CN102432408B - Titanium hydride hydrogen storage emulsion explosive - Google Patents
Titanium hydride hydrogen storage emulsion explosive Download PDFInfo
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- CN102432408B CN102432408B CN 201110277487 CN201110277487A CN102432408B CN 102432408 B CN102432408 B CN 102432408B CN 201110277487 CN201110277487 CN 201110277487 CN 201110277487 A CN201110277487 A CN 201110277487A CN 102432408 B CN102432408 B CN 102432408B
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Abstract
本发明属于炸药制备技术领域，具体涉及使用储氢物质制备的乳化炸药。该炸药组分包括乳化基质和敏化剂，所述敏化剂是氢化钛，其质量占氢化钛型储氢乳化炸药总质量的0.6-8%，氢化钛纯度大于等于95%。在引爆过程中，部分氢化钛与乳化基质内水产生化学反应，释放少量氢气，对乳化基质起到一定的发泡效果，并使乳化基质起爆，起到敏化剂作用。同时其余的氢化钛在乳化基质和氢气泡反应产生的高温作用下发生热分解，迅速释放氢气，氢气继续参与乳化基质的爆轰反应，使输出能量中包含了乳化基质和氢化钛共同释放的能量。本发明的氢化钛型储氢乳化炸药具有输出爆炸压力低、冲量大、衰减时间长、能量高的特点。The invention belongs to the technical field of explosive preparation, and in particular relates to an emulsion explosive prepared by using a hydrogen storage substance. The explosive component includes an emulsion matrix and a sensitizer, the sensitizer is titanium hydride, its mass accounts for 0.6-8% of the total mass of the titanium hydride type hydrogen storage emulsion explosive, and the purity of the titanium hydride is greater than or equal to 95%. During the detonation process, part of the titanium hydride reacts chemically with the water in the emulsified matrix, releasing a small amount of hydrogen, which has a certain foaming effect on the emulsified matrix, and detonates the emulsified matrix, acting as a sensitizer. At the same time, the remaining titanium hydride thermally decomposes under the action of the high temperature generated by the reaction of the emulsified matrix and hydrogen bubbles, and releases hydrogen rapidly. The hydrogen continues to participate in the detonation reaction of the emulsified matrix, so that the output energy includes the energy released by the emulsified matrix and titanium hydride. . The titanium hydride type hydrogen storage emulsion explosive of the invention has the characteristics of low output explosion pressure, large impulse, long decay time and high energy.
Description
Technical field
The invention belongs to the explosive preparing technical field, be specifically related to use the emulsion explosive of storage hydrogen material preparation.
Background technology
The milk sap of w/o type is called emulsifying base in the production of emulsion explosive, and it is the element body that consists of emulsion explosive, has preferably stability and potential detonation property.Ammonium nitrate aqueous phase solution (oxygenant) in the emulsifying base is dispersed into minimum particulate in oil-phase solution (combustible agent), its nuclear is for the supersaturation inorganic salt solution, and outsourcing one deck as thin as a wafer but the higher oil film of intensity presents higher viscosity.Emulsifying base is the emulsion explosive of not sensitization, its density is larger, need very large initiation energy, and propagation of explosion is very difficult, therefore, in the process of preparation emulsion explosive, must utilize adiabatic compression and " focus " characteristic of explosive Air by the in addition sensitization of physics or chemical process, a large amount of micro-bubbles evenly distribute in emulsion matrix, produce the blasting cap initiation sensitivity, just can become emulsion explosive.Emulsion explosive is subject to outside energy and does the time spent, owing to the sensibilized of bubble is blasted explosive.It is to be noted, in the prior art, no matter be the glass microsphere sensitizing of utilizing in the physical sensitization, still utilize the whipping agent that adds in the chemical sensitization, the material that " sensitization " process is added mainly plays the effect that increases " focus " in the emulsifying base, to the not contribution of detonation energy of emulsion explosive.Although emulsion explosive has excellent acting ability, its brisance even be higher than TNT, the underwater explosion experiment shows that the indexs such as its blast impulse crest value, momentum, energy are less.This explanation emulsion explosive is slightly inadequate aspect the output energy, need to make in this respect improvement.
Hydrogen storage material is a kind of novel energetic material, can discharge hydrogen under certain condition.Hydrogen has higher energy density: comparing with liquid carbon hydrogen fuel, is its three times; And it does the time spent with oxygen, and unique product is water, does not produce any pollution.Hydrogen-storage alloy is the new function material of late 1960s exploitation, has the large characteristics of storage hydrogen density.Main hydride hydrogen-storing material has that magnesium series, ferrotianium are serial, lanthanum nickel series and zirconium series.
Titanium series metal hydride is considered to very promising hydrogen storage material.Titanium be the hydrogen storage amount of hydride 1.8%～4.0%, titanium elements is at the occurring in nature rich content, low price, the decomposition pressure of its hydride is several normal atmosphere only, is adapted at large-scale application in the industrial production,
At present, not yet find in emulsion explosives technology, to use hydrogen storage material titanium series metal hydride as the report of sensitized material.
Summary of the invention
The objective of the invention is: with the sensitized material of metal hydride hydrogenation titanium as emulsion explosive, under the prerequisite that guarantees the emulsion explosive Sensitivity to Primary Explosion, improve the detonation property of emulsion explosive.
Technical scheme of the present invention is as follows:
Titanium hydride hydrogen storage emulsion explosive of the present invention, its component comprises emulsifying base and sensitizing agent, it is characterized in that, described sensitizing agent is titanium hydride, wherein, the quality of titanium hydride accounts for the 0.6-8% of titanium hydride hydrogen storage emulsion explosive total mass (titanium hydride+emulsifying base), and described titanium hydride is purity more than or equal to 95% powder.
Emulsifying base commonly used in the prescription of described emulsifying base and the existing emulsion explosive is identical, as: ammonium nitrate, SODIUMNITRATE, nitrocalcite, urea, water, wax, rosin, sorbitol monooleate, emulsifying agent etc.;
The preparation method of titanium hydride hydrogen storage emulsion explosive of the present invention is identical with the preparation method of interpolation physics sensitizing agent glass microsphere in the prior art: add titanium hydride in emulsifying base after, use the agitator continuously stirring, make to mix, place again more than 7 hours the time.
The titanium hydride that the present invention adds is evenly distributed in emulsifying base, in the ignition process, water generates chemical reaction in partial hydrogenation titanium and the emulsifying base, discharge a small amount of hydrogen, the emulsified matrix parcel of the hydrogen that discharges, form the bubble hydrogen of discrete distribution, hydrogen plays certain foaming effect to emulsifying base.Simultaneously, the bubble hydrogen in the emulsifying base and titanium hydride particles form one by one " focus ", have increased the cap-sensitivity of emulsifying base, make the emulsifying base can be by blasting cap initiation, and titanium hydride at this moment plays the sensitizing agent effect.After the emulsifying base that mixes titanium hydride is by blasting cap initiation, UNDER SHOCK COMPRESSION focus and bubble hydrogen, the emulsifying base temperature at focus place and bubble hydrogen place raises, emulsifying base and bubble hydrogen are detonated rapidly, thermolysis occurs in remaining titanium hydride under the high temperature action of emulsifying base and bubble hydrogen reaction generation, rapid release hydrogen, the detonation reaction of hydrogen sustainable participation emulsifying base.The detonation reaction that has occured is kept emulsifying base, bubble hydrogen, titanium hydride and is constantly continued above process occurs, and has namely realized the detonation of titanium hydride type emulsifying base explosive.From reaction process as seen, after the emulsifying base of adding titanium hydride is detonated, comprised the common energy that discharges of emulsifying base and titanium hydride in the output energy.
Compare with traditional physical sensitization material glass microballoon, because the titanium hydride volume of equal quality is much smaller, so its overall volume can reduce to some extent, and low price.Compare with the chemical sensitization material, the emulsion explosive that the present invention has also solved chemical sensitization causes the problem of the detonation property decline that the destruction of small bubbles is caused in the explosive because of extruding and vibrations in transportation and powder charge process.
The emulsion explosive that titanium hydride type emulsifying base explosive can be used as a kind of excellent performance uses.Experiment shows: titanium hydride hydrogen storage emulsion explosive of the present invention has the advantages that the output pressure of explosion is low, momentum is large, fall time is long, energy is high.This will make it that extraordinary application prospect is arranged in the specific occasion.For example, in the rock mining process, by control emulsion explosive in titanium hydride content so that detonation gas pressure less than the rock ultimate compression strength, do not destroy rock texture, do not cause rock crackle forming, so that rock mass under low detonation pressure gas expansion effect, along natural joint, bedding or the predetermined spalling changing of the relative positions of road, landslide, the displacement of design of rock self, forms the large rock mass of waste material.
Be further described by the following examples.
Description of drawings
Fig. 1 is that the storage hydrogen emulsion explosive of the embodiment of the invention 1 titanium hydride content 2% carries out the shockwave graphic representation that the underwater explosion test obtains.
Fig. 2 is that the emulsion explosive of glass microsphere content 4% carries out the shockwave graphic representation that the underwater explosion test obtains.
Fig. 3 is that the storage hydrogen emulsion explosive of the embodiment of the invention 2 titanium hydride content 4% carries out the shockwave graphic representation that the underwater explosion test obtains.
Fig. 4 is that the storage hydrogen emulsion explosive of the embodiment of the invention 3 titanium hydride content 6% carries out the shockwave graphic representation that the underwater explosion test obtains.
Embodiment
Embodiment 1:
Titanium hydride and emulsifying base total mass 50g, titanium hydride content are the 2%(=1 g of total mass).Behind emulsifying base interpolation titanium hydride, used the agitator continuously stirring 30 minutes, place and carry out the underwater explosion test after 10 hours.
Employed emulsifying base prescription is same as the prior art, and basic recipe sees Table 1.
Table 1 embodiment 1 employed emulsifying base prescription
| Component | Nitrate | Water | Span-80 | Composite oil phase | Other |
| Content | 78 | 15 | 2 | 4 | 1 |
In order to compare experiment, conventional sensitizing agent glass microsphere carries out sensitization to this process of dynamite substrate in the use emulsion explosive production.Existing experiment shows: when glass microsphere content was 4%, emulsion explosive output energy was maximum.When therefore present embodiment was made, emulsifying base and glass microsphere total mass were 50g, and glass microsphere content is 4% (=2 g) of total mass.The emulsifying base kind of its use is identical with table 1.Behind emulsifying base interpolation glass microsphere, used the agitator continuously stirring 45 minutes, place and carry out the underwater explosion test after 10 hours.
In the underwater explosion test, the shockwave curve of the emulsifying base explosive of 2% (W/W) titanium hydride is seen Fig. 1,4%(W/W) the shockwave curve of glass microsphere emulsion explosive sees Fig. 2.Among the figure: X-coordinate represents that the time, (unit: s), ordinate zou represents pressure, and (unit: MPa), the underwater blast wave curve was by oscillograph recording.Various test parameters see Table 2, and data all read from the shockwave curve in the table 2.
Table 2 embodiment 1 underwater blast wave detonation parameter
| Prescription (mass ratio) | Peak pressure MPa | Fall time us | Momentum Pas | Energy-flux density J/m 2 |
| Emulsifying base: titanium hydride=98:2 | 8.56 | 51.87 | 623.10 | 1946.7 |
| Emulsifying base: glass microsphere=96:4 | 10.35 | 37.08 | 588.34 | 2137.2 |
Annotate: the energy-flux density calculation formula:
,
It is diminution factor.
As seen from Table 2, the peak pressure of titanium hydride hydrogen storage emulsion explosive of the present invention is less than the emulsion explosive of glass microsphere, but fall time, momentum are all greater than the latter.That is to say that although titanium hydride has reduced the shock wave peak pressure of emulsion explosive underwater explosion, its secondary reaction can improve temperature and the time length of explosive field, have active effect to improving the emulsion explosive damage effect.
Embodiment 2:
Titanium hydride and emulsifying base total mass 50g, titanium hydride content are the 4%(=2 g of total mass).Behind emulsifying base interpolation titanium hydride, used the agitator continuously stirring 25 minutes, place and carry out the underwater explosion test after 48 hours.The shockwave curve is seen Fig. 3.
Employed emulsifying base prescription is same as the prior art, specifically sees Table 3.
Table 3 embodiment 2 employed emulsifying base prescriptions
| Component | Nitrate | Water | LZ2731 | Composite oil phase | Other |
| Content | 77 | 16 | 2 | 4 | 1 |
In the underwater explosion test, the shockwave curve that obtains is seen Fig. 3.Among the figure: X-coordinate represents that the time, (unit: s), ordinate zou represents pressure, and (unit: MPa), the underwater blast wave curve was by oscillograph recording.Each test parameter sees Table 4, and data all read from the shockwave curve in the table 4.Also listed in the table 4 and to have used glass microsphere as the test data of the underwater explosion of the conventional emulsion explosive of sensitizing agent (emulsifying base is specifically filled a prescription, storage period with this example), with relatively convenient.
Table 4 embodiment 2 underwater blast wave detonation parameters
| Prescription (mass ratio) | Peak pressure MPa | Fall time us | Momentum Pas | Energy-flux density J/m 2 |
| Emulsifying base: titanium hydride=96:4 | 10.22 | 43.91 | 604.64 | 1759.84 |
| Emulsifying base: glass microsphere=96:4 | 10.35 | 37.08 | 588.34 | 2137.2 |
As seen from Table 4, the peak pressure of titanium hydride hydrogen storage emulsion explosive is slightly less than the emulsion explosive pressure peak that contains glass microsphere, but fall time, momentum are all greater than the latter.Although titanium hydride has reduced the shock wave peak pressure of emulsion explosive underwater explosion, its secondary reaction can improve temperature and the time length of explosive field, has active effect to improving the emulsion explosive damage effect.
Embodiment 3:
Titanium hydride and emulsifying base total mass 50g, titanium hydride content is the 6%(=3g of total mass).Behind emulsifying base interpolation titanium hydride, used the agitator continuously stirring 25 minutes, place and carry out the underwater explosion test after 25 days.The shockwave curve that obtains is seen Fig. 4.
Employed emulsifying base prescription is same as the prior art, specifically sees Table 5.
Table 5 embodiment 3 employed emulsifying base prescriptions
| Component | Nitrate | Water | LZ2731 | Composite oil phase | Other |
| Content | 77 | 16 | 2 | 4 | 1 |
In the underwater explosion test, the shockwave curve that obtains is seen Fig. 4.Among the figure: X-coordinate represents that the time, (unit: s), ordinate zou represents pressure, and (unit: MPa), the underwater blast wave curve was by oscillograph recording.Each test parameter sees Table 6, and data all read from the shockwave curve in the table 6.Also listed in the table 6 and to have used glass microsphere as the test data of the underwater explosion of the conventional emulsion explosive of sensitizing agent (emulsifying base is specifically filled a prescription, storage period with this example), with relatively convenient.
Table 6 embodiment 3 underwater blast wave detonation parameters
| Prescription (mass ratio) | Peak pressure MPa | Fall time us | Momentum Pas | Energy-flux density J/m 2 |
| Emulsifying base: titanium hydride=94:6 | 7.90 | 67.13 | 728.80 | 2435.6 |
| Emulsifying base: glass microsphere=96:4 | 10.35 | 37.08 | 588.34 | 2137.2 |
Contrast table 2,4,6 can find out that hydrogenation type of the present invention stores up in the hydrogen breast titanizing explosive, the underwater explosion pressure of titanium hydride emulsifying base explosive and titanium hydride content and nonlinear relationship.When titanium hydride mass content during in 6% left and right sides, its momentum and energy-flux density are maximum, but peak pressure is minimum, also reach simultaneously maximum value fall time, approach to use glass microsphere as 2 times of the conventional emulsion explosive of sensitizing agent, this meets the needs of some specific occasion very much.
More than titanium hydride among each embodiment be purity greater than 95% powder, granularity is at 1-40 μ m, powder particle is irregular polyhedrons shape, is buied by market; The various raw materials of configuration emulsifying base are also buied by market.
Claims (1)
1. titanium hydride hydrogen storage emulsion explosive, its component comprises emulsifying base and sensitizing agent, it is characterized in that, described sensitizing agent is titanium hydride, wherein, the quality of titanium hydride accounts for the 0.6-8% of titanium hydride hydrogen storage emulsion explosive total mass, and described titanium hydride is purity more than or equal to 95% powder, and granularity is at 1-40 μ m.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103113171B (en) * | 2013-03-18 | 2015-06-24 | 中国科学技术大学 | Titanium hydride-type high-energy composite explosive and preparation method thereof |
| CN103626615B (en) * | 2013-12-19 | 2016-04-06 | 宜兴市阳生化工有限公司 | The gluey emulsification civil explosive of a kind of MY type and production technique thereof |
| CN103724143B (en) * | 2013-12-31 | 2016-02-10 | 宜兴市阳生化工有限公司 | A kind of Rock powdery civil emulsion explosive and production technique thereof |
| CN106588521A (en) * | 2016-12-31 | 2017-04-26 | 中国科学技术大学 | Free state hydrogen sensitized emulsion explosive and preparation method |
| CN106883083B (en) * | 2017-04-18 | 2019-09-24 | 攀枝花学院 | The method and physical sensitization of emulsion and granulation mix medicine and are granulated all-in-one machine |
| CN107540486B (en) * | 2017-10-09 | 2022-09-09 | 安徽理工大学 | Hydrogen storage type emulsified seismic charge and seismic bomb using same |
| CN108358733B (en) * | 2018-03-14 | 2020-07-03 | 安徽理工大学 | A method of thermally expanding hollow microspheres for coating energetic additives |
| CN109096023B (en) * | 2018-09-04 | 2021-01-19 | 安徽理工大学 | Multi-core hollow energetic microsphere for emulsion explosive and preparation method thereof |
| CN109440074B (en) * | 2018-12-06 | 2021-04-30 | 电子科技大学 | High-energy-output hydrogen explosion membrane bridge and preparation method thereof |
| CN116553988A (en) * | 2023-05-17 | 2023-08-08 | 安徽理工大学 | Novel emulsion explosive containing titanium hydride and preparation method thereof |
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Patent Citations (4)
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| US6224099B1 (en) * | 1997-07-22 | 2001-05-01 | Cordant Technologies Inc. | Supplemental-restraint-system gas generating device with water-soluble polymeric binder |
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