CN104829403A - Low burning temperature pyrotechnic gas generating agent composition - Google Patents
Low burning temperature pyrotechnic gas generating agent composition Download PDFInfo
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Abstract
The invention provides a low burning temperature pyrotechnic gas generating agent composition. The composition comprises, by mass, 10-55 parts of guanidine nitrate as a burnable agent, 35-70 parts of basic copper nitrate as an oxidant, 3-10 parts of copper iron oxide as a catalyst and a secondary oxidant, 5-20 parts of a cooling agent and 0.1-3 parts of fluorubber as a binder; and the cooling agent is at least one of carbonate, bicarbonate, aluminum hydroxide, dihydroxyglyoxime, diaminoglyoxime and guanidinium azotetrazolate. The composition has the advantages of low burning temperature, high burning speed, high gas generating rate, low concentration of harmful gas, and stable combustion at a low pressure.
Description
Technical field
The present invention relates to low combustion temperature pyrotechnic gas propellant composition, this gas-evolution agent is applicable to gasifier and other auxiliary powerplant.
Background technology
Gas-evolution agent is used for the subcontrol power set in the fields such as Aeronautics and Astronautics, also to meet an urgent need for car safety air bag, various liferaft and civil aviaton the fast aeration of the equipment such as fire escape, in recent years, along with the expansion of gas-evolution agent Application Areas, the performance requriements of gas-evolution agent is had greatly changed, not only require that gas-evolution agent gas production rate is large, combustion gas is cleaned, and require that combustion temperature is low, fire fast wide ranges.
Guanidine class height nitrogen compound has higher nitrogen content, gas production rate is high, just become the research of non-nitrine gas propellant and user to.
The formula that Chinese patent ZL200410098751.8 provides selects rich oxygen containing Guanidinium nitrate as combustible agent, and basic copper nitrate is as primary oxidant, and copper ferriferous oxide to be held concurrently secondary oxygenant as catalyzer, and perchloric acid ammonium salt is as secondary oxygenant.But although the gas generant formulation of above-mentioned patent adds oxygenant perchloric acid ammonium salt can improve combustion speed, the combustion temperature of formula also increases, need more refrigerating unit, add manufacturing cost, and easily produce irritant gas HCl, bring harm to people.
Chinese patent ZL201080040197.1 provides the formula of 50% ~ 65% Guanidinium nitrate, 20% ~ 40% basic copper nitrate, 8% ~ 20% potassium perchlorate.In order to improve combustion speed, adding potassium perchlorate, but also improving the combustion temperature of gas-evolution agent simultaneously, this is obviously very unfavorable to reduction exit gas combustion temperature.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of guanidine class gas-evolution agent, combustion temperature is low, and combustion speed is high, and factor of created gase is high, and harmful gas concentration is low, also can burn with stable combustion quick burning under low pressure.
The technical solution adopted for the present invention to solve the technical problems comprises following component: the Guanidinium nitrate of 10 ~ 55 mass parts is as combustible agent, the basic copper nitrate of 35 ~ 70 mass parts is as oxygenant, the copper ferriferous oxide of 3 ~ 10 mass parts to be held concurrently secondary oxygenant as catalyzer, the cooling agent of 5 ~ 20 mass parts, the viton of 0.1 ~ 3 mass parts is as binding agent; Described cooling agent is at least one in carbonate, supercarbonate, aluminium hydroxide, dihydroxyl glyoxime, diamino glyoxime, azotetrazole two guanidine.
The granularity of described Guanidinium nitrate is 1.5 μm ~ 14 μm, and the granularity of basic copper nitrate is 1 μm ~ 10 μm, and the granularity of copper ferriferous oxide is 0.2 μm ~ 10 μm, and the granularity of described cooling agent is 1.5 μ ~ 15 μ.
The consumption of described Guanidinium nitrate is 15 ~ 45 mass parts, and granularity is 2 μm ~ 18 μm; Consumption 40 ~ 60 mass parts of basic copper nitrate, granularity is 3 μm ~ 9 μm; The consumption of copper ferriferous oxide is 3 ~ 5 mass parts, and granularity is 0.5 μm ~ 3 μm; The granularity of described cooling agent is 2 μm ~ 10 μm.
Described copper ferriferous oxide is the preparation that ferric oxide and cupric oxide are mixed to get according to the mass ratio of 1:1.
Described viton is soluble fluoride rubber, is dissolved in acetone solvent obtained by viton according to the mass ratio of 1:10.
The invention has the beneficial effects as follows:
(1) combustible agent that low combustion temperature pyrotechnic gas propellant of the present invention is used is Guanidinium nitrate.Guanidinium nitrate toxicity is low, wide material sources, and nitrogen content is high, and gas production rate is large, and combustion temperature is low, and good with other chemical substance consistency.The consumption of Guanidinium nitrate in formula is between 10% ~ 55%, and optimum amount 15% ~ 45%, granularity is between 1.5 μ ~ 14 μ, and optimum size 2 μ ~ 8 μ, more can give full play to its advantage.
(2) oxygenant that the present invention is used is basic copper nitrate, it has excellent thermostability, oxygen level is high, and Enthalpies of Formation is low, compared with the nitrate of other alkali metal, product easily filters, the CO content produced than the Guanidinium nitrate formula of same ratio alkali metal or alkaline earth metal nitrate is low, and the usage quantity of basic copper nitrate in formula is between 35% ~ 70%, optimum amount 40% ~ 60%, granularity between 1 μ ~ 10 μ, optimum size 3 μ ~ 9 μ.
(3) have employed above-mentioned two kinds of materials as after combustible agent and oxygenant, secondary oxygenant copper ferriferous oxide has been added in formula, in formula, copper ferriferous oxide not only plays the effect of oxygenant, and as catalyzer by the toxic gas such as carbon monoxide, oxynitride product catalyst, produce nontoxic carbonic acid gas and nitrogen, the consumption of copper ferriferous oxide in formula between 3% ~ 10%, optimum amount 3% ~ 5%, granularity between 0.2 μ ~ 10 μ, optimum size 0.5 μ ~ 3 μ.
(4) for reducing the combustion temperature of pyrotechnic gas propellant, cooling agent is added in formula, it is from carbonate, supercarbonate, aluminium hydroxide, dihydroxyl glyoxime, diamino glyoxime, the at least one that azotetrazole two guanidine is selected, known azo tetrazolium two guanidine is as gas-evolution agent component, the ignition characteristic of gas-evolution agent can be increased and improve combustion speed, with in the past with ammoniumper chlorate improved fire speed formula compared with, gas-evolution agent combustion temperature is low, and release without obnoxious flavour HCl, in formula, consumption is between 5% ~ 20%, granularity is between 1.5 μ ~ 15 μ, optimum size 2 μ ~ 10 μ.
(5) gas-evolution agent with 0.1% ~ 3% viton as binding agent, the mechanical property of gas-evolution agent can be increased, simultaneously can participate in combustion reactions, improve combustion speed.
(6) the present invention uses the compound of cupric in a large number, not only utilizes it as oxygenant, and resultant elemental copper is easily adsorbed on filtering net, and the dust decreased in combustion gas generates.
Accompanying drawing explanation
Fig. 1 is the test result schematic diagram of comparative example 3;
Fig. 2 is low combustion temperature pyrotechnic gas propellant composition P-t graphic representation, and wherein, (a) is the graphic representation of comparative example 4 and embodiment 28,30,31, and (b) is the graphic representation of embodiment 29.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described, the present invention includes but be not limited only to following embodiment.
The present invention includes following component (mass percent):
Combustible agent Guanidinium nitrate, content is 10% ~ 55%, and granularity is between 1.5 μ ~ 14 μ, oxygenant basic copper nitrate, content is 35% ~ 70%, and granularity is between 1 μ ~ 10 μ, catalyzer is held concurrently the copper ferriferous oxide of secondary oxygenant, content is 3% ~ 10%, granularity between 0.2 μ ~ 10 μ, cooling agent, content is 5% ~ 20%, granularity is between 1.5 μ ~ 15 μ, and the binding agent of above-mentioned formula is viton, and consumption is 0.1% ~ 3%.
The optimum amount 15% ~ 45% of Guanidinium nitrate in formula, optimum size 2 μ ~ 8 μ.
The optimum amount 40% ~ 60% of basic copper nitrate in formula, optimum size 3 μ ~ 9 μ.
The optimum amount 3% ~ 5% of copper ferriferous oxide in formula, optimum size 0.5 μ ~ 3 μ.
At least one that cooling agent is selected from carbonate, supercarbonate, aluminium hydroxide, dihydroxyl glyoxime, diamino glyoxime, azotetrazole two guanidine, optimum size 2 μ ~ 10 μ.
Described copper ferriferous oxide is the preparation that ferric oxide and cupric oxide are mixed to get according to the mass ratio of 1:1.
Described binding agent is soluble fluoride rubber, with acetone swelling be 10% soluble fluoride rubber solutions (10g viton is dissolved in 90g acetone solvent).
Embodiment 1 ~ 13, comparative example 1
Preparation has the gas generant composition of composition shown in table 1.According to the Theoretical Calculation of these compositions, obtain theoretical quick-fried heat (H2O is liquid), specific volume (units/ml/g represents the gas content that every 1g composition produces, not moisture), result is as shown in table 1.
Table 1
In table 1, GN is Guanidinium nitrate, BCN is basic copper nitrate, DHG is dihydroxyl glyoxime, GZT is azotetrazole two guanidine.Other table is also similarly represent.The median size of the aluminium hydroxide of table 1 is 2.16 μm (other table is also same), the median size of sodium bicarbonate is 5.12 μm (other table is also same), the median size of dihydroxyl glyoxime is 4.16 μm (other table is also same), the median size of azotetrazole two guanidine is 12.51 μm (other table is also same).
Embodiment 1 ~ 13 with the addition of aluminium hydroxide, sodium bicarbonate, DHG, GZT the quick-fried heat of theory of composition do not add than what of correspondence, quick-fried heat is low, and along with the increase of cooling agent add-on, quick-fried calorific value reduces gradually.
Embodiment 14 ~ 18
Manufacture the gas generant composition with composition shown in table 2.These compositions are according to the quick-fried calorific value of GJB5891.29-2006 test gas propellant, and according to GJB5891.30-2006 test gas propellant gas specific volume value, the quick-fried calorific value of gas, bulking value record adding under the combustion-supporting condition of standard gunpowder.
Table 2
Note: viton is additional
In embodiment 14 ~ 18, survey quick-fried calorific value and all reduce than comparative example 2, conform to calculated value, four kinds of cooling agents all can reduce the quick-fried heat of gas-evolution agent, and adding of DHG can increase gas-evolution agent specific volume.
Embodiment 19 ~ 27
Manufacture the pyrotechnic gas propellant composition with composition shown in table 3.Be right cylinder by these composition moldings, cylinder diameter is Φ 8mm, right cylinder is put into plexi-glass tubular of the same size, synthetic glass thickness of pipe 3mm, 2 places of the h that vertically meets in cylindrical side dig out two apertures, insert in holes thin for 0.25mm two K type thermopairs to powder column center respectively, from being No. 1 thermopair close to firing tip, far away is No. 2 thermopairs, opens wide system at ambient pressure, the combustion temperature of measurement gas propellant and combustion speed.Combustion temperature gets one higher in the top temperature that two thermopairs record, and the time difference of two thermopair top temperatures is t, and the rb=h/t that is determined as of combustion speed obtains, and often organize sample and survey three times, average, a test result of comparative example 2 as shown in Figure 1.
Table 3
Note: viton is additional
The composition actual measurement temperature of combustion that embodiment 19 ~ 27 with the addition of cooling agent is lower than comparative example 3 temperature of not adding cooling agent, and all with the increase of cooling agent add-on, combustion temperature drop is low, combustion prompt drop is low, wherein to add the formula cooling-down effect of 10%NaHCO3 best for embodiment 22, lower than 800 DEG C, but combustion speed is too low; By contrast, the combustion temperature of embodiment 27 is also lower than 800 DEG C, and combustion speed is very fast; And the GZT that embodiment 21 adds 20% fills a prescription, and to fire speed under normal pressure the highest.
Embodiment 28 ~ 31
Manufacture the low combustion temperature pyrotechnic gas propellant composition with composition shown in table 4, by 1.5g composition+150mgBPN priming charge, diameter 10mm powder column is made at 180MPa pressure, these powder columns being arranged on volume is in the manometric bomb of 20ml, lighted by igniter head, test and record generate gaseous tension relation over time, and this system comprises the encloses container that high-strength steel is made, volume: 20ml; DEWE 43A data collecting system; TS-2 charge amplifier (Beijing Space aerodynamic investigation institute), numbering M7101; AK-2 strain pressure transducer, numbering H8279, range: 0 ~ 30MPa, precision: 0.5;
Table 4
Note: viton is additional.
Pmax represents maximum pressure value; AQ represents absolute speed, is P-t slope of a curve between 25% and the maximum pressure value of 75%.Fig. 2 is low combustion temperature pyrotechnic gas propellant composition P-t curve, can observe two peaks significantly, and first peak is igniting peak, and second peak is the burning peak of gas-evolution agent, and peak more obviously illustrates the more difficult point combustion of this gas-evolution agent.
Table 4 and Fig. 2 can find out that the absolute speed of embodiment 30 is the highest, and the absolute speed of embodiment 29 is minimum, consistent with Burning rate testing result, and the igniting peak of embodiment 29 is obvious, and ignition difficulties is described, and embodiment 31 peak of lighting a fire is not obvious, illustrate that igniting easily, and Pmax is higher.
Embodiment 32 ~ 37
Manufacturing the low combustion temperature pyrotechnic gas propellant composition with composition shown in table 5, is the right cylinder of 1.5g by these composition moldings.These right cylinders are arranged in the manometric bomb that internal volume is 1L, after the air in nitrogen replacement manometric bomb, and then by nitrogen pressurization to 6.86MPa, by the energising of nichrome wire, right cylinder is caught fire, after its perfect combustion, combustion gases are taked, in gaseous sample bag, analyze the concentration of NO, NO2, CO, CO2 immediately with detector tube.Result represents in table 5, and embodiment composition is as shown in table 6.
Table 5
Ppm is quality criteria
Table 6
Embodiment 32 ~ 37 can be found out, add the oxynitride of the composition of copper ferriferous oxide, carbon monoxide content is lower than the composition levels not adding copper ferriferous oxide, and the composition oxynitride of embodiment 37, carbon monoxide content is minimum.
Claims (5)
1. one kind low combustion temperature pyrotechnic gas propellant composition, it is characterized in that comprising following component: the Guanidinium nitrate of 10 ~ 55 mass parts is as combustible agent, the basic copper nitrate of 35 ~ 70 mass parts is as oxygenant, the copper ferriferous oxide of 3 ~ 10 mass parts to be held concurrently secondary oxygenant as catalyzer, the cooling agent of 5 ~ 20 mass parts, the viton of 0.1 ~ 3 mass parts is as binding agent; Described cooling agent is at least one in carbonate, supercarbonate, aluminium hydroxide, dihydroxyl glyoxime, diamino glyoxime, azotetrazole two guanidine.
2. low combustion temperature pyrotechnic gas propellant composition according to claim 1, it is characterized in that: the granularity of described Guanidinium nitrate is 1.5 μm ~ 14 μm, the granularity of basic copper nitrate is 1 μm ~ 10 μm, the granularity of copper ferriferous oxide is 0.2 μm ~ 10 μm, and the granularity of described cooling agent is 1.5 μ ~ 15 μ.
3. low combustion temperature pyrotechnic gas propellant composition according to claim 1, it is characterized in that: the consumption of described Guanidinium nitrate is 15 ~ 45 mass parts, granularity is 2 μm ~ 18 μm; Consumption 40 ~ 60 mass parts of basic copper nitrate, granularity is 3 μm ~ 9 μm; The consumption of copper ferriferous oxide is 3 ~ 5 mass parts, and granularity is 0.5 μm ~ 3 μm; The granularity of described cooling agent is 2 μm ~ 10 μm.
4. low combustion temperature pyrotechnic gas propellant composition according to claim 1, is characterized in that: described copper ferriferous oxide is the preparation that ferric oxide and cupric oxide are mixed to get according to the mass ratio of 1:1.
5. low combustion temperature pyrotechnic gas propellant composition according to claim 1, is characterized in that: described viton is soluble fluoride rubber, is dissolved in acetone solvent obtained by viton according to the mass ratio of 1:10.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541525A (en) * | 2016-01-29 | 2016-05-04 | 北京理工大学 | Pyrotechnic gas generating agent and preparation method |
| CN107162865A (en) * | 2017-05-11 | 2017-09-15 | 三明科飞产气新材料股份有限公司 | A kind of gas generant composition and preparation method thereof |
| CN111875457A (en) * | 2020-07-15 | 2020-11-03 | 北京理工大学 | Color agent for fireworks and crackers and preparation method thereof |
| CN116789506A (en) * | 2023-06-30 | 2023-09-22 | 陕西庆华汽车安全系统有限公司 | Gas generating composition for automobile safety belt pretensioner and preparation method thereof |
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| EP1241153A1 (en) * | 1999-11-26 | 2002-09-18 | Daicel Chemical Industries, Ltd. | Gas-generating agent composition |
| CN1644574A (en) * | 2004-12-16 | 2005-07-27 | 中国航天科技集团公司第四研究院第四十二研究所 | Non-nitrine gas generating agent and production thereof |
| CN1651360A (en) * | 2005-03-28 | 2005-08-10 | 张根发 | Gas producing composition and its preparation method |
| CN101990526A (en) * | 2008-04-11 | 2011-03-23 | 大赛璐化学工业株式会社 | Gas generator composition |
| CN102010277A (en) * | 2010-09-15 | 2011-04-13 | 中北大学 | ANPZO-based safe airbag gas generating agent |
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2015
- 2015-04-01 CN CN201510151406.4A patent/CN104829403A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1241153A1 (en) * | 1999-11-26 | 2002-09-18 | Daicel Chemical Industries, Ltd. | Gas-generating agent composition |
| CN1644574A (en) * | 2004-12-16 | 2005-07-27 | 中国航天科技集团公司第四研究院第四十二研究所 | Non-nitrine gas generating agent and production thereof |
| CN1651360A (en) * | 2005-03-28 | 2005-08-10 | 张根发 | Gas producing composition and its preparation method |
| CN101990526A (en) * | 2008-04-11 | 2011-03-23 | 大赛璐化学工业株式会社 | Gas generator composition |
| CN102010277A (en) * | 2010-09-15 | 2011-04-13 | 中北大学 | ANPZO-based safe airbag gas generating agent |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541525A (en) * | 2016-01-29 | 2016-05-04 | 北京理工大学 | Pyrotechnic gas generating agent and preparation method |
| CN105541525B (en) * | 2016-01-29 | 2019-05-14 | 北京理工大学 | A kind of pyrotechnic gas propellant and preparation method |
| CN107162865A (en) * | 2017-05-11 | 2017-09-15 | 三明科飞产气新材料股份有限公司 | A kind of gas generant composition and preparation method thereof |
| CN107162865B (en) * | 2017-05-11 | 2019-02-05 | 三明科飞产气新材料股份有限公司 | A kind of gas generant composition and preparation method thereof |
| CN111875457A (en) * | 2020-07-15 | 2020-11-03 | 北京理工大学 | Color agent for fireworks and crackers and preparation method thereof |
| CN116789506A (en) * | 2023-06-30 | 2023-09-22 | 陕西庆华汽车安全系统有限公司 | Gas generating composition for automobile safety belt pretensioner and preparation method thereof |
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