CN114990381A - Low-melting-point alloy for safe ammunition slow-release structure and preparation method and application thereof - Google Patents
Low-melting-point alloy for safe ammunition slow-release structure and preparation method and application thereof Download PDFInfo
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- CN114990381A CN114990381A CN202110223323.7A CN202110223323A CN114990381A CN 114990381 A CN114990381 A CN 114990381A CN 202110223323 A CN202110223323 A CN 202110223323A CN 114990381 A CN114990381 A CN 114990381A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F42—AMMUNITION; BLASTING
- F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
- F42B39/00—Packaging or storage of ammunition or explosive charges; Safety features thereof; Cartridge belts or bags
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Abstract
The invention provides a low-melting-point alloy for a safe ammunition slow-release structure and a preparation method and application thereof. The invention uses tin, zinc, aluminum and lanthanum to prepare low-melting-point alloy, and the total weight is 100 percent, and the low-melting-point alloy contains 63 to 91 percent of tin, 6 to 9 percent of zinc and 0.8 to 30 percent of aluminum; 0.2 to 0.5 percent of lanthanum; the preparation method comprises the following steps: (1) smelting and melting a mixture of tin, aluminum and lanthanum metals to obtain molten metal A, and quickly casting, cooling and molding the molten metal A to obtain an Sn-Al-La alloy block; (2) and smelting and melting the Sn-Al-La alloy block and metal zinc to obtain molten metal B, and quickly casting, cooling and molding the molten metal B to obtain the low-melting-point alloy. The prepared low-melting-point alloy has the melting point of 190-210 ℃, has good mechanical property at-50-70 ℃, has higher tensile strength, and can be applied to the design of safe ammunition slow-release structures.
Description
Technical Field
The invention relates to the field of safe ammunition design, in particular to a low-melting-point alloy for a safe ammunition slow-release structure and a preparation method and application thereof.
Background
The safe ammunition slow release design is an important technical means for improving the service safety of weapons ammunition, and a pressure release channel is preset on an ammunition shell or a charging constraint structure, which is the most important slow release method. When the ammunition is subjected to accidental thermal stimulation, the slow release structure fails in advance to form a pressure release channel, so that severe reactions of combustion to deflagration or combustion to detonation of the ammunition are inhibited in time, the severe degree of the accidental reactions of the ammunition is further reduced, and disastrous damage to personnel and equipment is avoided. Therefore, the safe ammunition slow release design has important practical significance for improving the service safety of ammunition, particularly the safety under the action of thermal stimulation.
On the one hand, the safe ammunition slow-release structure is required to have strength failure under abnormal high-temperature conditions such as fire and the like, so that the restraint of the closed shell on the explosive charge is relieved or weakened, and the violent degree of the accidental reaction of the ammunition is relieved. The low melting point alloy can be used as a slow release structure material due to the specific melting characteristic and mechanical property. At present, safe ammunition slow release design is mainly based on the ignition temperature of a slow-firing-rate-of-charge burning test, and the range of the safe ammunition slow release design is usually 120-210 ℃. However, the melting point range of the Sn-Bi low-melting-point alloy which is commonly used for ammunition slow-release structural design is between 98 ℃ and 138 ℃, and the safety requirement of charging at higher ignition temperature is difficult to meet; the melting point of the Sn-Pb eutectic alloy is 183 ℃, the safety requirement of charging at a higher ignition temperature can be met, but the Sn-Pb eutectic alloy has toxicity and is harmful to both human and environment, and the application range of the Sn-Pb eutectic alloy is greatly limited.
On the other hand, the operational performance of ammunition has certain requirements on the strength of the casing, the sealing performance and the adaptability to high and low temperature environments. Therefore, the slow release structure not only has the safety capability of rapidly failing or destroying to form a pressure relief channel under the condition of abnormal high temperature, but also has certain mechanical strength in the environment of normal use temperature, and meets the requirement of normal use of ammunition. At present, most of low-melting-point alloys applied to safe ammunition slow-release structures only consider the function of strength failure in abnormal high-temperature environments, and are difficult to meet the requirement that ammunition has better mechanical properties in normal use temperature environments (-50 ℃ -70 ℃). The eutectic component phase of the Sn-Zn binary alloy is Sn-9Zn, the melting point is 198 ℃, the melting point is close to the melting point temperature of the Sn-Pb eutectic alloy, the Sn-Zn binary alloy has higher tensile shear strength and thermal fatigue performance, the raw materials are low in price, the resources are rich and non-toxic, and the Sn-Zn binary alloy has a good application prospect in the thermal safety enhancement design aiming at ammunition with high ignition temperature, but the Sn-9Zn binary alloy has poorer mechanical property under the condition of-50 ℃ to 70 ℃.
Therefore, the invention is urgently needed to invent the low-melting-point alloy which has melting characteristics and mechanical properties capable of meeting the requirements of safe ammunition slow release under abnormal high-temperature conditions and the requirements of normal use of ammunition within a certain temperature range.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a low-melting-point alloy for a safe ammunition slow-release structure and a preparation method and application thereof.
The low-melting-point alloy is prepared from four metals of tin, zinc, aluminum and lanthanum, has a melting point of 190-210 ℃, has good mechanical properties at-50-70 ℃, has high tensile strength, and meets the design requirements of a safe ammunition slow release structure and the normal use requirements of ammunition within a certain temperature range.
One of the purposes of the invention is to provide a low-melting-point alloy for a safe ammunition slow-release structure.
The low melting point alloy includes tin, zinc, aluminum, and lanthanum;
based on the total weight of the low melting point alloy as 100 percent,
the second purpose of the invention is to provide a preparation method of the low-melting-point alloy for the safe ammunition slow-release structure.
The method comprises the following steps:
(1) smelting and melting a mixture of tin, aluminum and lanthanum metals to obtain molten metal A, and quickly pouring, cooling and forming the molten metal A to obtain an Sn-Al-La alloy block;
(2) and smelting and melting the obtained Sn-Al-La alloy block and metal zinc to obtain molten metal B, and quickly casting, cooling and molding the molten metal B to obtain the low-melting-point alloy for the safe ammunition slow-release structure.
In a preferred embodiment of the present invention,
the method comprises the following steps:
repeatedly smelting the low-melting-point alloy obtained in the step (2) for not less than 3 times; more preferably 3 times. Repeated melting can ensure that the metal is fully melted and mixed.
In a preferred embodiment of the present invention,
the raw material purity of the tin and the zinc is more than 99.9 percent; and/or the presence of a gas in the atmosphere,
the raw material of lanthanum is Al-20La intermediate alloy; and/or the presence of a gas in the gas,
the raw materials of the aluminum are Al-20La intermediate alloy or Al-20La intermediate alloy and aluminum particles with the purity of more than 99.9 percent.
Firstly weighing Al-20La according to the mass percent of lanthanum, and if the mass of aluminum contained in the Al-20La intermediate alloy is not enough, then weighing aluminum particles with the purity of more than 99.9 percent until the mass of the aluminum required in the components is reached.
In a preferred embodiment of the present invention,
step (1) of carrying out a treatment,
smelting the metal mixture in a graphite crucible at the smelting temperature of 800-850 ℃;
melting the melted metal mixture in a heating furnace, wherein the temperature of the heating furnace is 800-850 ℃, the heat preservation time in the heating furnace is 30-40 min, and the metal mixture is stirred once every 5-10 min;
the cooling method is water bath copper pot cooling solidification molding.
In a preferred embodiment of the present invention,
a step (2) of carrying out a treatment,
smelting the Sn-Al-La alloy block in a graphite crucible, wherein the smelting temperature is 600-650 ℃;
melting the melted Sn-Al-La alloy block in a heating furnace, wherein the temperature of the heating furnace is 600-650 ℃, the heat preservation time in the heating furnace is 30-40 min, and stirring is carried out once every 5-10 min;
the cooling method is cooling solidification forming of a water bath copper pot.
The reason why the Sn-Al-La intermediate alloy is formed in the step (1) and the Sn-Zn-Al-La low-melting-point alloy is formed in the step (2) is that the boiling point of Zn is 907 ℃, so the melting temperature is as low as possible, and the volatilization of Zn is minimized, so the Sn-Al-La intermediate alloy with lower melting temperature is formed first, and then zinc is added at lower temperature, so that the volatilization of zinc is minimized, and all the added metal raw materials can be fully melted to form the Sn-Zn-Al-La low-melting-point alloy.
The melting point of the alloy prepared by the invention is 190-210 ℃. The addition of a small amount of aluminum and lanthanum refines crystal grains, and the tensile strength of the alloy is obviously improved.
The invention also aims to provide application of the low-melting-point alloy for the safe ammunition slow-release structure.
The low-melting-point alloy for the safe ammunition slow-release structure is applied to the design of the safe ammunition slow-release structure.
The invention can adopt the following technical scheme:
a low-melting-point alloy applied to safe ammunition slow-release structural design comprises tin, zinc, aluminum and lanthanum;
based on the total weight of the low melting point alloy as 100 percent,
a preparation method of a low-melting-point alloy applied to safe ammunition slow-release structure design is implemented according to the following steps:
the preparation method comprises the following steps of (1),
respectively weighing tin and zinc according to mass percentage;
preferably, the purity of the tin and zinc weighed in the step (1) is more than 99.9%.
Weighing aluminum and lanthanum according to mass percent, and respectively weighing aluminum and Al-20La intermediate alloy;
preferably, the lanthanum weighed in the step (1) is from an Al-20La intermediate alloy;
preferably, a part of the aluminum weighed in the step (1) comes from the Al-20La intermediate alloy, and if the aluminum content in the Al-20La intermediate alloy is insufficient, aluminum particles with the purity of more than 99.9 percent can be weighed until the aluminum content reaches the mass of the needed aluminum in the components.
And putting the mixture of the tin, the aluminum and the Al-20La intermediate alloy into a graphite crucible for smelting, putting the graphite crucible into a heating furnace for melting to obtain molten metal, and quickly pouring, cooling and molding the molten metal to form the Sn-Al-La low-melting-point alloy.
Preferably, the smelting temperature in the step (1) is controlled to be 800-850 ℃, the temperature of the heating furnace is 800-850 ℃, the heat preservation time in the heating furnace is 30-40 min, and stirring is carried out once every 5-10 min.
Preferably, the cooling method in the step (1) is water bath copper pan cooling solidification molding.
A step (2) of removing the solvent,
and placing the solidified and formed Sn-Al-La alloy block and pure zinc metal into a graphite crucible for smelting, then placing the graphite crucible into a heating furnace for melting to obtain molten metal, and then quickly pouring, cooling and forming the molten metal to form the Sn-Zn-Al-La low-melting-point alloy.
Preferably, the smelting temperature in the step (2) is controlled to be 600-650 ℃, the temperature of the heating furnace is 600-650 ℃, the heat preservation time in the heating furnace is 30-40 min, and stirring is carried out once every 5-10 min.
Preferably, the cooling method in the step (2) is water bath copper pan cooling solidification molding.
Preferably, the Sn-Zn-Al-La low melting point alloy cast molded in the step (2) is repeatedly smelted three times.
The invention has the beneficial effects that:
compared with the low-melting-point alloy applied to the design of safe ammunition slow-release structure in the prior art, the invention has the following remarkable advantages:
(1) the raw materials are green and environment-friendly, and the alloy has less harm to human and environment compared with lead-containing low-melting-point alloy;
(2) the melting point is closer to Sn-Pb low-melting-point alloy, and the requirement of ammunition with the ignition temperature of more than 175 ℃ can be met;
(3) and aluminum and lanthanum are added, the mechanical property of the eutectic low-melting-point alloy Sn-9Zn at the temperature of between 50 ℃ below zero and 70 ℃ is improved, and the tensile strength is improved by more than 20 to 30 percent.
Drawings
FIG. 1 is a graph comparing the tensile strength of the low melting point alloy and eutectic alloy Sn9Zn at-50 deg.C to 70 deg.C made in examples 1, 2 and 3;
FIG. 2 is a DSC plot of the low melting point alloy made in example 1; the melting point of the prepared low-melting-point alloy can be seen to be 206.2 ℃;
FIG. 3 is a DSC plot of the low melting point alloy made in example 2; the melting point of the prepared low-melting-point alloy is 205.6 ℃ as can be seen from the figure;
FIG. 4 is a DSC plot of the low melting point alloy made in example 3; it can be seen from the figure that the melting point of the low melting point alloy obtained is 199.6 ℃.
Detailed Description
While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is only for illustrative purposes and is not intended to limit the scope of the present invention, as those skilled in the art will appreciate numerous insubstantial modifications and variations therefrom.
The raw materials used in the examples are all conventional commercially available raw materials.
Example 1
The low-melting-point alloy of the embodiment comprises the following components in percentage by mass: 90.1 percent of tin, 8.9 percent of zinc, 0.8 percent of aluminum and 0.2 percent of lanthanum, wherein the sum of the mass percent of the components is 100 percent. The purity of the raw materials of the tin and the zinc is more than 99.9 percent, and the aluminum and the lanthanum are from Al-20La intermediate alloy.
The preparation method of the low-melting-point alloy comprises the following steps:
step 1, respectively weighing tin, zinc and Al-20La intermediate alloy according to the mass percent of 90.1 percent of tin, 8.9 percent of zinc, 0.8 percent of aluminum and 0.2 percent of lanthanum, wherein the sum of the mass percent of the components is 100 percent;
and 2, putting the intermediate alloy mixture of tin and Al-20La into a graphite crucible for smelting, putting the graphite crucible into a heating furnace for melting, controlling the smelting temperature at 800 ℃ to obtain molten metal, preserving the heat for 40min, stirring once every 10min, quickly pouring the molten metal into a water bath copper pot for cooling, solidifying and forming to form the Sn-Al-La alloy block.
And 3, placing the solidified and formed Sn-Al-La alloy block and Zn pure metal into a graphite crucible for smelting, placing the graphite crucible into a heating furnace for melting, controlling the smelting temperature at 600 ℃ to obtain molten metal, keeping the temperature for 40min, stirring once every 10min, quickly pouring the molten metal into a water bath copper pot for cooling, solidifying and forming to form Sn-Zn-Al-La low-melting-point alloy, and repeatedly smelting the cast and formed Sn-Zn-Al-La alloy for three times.
A Differential Scanning Calorimeter (DSC) is adopted to research the melting characteristic of the Sn-Zn-Al-La alloy, the DSC analysis sample is 2mg of alloy powder, the alloy powder is placed into a corundum crucible container, the testing temperature range is 50-850 ℃, and the temperature rise rate is 5 ℃/min under the nitrogen atmosphere; the tensile strength is determined according to the experimental method of GB/T228.1_4-2019 metallic material tensile test.
As shown in FIG. 1, the tensile strength of the low melting point alloy obtained in example 1 is higher by 30% or more at-50 ℃ to 70 ℃ than that of the Sn-9Zn binary alloy; as shown in FIG. 2, the melting point of the obtained low-melting-point alloy is 206.2 ℃ and is in the range of 190-210 ℃; the obtained low-melting-point alloy can be applied to the design of safe ammunition slow-release structures.
Example 2
The low-melting-point alloy of the embodiment comprises the following components in percentage by mass: 88.1 percent of tin, 8.7 percent of zinc, 3 percent of aluminum and 0.2 percent of lanthanum, wherein the sum of the mass percent of the components is 100 percent. The raw materials of the tin and the zinc have the purity of more than 99.9 percent, the lanthanum is from Al-20La intermediate alloy, and the aluminum is from the Al-20La intermediate alloy and aluminum particles with the purity of more than 99.9 percent.
The preparation method of the low-melting-point alloy comprises the following steps:
step 1, weighing 88.1 percent by mass of tin, 8.7 percent by mass of zinc, 3 percent by mass of aluminum and 0.2 percent by mass of lanthanum, and respectively weighing tin, zinc, aluminum and Al-20La intermediate alloy, wherein the sum of the mass percentages of the components is 100 percent;
and 2, putting the intermediate alloy mixture of tin, aluminum and Al-20La into a graphite crucible for smelting, putting the graphite crucible into a heating furnace for melting, controlling the smelting temperature at 820 ℃ to obtain molten metal, keeping the temperature for 40min, stirring every 5min, quickly pouring the molten metal into a water bath copper pot for cooling, solidifying and forming to form the Sn-Al-La alloy block.
And 3, placing the solidified and formed Sn-Al-La alloy block and pure zinc metal into a graphite crucible for smelting, placing the graphite crucible into a heating furnace for melting, controlling the smelting temperature at 620 ℃ to obtain molten metal, keeping the temperature for 40min, stirring once every 5min, quickly pouring the molten metal into a water bath copper pot for cooling, solidifying and forming to form Sn-Zn-Al-La low-melting-point alloy, and repeatedly smelting the cast and formed Sn-Zn-Al-La alloy for three times.
As shown in FIG. 1, the tensile strength of the low melting point alloy obtained in example 2 is higher than that of the Sn-9Zn binary alloy by more than 30% at-50 ℃ to 70 ℃; as shown in FIG. 3, the melting point of the obtained low-melting-point alloy is 205.6 ℃ and is in the range of 190-210 ℃; the obtained low-melting-point alloy can be applied to the design of safe ammunition slow-release structures.
Example 3
The low-melting-point alloy of the embodiment comprises the following components in percentage by mass: 72.5 percent of tin, 7.2 percent of zinc, 20 percent of aluminum and 0.3 percent of lanthanum, wherein the sum of the mass percentages of the components is 100 percent. The raw materials of the tin and the zinc have the purity of more than 99.9 percent, the lanthanum is from Al-20La intermediate alloy, and the aluminum is from the Al-20La intermediate alloy and aluminum particles with the purity of more than 99.9 percent.
The preparation method of the low-melting-point alloy comprises the following steps:
step 1, weighing tin, zinc, aluminum and Al-20La intermediate alloy according to the mass percentages of 72.5 percent of tin, 7.2 percent of zinc, 20 percent of aluminum and 0.3 percent of lanthanum, wherein the sum of the mass percentages of the components is 100 percent;
and 2, putting the intermediate alloy mixture of tin, aluminum and Al-20La into a graphite crucible for smelting, putting the graphite crucible into a heating furnace for melting, controlling the smelting temperature at 850 ℃ to obtain molten metal, keeping the temperature for 40min, stirring every 8min, quickly pouring the molten metal into a water bath copper pot for cooling, solidifying and forming to form the Sn-Al-La alloy block.
And 3, placing the solidified and formed Sn-Al-La alloy block and pure zinc metal into a graphite crucible for smelting, placing the graphite crucible into a heating furnace for melting, controlling the smelting temperature at 650 ℃ to obtain molten metal, keeping the temperature for 40min, stirring once every 8min, quickly pouring the molten metal into a water bath copper pot for cooling, solidifying and forming to form Sn-Zn-Al-La low-melting-point alloy, and repeatedly smelting the cast and formed Sn-Zn-Al-La alloy for three times.
As shown in FIG. 1, the tensile strength of the low melting point alloy obtained in example 3 is higher by 20% or more at-50 ℃ to 70 ℃ than that of the Sn-9Zn binary alloy; as shown in fig. 4, the melting point of the obtained low melting point alloy was 199.6 ℃ in the range of 190 ℃ to 210 ℃; the obtained low-melting-point alloy can be applied to the design of safe ammunition slow-release structures.
Claims (10)
1. A low-melting-point alloy for a safe ammunition slow-release structure is characterized in that:
the low melting point alloy includes tin, zinc, aluminum, and lanthanum;
based on the total weight of the low melting point alloy as 100 percent,
2. a low melting point alloy for a safe ammunition slow release structure according to claim 1, wherein:
based on the total weight of the low melting point alloy as 100 percent,
3. a method of preparing a low melting point alloy for a safe ammunition slow release structure according to claim 1 or 2, characterized in that the method comprises:
(1) smelting and melting a mixture of tin, aluminum and lanthanum metals to obtain molten metal A, and quickly pouring, cooling and forming the molten metal A to obtain an Sn-Al-La alloy block;
(2) and smelting and melting the obtained Sn-Al-La alloy block and metal zinc to obtain molten metal B, and quickly casting, cooling and molding the molten metal B to obtain the low-melting-point alloy for the safe ammunition slow-release structure.
4. A method of preparing a low melting point alloy for a safe ammunition slow release structure according to claim 3, characterized in that the method comprises:
and (3) repeatedly smelting the low-melting-point alloy obtained in the step (2) for not less than 3 times.
5. A method of preparing a low melting point alloy for a safe ammunition slow release structure according to claim 3, characterized in that:
the purity of the raw materials of the tin and the zinc is more than 99.9 percent; and/or the presence of a gas in the atmosphere,
the raw material of lanthanum is Al-20La intermediate alloy; and/or the presence of a gas in the gas,
the raw materials of the aluminum are Al-20La intermediate alloy or Al-20La intermediate alloy and aluminum particles with the purity of more than 99.9 percent.
6. A method of preparing a low melting point alloy for a safe ammunition slow release structure according to claim 3, characterized in that:
step (1) of carrying out a treatment,
the metal mixture is smelted in a graphite crucible, and the smelting temperature is 800-850 ℃.
7. A method of preparing a low melting point alloy for a safe ammunition slow release structure according to claim 3, characterized in that:
step (1) of carrying out a treatment,
melting the melted metal mixture in a heating furnace, wherein the temperature of the heating furnace is 800-850 ℃, the heat preservation time in the heating furnace is 30-40 min, and stirring is carried out once every 5-10 min;
the cooling method is water bath copper pot cooling solidification molding.
8. A method of preparing a low melting point alloy for a safe ammunition slow release structure according to claim 3, characterized in that:
a step (2) of carrying out a treatment,
and smelting the Sn-Al-La alloy block in a graphite crucible at the smelting temperature of 600-650 ℃.
9. A method of preparing a low melting point alloy for a safe ammunition slow release structure according to claim 3, characterized in that:
a step (2) of carrying out a treatment,
melting the smelted Sn-Al-La alloy block in a heating furnace, wherein the temperature of the heating furnace is 600-650 ℃, the heat preservation time in the heating furnace is 30-40 min, and stirring is carried out once every 5-10 min;
the cooling method is cooling solidification forming of a water bath copper pot.
10. A low melting point alloy for a safety ammunition slow release structure according to claim 1 or 2 is applied to the design of the safety ammunition slow release structure.
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| US20080159904A1 (en) * | 2005-08-24 | 2008-07-03 | Fry's Metals, Inc. | Solder alloy |
| JP2016019992A (en) * | 2014-07-14 | 2016-02-04 | 株式会社日本スペリア社 | Aluminium soldering and solder joint |
| CN106702243A (en) * | 2016-12-07 | 2017-05-24 | 北京态金科技有限公司 | Low-melting-point metal and preparation method and application thereof |
| CN110306079A (en) * | 2019-07-18 | 2019-10-08 | 云南科威液态金属谷研发有限公司 | A kind of low melting point liquid metal and the preparation method and application thereof |
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| US20040208779A1 (en) * | 2001-07-05 | 2004-10-21 | Ika Consulting Ltd. | Lead-free alloy |
| CN1390672A (en) * | 2002-05-10 | 2003-01-15 | 大连理工大学 | Leadfree SnZn-base alloy solder containing rare-earth elements |
| US20080159904A1 (en) * | 2005-08-24 | 2008-07-03 | Fry's Metals, Inc. | Solder alloy |
| JP2016019992A (en) * | 2014-07-14 | 2016-02-04 | 株式会社日本スペリア社 | Aluminium soldering and solder joint |
| CN106702243A (en) * | 2016-12-07 | 2017-05-24 | 北京态金科技有限公司 | Low-melting-point metal and preparation method and application thereof |
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