the reactor is cooled down at room temperature and the like to be detected; in the sample taking and placing operation process, an operator stands vertically opposite to the protection plate, and the distance between the body and the protection plate of the heating furnace (4) is 100-200 mm;
step 4, starting the gas chromatograph (6), and setting the temperature of the detector to be 250 ℃ and the temperature of the chromatographic column to be 80 ℃; after the instrument is stabilized, pumping air to detect 2 unheated empty reactors; inserting the Shiweiroc quick joint B part of the gas production device (5) into the Shiweiroc quick joint A part of the extraction opening (3), and communicating a gas production pipe of the gas production device (5) with the interior of the reactor; a gas chromatograph (6) workstation controls an air pump, air in the reactor is pumped into a quantitative tube of an air extraction device (5) from an air extraction port (3), and then the air is injected into chromatographic column separation, a thermal conductivity detector detects and records the chromatographic peak areas of oxygen and nitrogen; comparing the chromatographic peak areas of oxygen and nitrogen of 2 empty reactors, judging that the state of the instrument is stable when the difference of the 2 peak areas is not more than 5%, and detecting the heated reactor;
step 5, after the reactor is cooled to room temperature, starting air extraction detection; inserting the Shiweiroc quick joint B part of the gas production device (5) into the Shiweiroc quick joint A part of the extraction opening (3), and communicating a gas production pipe of the gas production device (5) with the interior of the reactor; a gas chromatograph (6) workstation controls an air pump, air in the reactor is pumped into a quantitative tube of an air extraction device (5) from an air extraction port (3), and then the air is injected into a chromatographic column for separation, a thermal conductivity detector for detection and chromatographic peak area recording; detecting the gas in the 4 heated reactors according to the same step;
step 6, CO in the reactor gas 2 Volume content = (CO) 2 Chromatographic peak area ÷ 1.3) ÷ nitrogen and oxygen chromatographic peak area × 100%;
step 7, decomposing CO in the gas in the original sample 2 Content = CO in the reactor gas as received 2 Volumetric content-CO in heated empty reactor gas 2 Volume content; CO in 2 original decomposed gases 2 The average value of the contents is used as the CO in the original decomposed gas 2 Content omega 0 (ii) a CO in 2 original decomposed gases 2 The absolute value of the content difference is recorded as sigma;
step 8, modifying CO in the sample decomposed gas 2 Content omega 1 = CO in reactor gas containing modified species 2 Volumetric content-CO in heated empty reactor gas 2 Volume content;
step 9, let omega 0 Minus omega 1 Is equal to Δ; when-3 sigma is less than or equal to delta is less than or equal to 3 sigma, the DIANP with the content is evaluated to have no influence on the storage stability of NC and NG-based fire drugs; when Δ > 3 σ, it was evaluated that the content of DIANP could improve the storage stability of NC and NG base powder; when Δ < -3 σ, it is evaluated that the content of DIANP lowers the storage stability of NC and NG-based powder.
2. The method as claimed in claim 1, wherein the NC and NG-based powder is di-or tri-based powder containing NC and NG, and the NC and NG-based powder containing dinp is modified powder formed by replacing part of NG in the NC and NG-based powder with dinp.
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