CN114570915B - Preparation method of rare earth composite material - Google Patents
Preparation method of rare earth composite material Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 63
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000008595 infiltration Effects 0.000 claims abstract description 24
- 238000001764 infiltration Methods 0.000 claims abstract description 24
- 238000005238 degreasing Methods 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 9
- 239000012188 paraffin wax Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- -1 rare earth hydride Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052747 lanthanoid Inorganic materials 0.000 abstract 1
- 150000002602 lanthanoids Chemical class 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 239000010937 tungsten Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
- B22D23/04—Casting by dipping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F3/26—Impregnating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a preparation method of a rare earth composite material, wherein the chemical formula of the rare earth composite material is R-H-M, R-H exists in a rare earth hydride form, R is selected from at least one of lanthanide rare earth elements and Y elements, M is selected from at least one of W or Mo, and the preparation method comprises the following steps: mixing the M powder and the forming agent in a mixer; compacting the mixed M powder; degreasing and sintering the molded blank, and cooling the blank in a furnace to obtain an M framework with the porosity of 10% -40%; immersing the M framework into the melt of R for infiltration treatment, and separating the M framework after the infiltration treatment from redundant R; and cooling the obtained M framework, and performing heat treatment in a hydrogen atmosphere to obtain the rare earth composite material. The rare earth composite material has high energy release, can realize high-efficiency energy release in an oxygen-free environment, and obviously improves the application environment of the metal energy release material.
Description
Technical Field
The invention relates to a metal material, in particular to a preparation method of a rare earth composite material.
Background
The energy release mechanism of the currently known metal energy release material is that elements which are easier to react with oxygen to release a large amount of heat; and secondly, the reaction between metals or between metals and intermediate products. The current metal energy release material mainly takes high-activity elements such as Zr, al and the like as main energy release elements, realizes the combustion effect in the environment with higher air or oxygen content, but has poor energy release effect in the environment such as low-pressure hypoxia, underwater and the like generally, has insufficient mechanical properties and is difficult to be used for structural parts. How to prepare energy release metal which can realize high-efficiency energy release in an anaerobic environment, has strong energy release in a conventional environment, has certain mechanical property and can be stably stored for a long time is a problem to be solved.
Disclosure of Invention
The invention provides a preparation method of a rare earth composite material, and the prepared rare earth composite material can realize high-efficiency energy release in an anaerobic environment, has strong energy release in a conventional environment, has certain mechanical property and can be stably stored for a long time.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing a rare earth composite material having a chemical formula of R-H-M, wherein R-H exists in the form of rare earth hydride, wherein rare earth R is selected from at least one of Nd, pr, dy, tb, ho, la, ce, pm, sm, eu, gd, er, tm, yb, lu and Y elements, and M is selected from at least one of W or Mo, the method comprising the steps of:
a. placing the M powder and the forming agent into a mixer for mixing;
b. compacting the mixed M powder;
c. degreasing and sintering the molded blank, and cooling with a furnace to obtain an M framework, wherein the porosity of the M framework is 10% -40%;
d. immersing the M framework into the molten liquid of the rare earth R for infiltration treatment, and separating the M framework after the infiltration treatment from redundant R;
e. and d, cooling the M framework obtained in the step, and performing heat treatment in a hydrogen atmosphere to obtain the rare earth composite material.
Preferably, the rare earth composite material comprises 3-21 wt% of R-H and the balance of M.
Preferably, the rare earth R is at least one selected from Nd, pr, ho, dy, tb, Y and Gd.
Preferably, M comprises at least W.
Preferably, the M powder has a particle size D50 of 3.0 μm to 30.0. Mu.m.
Preferably, the molding agent is selected from at least one of paraffin, PEG and PP.
Preferably, in the step b, the mixed powder is filled into a rubber sleeve, and is pressed and molded in an isostatic press, wherein the pressing pressure is greater than or equal to 150MPa, and the pressure maintaining time is greater than or equal to 30s.
Preferably, in the step c, after solvent degreasing and thermal degreasing, sintering is performed in a positive pressure hydrogen or argon atmosphere, wherein the sintering temperature is 1400-2200 ℃, and the sintering time is 4-8 hours.
Preferably, in the step d, the temperature of the infiltration treatment is 100-150 ℃ higher than the melting point of the rare earth R, and the infiltration treatment time is 0.5-4 h.
Preferably, the M framework obtained in the step d is cooled and then placed into a vacuum atmosphere furnace, hydrogen is filled into the furnace, and the temperature is raised to 100-350 ℃ for heat treatment.
The beneficial effects of the invention are as follows:
1. the rare earth composite material prepared by the invention exists in a pseudo alloy form, can realize a better energy release effect in an aerobic environment, has a certain mechanical property, and has a better energy release effect in a low-oxygen environment such as carbon dioxide, nitrogen, water and the like.
2. The preparation method of the invention carries out heat treatment on the sintered rare earth composite material in hydrogen atmosphere, so that the rare earth composite material can be stored in air for a long time, and the composite material can produce the blasting effect when releasing energy in an aerobic environment.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In a preferred embodiment, the rare earth composite comprises 3 to 21wt% of R-H, the balance being M.
In a recommended embodiment, R is selected from at least one of Nd, pr, ho, dy, tb, Y and Gd.
Preferably, R is at least one selected from Nd, pr, ho, dy and Tb elements.
In a preferred embodiment, the M comprises W and Mo, and the W content is 4-9 times of the Mo content.
In a preferred embodiment, M is preferably W.
In a preferred embodiment, M may be Mo.
In a preferred embodiment, the M powder has a particle size D50 of 3.0 μm to 30.0. Mu.m. The M powder can be tungsten powder or molybdenum powder, or mixed powder of tungsten powder and molybdenum powder, and preferably the M powder is tungsten powder.
In a preferred embodiment, the shaping agent is selected from at least one of paraffin, PEG, PP.
In a recommended embodiment, the M powder after mixing is filled into a rubber sleeve in a pressing process, and the mixture is pressed and molded in an isostatic press, wherein the pressing pressure is greater than or equal to 150MPa, and the pressure maintaining time is greater than or equal to 30s.
In the recommended embodiment, in the step c, the degreasing comprises solvent degreasing and thermal degreasing, wherein the solvent degreasing can be one of trichloroethylene, trichloromethane or n-heptane, the degreasing temperature is 45-70 ℃, and the degreasing time is 5-8 h; the thermal degreasing temperature is 450-500 ℃.
In a preferred embodiment, in step c, sintering is carried out in a positive pressure hydrogen or argon atmosphere at a temperature of 1400 to 2200 ℃ for a period of 4 to 8 hours.
In the sintering process of the pressed compact, metallurgical bonding is carried out between tungsten and/or molybdenum atoms at 1400-2200 ℃ to form a framework with certain strength.
In a recommended embodiment, the temperature of the infiltration treatment is 100-150 ℃ higher than the melting point of the rare earth R, and the infiltration treatment time is 0.5-4 h.
In the infiltration treatment process, the low-melting-point rare earth element is melted and infiltrated into the tungsten and/or molybdenum framework, and the rare earth element exists in the gaps of the tungsten and/or molybdenum framework, so that a pseudoalloy is formed.
In a recommended embodiment, the M framework obtained in the step d is cooled and then placed in a vacuum atmosphere furnace, hydrogen is filled into the furnace, the temperature is raised to 100-350 ℃, and heat treatment is carried out.
The sintered rare earth composite material is subjected to heat treatment in a hydrogen atmosphere, so that the composite material can be stored in the air for a long time, and the composite material can produce an explosion effect when energy is released in an aerobic environment.
In the recommended embodiment, the surface of the composite material can be subjected to surface protection treatment, such as paint spraying, surface passivation treatment and the like, according to the requirement, so as to achieve the aim of further prolonging the preservation period.
The present invention will be described in further detail with reference to examples.
Example 1
The preparation method of the rare earth composite material of the embodiment comprises the following steps:
mixing raw materials: m powder with particle size D50 of 6.0 μm and 58# paraffin were mixed according to 99: mixing in a mixer for 24h at a ratio of 1-98:2.
And (5) press forming: the mixed powder was put into a rubber jacket, and press-molded in an isostatic press according to the pressing pressures of examples 1.1 to 1.8 and comparative examples 1.1 to 1.2 in Table 1 for a dwell time of 30s.
Degreasing: and (3) placing the formed blank body in a trichloroethylene solvent at 50 ℃ to remove part of 58# paraffin, and then performing thermal degreasing at 500 ℃.
Sintering: and (3) putting the pressed compact into a vacuum furnace, charging hydrogen into the furnace, heating to 2100 ℃, sintering for 10 hours, and cooling along with the furnace to obtain the M framework.
Infiltration treatment: putting rare earth simple substance into an intermediate frequency furnace, melting at 150 ℃ higher than the melting point of rare earth R, immersing the M skeleton into the molten liquid of rare earth R, carrying out infiltration treatment for 3h, cooling to 10 ℃ higher than the melting point of rare earth R along with the furnace, and separating the M skeleton after infiltration treatment from the molten liquid of R.
And (3) heat treatment: and cooling the M framework subjected to infiltration treatment, putting the cooled M framework into a vacuum furnace, filling hydrogen into the furnace, heating to 180 ℃, and performing heat treatment to obtain the rare earth composite material.
The pressing pressures of examples 1.1 to 1.8 and comparative examples 1.1 to 1.2 and the density and porosity of the M skeleton after sintering are shown in Table 1.
TABLE 1 compaction pressure (MPa) and density (g/cm) of M skeleton after sintering for each example and each comparative example 3 ) Porosity (%)
The components of the rare earth composites prepared in each example and each comparative example were measured, and the measurement results are shown in table 2.
Table 2 weight percent (wt%) of the components of the rare earth composite materials prepared in each example and each comparative example
The rare earth composite materials prepared in each example and each comparative example were subjected to static compression strength detection and dynamic compression detection, the mechanical properties thereof were evaluated, and the energy released in an oxygen atmosphere was characterized by a reaction heat Δh, and the evaluation results are shown in table 3, respectively.
TABLE 3 evaluation of the Properties of the rare earth composite materials obtained in examples and comparative examples
As a conclusion we can draw:
when the M skeleton component is the same and the porosity is more than or equal to 10% and less than or equal to 40%, the R-H mass fraction of the finally prepared rare earth composite material is increased along with the increase of the porosity, the reaction heat is increased, a better energy release effect can be realized in an aerobic environment, a certain mechanical property is achieved, and the energy release effect is better in a low-oxygen environment such as carbon dioxide, nitrogen, water and the like.
When the porosity of the M framework is lower than 10%, the R-H mass fraction of the finally prepared rare earth composite material is lower than 3wt%, and the reaction heat is too low to meet the application requirements of the energetic material; when the porosity of the M framework is higher than 50%, the addition amount of 50# paraffin is too high, the strength of the pressed compact is too low after degreasing by a solvent, and the pressed compact is easy to scatter, and although the finally prepared rare earth composite material has good energy-containing effect, the mechanical strength is too low, so that the application requirement of the energy-containing material cannot be met.
Example two
The preparation method of the rare earth and tungsten composite material comprises the following steps:
raw material preparation and mixing: tungsten powder with particle size D50 of 7.0 μm and 58# paraffin were mixed according to 99: mixing in a mixer at a ratio of 1-98:2 for 36h.
And (5) press forming: the mixed powder was put into a rubber jacket, and press-molded in an isostatic press according to the pressing pressures of examples 2.1 to 2.8 and comparative examples 2.1 to 2.2 in Table 4 for a dwell time of 25s.
Degreasing: and (3) placing the molded blank body in a trichloroethylene solvent at 70 ℃ to remove part of 58# paraffin, and then performing thermal degreasing at 450 ℃.
Sintering and dehydrogenating: and (3) putting the pressed compact into a vacuum furnace, charging hydrogen into the furnace, heating to 2100 ℃, sintering for 10 hours, and cooling along with the furnace to obtain the tungsten skeleton.
Infiltration treatment: putting rare earth simple substance into an intermediate frequency furnace for infiltration treatment, wherein the infiltration treatment temperature is 100 ℃ higher than the melting point of rare earth R, the infiltration treatment time is 4 hours, after the infiltration treatment, the temperature is reduced to 20 ℃ higher than the melting point of rare earth R, and then the tungsten skeleton after the infiltration treatment is separated from the molten liquid of rare earth.
And (3) hydrotreating: and (3) putting the tungsten skeleton subjected to infiltration treatment into a vacuum furnace, filling hydrogen into the furnace, heating to 200 ℃, and performing heat treatment to obtain the rare earth and tungsten composite material.
The pressing pressures of examples 2.1 to 2.8 and comparative examples 2.1 to 2.2 and the density and porosity of the tungsten skeleton after sintering are shown in table 4.
TABLE 4 compaction pressure (MPa) and density (g/cm) of tungsten frameworks after sintering for each example and each comparative example 3 ) Porosity (%)
The components of the rare earth and tungsten composite materials prepared in each example and each comparative example were measured, and the measurement results are shown in table 5;
TABLE 5 weight percent (wt%) of the components of the rare earth and tungsten composite materials prepared in each example and each comparative example
The rare earth composite materials prepared in each example and each comparative example were subjected to static compressive strength detection and dynamic compressive strength detection, the mechanical properties were evaluated, the energy released by combustion of the rare earth composite materials in an oxygen environment was evaluated by using the reaction heat Δh, and the evaluation results are shown in table 6:
TABLE 6 evaluation of rare earth and tungsten composite properties for examples and comparative examples
As a conclusion we can draw:
when the porosity of the tungsten skeleton is more than or equal to 10% and less than or equal to 40%, the R-H mass fraction of the finally prepared rare earth and tungsten composite material is increased along with the increase of the porosity, the reaction heat is increased, a good energy release effect can be realized in an aerobic environment, a certain mechanical property is achieved, and the energy release effect is good in a low-oxygen environment such as carbon dioxide, nitrogen and water.
When the porosity of the tungsten skeleton is lower than 10%, the R-H mass fraction of the finally prepared rare earth composite material is lower than 3wt%, and the reaction heat is too low to meet the application requirements of the energetic material; when the porosity of the M framework is higher than 50%, the addition amount of 50# paraffin is too high, the strength of the pressed compact is too low after degreasing by a solvent, and the pressed compact is easy to scatter, and although the finally prepared rare earth composite material has good energy-containing effect, the mechanical strength is too low, so that the application requirement of the energy-containing material cannot be met.
While the foregoing description illustrates and describes the preferred embodiments of the present invention, as noted above, it is to be understood that the invention is not limited to the forms disclosed herein but is not to be construed as excluding other embodiments, and that various other combinations, modifications and environments are possible and may be made within the scope of the inventive concepts described herein, either by way of the foregoing teachings or by those of skill or knowledge of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (9)
1. The preparation method of the rare earth composite material is characterized in that the chemical formula of the rare earth composite material is R-H-M, wherein R-H exists in the form of rare earth hydride, rare earth R is selected from at least one of Nd, pr, dy, tb, ho, la, ce, sm, eu, gd, er, tm, yb, lu and Y elements, M is selected from at least one of W or Mo, the components of the rare earth composite material comprise 3-21 wt% of R-H, and the balance is M, and the preparation method comprises the following steps:
a. placing the M powder and the forming agent into a mixer for mixing;
b. compacting the mixed M powder;
c. degreasing and sintering the molded blank, and cooling with a furnace to obtain an M framework, wherein the porosity of the M framework is 10% -40%;
d. immersing the M framework into the molten liquid of the rare earth R for infiltration treatment, and separating the M framework after the infiltration treatment from redundant R;
e. and d, cooling the M framework obtained in the step, and performing heat treatment in a hydrogen atmosphere to obtain the rare earth composite material.
2. The preparation method of claim 1, wherein the rare earth R is at least one selected from Nd, pr, ho, dy, tb, Y and Gd.
3. The method of claim 1, wherein M comprises at least W.
4. The method according to claim 1, wherein the M powder has a particle size D50 of 3.0 μm to 30.0 μm.
5. The method according to claim 1, wherein the molding agent is at least one selected from paraffin, PEG, and PP.
6. The method according to claim 1, wherein in step b, the mixed powder is put into a rubber sleeve, and the powder is pressed and molded in an isostatic press at a pressure of 150MPa or more and a dwell time of 30s or more.
7. The preparation method according to claim 1, wherein in step c, after solvent degreasing and thermal degreasing, sintering is performed in a positive pressure hydrogen or argon atmosphere at 1400 ℃ to 2200 ℃ for 4h to 8h.
8. The preparation method according to claim 1, wherein in the step d, the infiltration treatment is performed at a temperature 100-150 ℃ higher than the melting point of the rare earth R, and the infiltration treatment time is 0.5-4 h.
9. The preparation method according to claim 1, wherein in step e, the M skeleton obtained in step d is cooled and then placed in a vacuum atmosphere furnace, hydrogen is filled into the furnace and the temperature is raised to 100 ℃ to 350 ℃, and heat treatment is performed.
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| CN101928866A (en) * | 2010-03-23 | 2010-12-29 | 西安理工大学 | W-Cu composite material prepared from La-Ni intensified-sintered W skeleton and preparation method thereof |
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| CN109182870A (en) * | 2018-09-17 | 2019-01-11 | 西安理工大学 | A kind of preparation method with low-friction coefficient CuW alloy |
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| US7258751B2 (en) * | 2001-06-22 | 2007-08-21 | Neomax Co., Ltd. | Rare earth magnet and method for production thereof |
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| CN101928866A (en) * | 2010-03-23 | 2010-12-29 | 西安理工大学 | W-Cu composite material prepared from La-Ni intensified-sintered W skeleton and preparation method thereof |
| CN102806335A (en) * | 2011-05-31 | 2012-12-05 | 比亚迪股份有限公司 | Silicon carbide particle reinforced aluminum matrix composite and preparation method thereof |
| CN103981389A (en) * | 2014-05-15 | 2014-08-13 | 厦门理工学院 | Method for preparing tungsten-copper alloy by low-temperature sintering of tungsten skeleton |
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