CN115626859B - Metal composite boron powder and preparation method thereof - Google Patents
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000002905 metal composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 63
- 229910052796 boron Inorganic materials 0.000 claims abstract description 40
- 239000011812 mixed powder Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000000498 ball milling Methods 0.000 claims abstract description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 25
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 239000002923 metal particle Substances 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000012159 carrier gas Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 11
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 22
- 239000002131 composite material Substances 0.000 abstract description 21
- 238000013329 compounding Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 5
- 238000010574 gas phase reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 27
- 239000011733 molybdenum Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- 230000001737 promoting effect Effects 0.000 description 3
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 238000001465 metallisation Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
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- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B27/00—Compositions containing a metal, boron, silicon, selenium or tellurium or mixtures, intercompounds or hydrides thereof, and hydrocarbons or halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0083—Treatment of solid structures, e.g. for coating or impregnating with a modifier
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
Description
技术领域technical field
本发明属于复合硼粉技术领域,具体涉及一种金属复合硼粉及其制备方法。The invention belongs to the technical field of composite boron powder, and in particular relates to a metal composite boron powder and a preparation method thereof.
背景技术Background technique
无定形硼粉具有高能量特点,但其表面具有一层致密的低熔点氧化层,燃烧过程中氧化层形成液态,会阻碍氧的进一步扩散,当其应用在高能固体燃料、火炸药等领域时,具有点燃后难以持续燃烧等问题,燃烧性能较差,其高能量特性无法充分发挥。针对如何消除或者抑制该氧化层,众学者提出了很多可能的解决办法。各方学者通过实验证明,进行金属表面包覆处理的硼复合粉燃烧性能较原样本有显著提高,包括但不限于点火时间缩短、燃速提升、燃烧时间增加和残渣剩余总硼降低等,且经过处理的金属复合硼粉与推进剂体系的相容性有一定程度的改善。Amorphous boron powder has high energy characteristics, but its surface has a dense low-melting point oxide layer. During the combustion process, the oxide layer forms a liquid state, which will hinder the further diffusion of oxygen. When it is used in high-energy solid fuels, explosives and other fields , has problems such as difficulty in continuous combustion after ignition, poor combustion performance, and its high-energy characteristics cannot be fully exerted. Many scholars have proposed many possible solutions for how to eliminate or suppress the oxide layer. Various scholars have proved through experiments that the combustion performance of boron composite powder treated with metal surface coating is significantly improved compared with the original sample, including but not limited to shortened ignition time, increased burning speed, increased burning time and reduced total boron remaining in residues, etc., and The compatibility of the treated metal composite boron powder with the propellant system has been improved to a certain extent.
现有技术在金属复合硼粉的制备方面开展了部分工作,可通过多弧离子镀膜(PVD)法、球磨法等实现金属复合硼粉的制备。PVD法制备金属包覆硼粉时,会出现金属难以均匀包覆硼粉表面的问题,并且该方法受限于靶材,制备成本高,效率低,难以实现批产化制备。球磨法通过将硼粉和金属粉末长时间研磨实现硼粉与金属微冶金结合,复合均匀性和微观弥散程度不理想,并且针对于钨、钼等难熔金属的复合,球磨过程会出现大量物料沉积导致均匀复合失败。In the prior art, some work has been carried out in the preparation of metal composite boron powder, and the preparation of metal composite boron powder can be realized by multi-arc ion coating (PVD) method, ball milling method, etc. When preparing metal-coated boron powder by PVD method, there will be a problem that the metal is difficult to uniformly cover the surface of boron powder, and this method is limited by the target material, the preparation cost is high, the efficiency is low, and it is difficult to achieve mass production. The ball milling method realizes the combination of boron powder and metal micrometallurgy by grinding boron powder and metal powder for a long time. The uniformity and microscopic dispersion of the compound are not ideal, and for the compounding of refractory metals such as tungsten and molybdenum, a large amount of material will appear during the ball milling process. Deposition leads to failure of homogeneous recombination.
发明内容Contents of the invention
本发明的目的是为了克服现有技术存在的硼粉与金属复合均匀性差而导致金属复合硼粉燃烧性能差等缺陷,提供一种金属复合硼粉及其制备方法,该方法制备的金属复合硼粉分散性好、复合均匀、燃烧性能好,复合过程可连续化进行,适合工业化生产。The purpose of the present invention is to provide a kind of metal composite boron powder and its preparation method in order to overcome defects such as poor combustion performance of metal composite boron powder caused by the poor uniformity of boron powder and metal composite existing in the prior art, and the metal composite boron powder prepared by the method The powder has good dispersibility, uniform compounding, and good combustion performance. The compounding process can be carried out continuously, which is suitable for industrial production.
为了实现上述目的,第一方面,本发明提供了一种制备金属复合硼粉的方法,包括以下步骤:In order to achieve the above object, in a first aspect, the present invention provides a method for preparing metal composite boron powder, comprising the following steps:
(1)将硼粉和金属氧化物粉末进行球磨混合,得到混合粉末;(1) Ball milling and mixing boron powder and metal oxide powder to obtain mixed powder;
(2)再将所述混合粉末经可选的真空烘干后,经载气携带被送至等离子体火焰最底部的下方10-30cm处,且控制等离子功率为20-30kw,使得金属氧化物气化并与氢气反应生成金属颗粒,金属颗粒分布于硼颗粒表面,得到金属复合硼粉。(2) After the mixed powder is optionally vacuum dried, it is carried by the carrier gas and sent to the bottom 10-30cm of the plasma flame, and the plasma power is controlled at 20-30kw, so that the metal oxide Gasify and react with hydrogen to form metal particles, which are distributed on the surface of boron particles to obtain metal composite boron powder.
优选情况下,步骤(1)中,所述混合粉末经载气携带被送至等离子体火焰最底部的下方10-25cm处。Preferably, in step (1), the mixed powder is carried by the carrier gas and sent to a place 10-25 cm below the bottom of the plasma flame.
在一些优选实施方式中,步骤(2)中,所述混合粉末的送入速率为10-30g/min。In some preferred embodiments, in step (2), the feeding rate of the mixed powder is 10-30 g/min.
更优选地,所述混合粉末的送入速率为10-20g/min。More preferably, the feeding rate of the mixed powder is 10-20 g/min.
在一些优选实施方式中,步骤(2)中,所述等离子体的气源包括氩气和氢气,该氢气的通入流量不大于100L/min,其中该氩气与该氢气的流量比为1-3:1。In some preferred embodiments, in step (2), the gas source of the plasma includes argon and hydrogen, the flow rate of the hydrogen is not more than 100 L/min, and the flow ratio of the argon to the hydrogen is 1 -3:1.
在一些优选实施方式中,所述混合粉末中硼粉的粒度在0.3-6μm,金属氧化物粉末的粒度在5-45μm。In some preferred embodiments, the particle size of the boron powder in the mixed powder is 0.3-6 μm, and the particle size of the metal oxide powder is 5-45 μm.
在一些优选实施方式中,步骤(1)中,所述金属氧化物包括氧化钼和/或氧化钨。In some preferred embodiments, in step (1), the metal oxide includes molybdenum oxide and/or tungsten oxide.
在一些优选实施方式中,步骤(1)中,所述金属氧化物和硼粉的质量比为1:4-45。In some preferred embodiments, in step (1), the mass ratio of the metal oxide to boron powder is 1:4-45.
在一些优选实施方式中,步骤(1)中,所述球磨混合的条件包括:球料比为5-8:1,频率为15-25Hz,时间为30-240min。In some preferred embodiments, in step (1), the conditions of the ball mill mixing include: a ball-to-material ratio of 5-8:1, a frequency of 15-25 Hz, and a time of 30-240 min.
在一些优选实施方式中,步骤(1)中,还包括:在球磨混合前先对硼粉进行球磨预分散处理。In some preferred embodiments, step (1) further includes: pre-dispersing the boron powder by ball milling before ball milling.
更优选地,所述球磨预分散处理的条件包括:球料比为10-15:1,频率为10-30Hz,时间为60-300min。More preferably, the conditions of the ball milling pre-dispersion treatment include: a ball-to-material ratio of 10-15:1, a frequency of 10-30 Hz, and a time of 60-300 min.
第二方面,本发明提供一种金属复合硼粉,其通过第一方面所述的方法制备得到,所述金属复合硼粉包括微米级硼颗粒和分散在硼颗粒表面的纳米级金属颗粒,所述金属复合硼粉中金属质量含量在2-15%,且所述金属复合硼粉的激光粒度满足:D50<1μm,D[4,3]<1μm。In a second aspect, the present invention provides a metal composite boron powder prepared by the method described in the first aspect, the metal composite boron powder includes micron-sized boron particles and nano-sized metal particles dispersed on the surface of the boron particles, the The mass content of metal in the metal composite boron powder is 2-15%, and the laser particle size of the metal composite boron powder satisfies: D 50 <1 μm, D[4,3] <1 μm.
优选地,所述金属复合硼粉中硼颗粒的粒度在0.2-3μm,金属颗粒的粒度在100nm以下。Preferably, the particle size of the boron particles in the metal composite boron powder is 0.2-3 μm, and the particle size of the metal particles is below 100 nm.
有益效果:Beneficial effect:
本发明通过等离子体法制备金属复合硼粉,尤其是混合粉末送至等离子体火焰最底部的下方的适宜位置,配合适宜的等离子功率,能够使得金属氧化物和氢气发生气相反应生成极其细小的纳米级金属颗粒,而避免发生硼粉的硼化反应;纳米级的金属颗粒比表面积大,表面能高,以单质的形式弥散分布并吸附在硼粉颗粒表面,解决了常规球磨等复合方法复合均匀性差等问题。所得金属复合硼粉的结构为硼颗粒表面吸附一层纳米的金属单质颗粒,相当于硼颗粒表面包覆了一层金属单质颗粒,包覆层和硼仍以原单质形式存在,未形成化合物。而在相同条件下,若混合粉末的送粉位置过高,反应温度较高,硼粉有气化可能,并与生成的钼或钨金属反应,生成硼化物,导致金属复合硼粉制备失败;送粉位置过低,反应温度较低,经分析产物为硼复合硼粉和氧化钼的混合物,主要是因为该位置温度较低,部分氧化钼未与氢气发生反应,冷却后又形成氧化钼粉体,混入生成的钼复合硼粉内。The invention prepares the metal composite boron powder by the plasma method, especially the mixed powder is sent to a suitable position below the bottom of the plasma flame, and with the appropriate plasma power, the gas phase reaction of the metal oxide and hydrogen can generate extremely fine nano Nano-scale metal particles to avoid the boronation reaction of boron powder; nano-scale metal particles have large specific surface area and high surface energy, which are dispersed in the form of simple substances and adsorbed on the surface of boron powder particles, which solves the problem of uniform compounding by conventional ball milling and other compounding methods. gender issues. The structure of the obtained metal composite boron powder is that a layer of nanometer metal element particles are adsorbed on the surface of the boron particles, which is equivalent to a layer of metal element particles coated on the surface of the boron particles, and the coating layer and boron still exist in the original element form without forming a compound. Under the same conditions, if the powder feeding position of the mixed powder is too high and the reaction temperature is high, the boron powder may be gasified and react with the generated molybdenum or tungsten metal to form borides, resulting in the failure of the preparation of the metal composite boron powder; The powder feeding position is too low, and the reaction temperature is low. The analyzed product is a mixture of boron composite boron powder and molybdenum oxide, mainly because the temperature at this position is low, and part of the molybdenum oxide does not react with hydrogen, and forms molybdenum oxide powder after cooling. body, mixed into the generated molybdenum complex boron powder.
本发明的金属复合硼粉分散性好、复合均匀、燃烧性能优异,复合过程可连续化进行,特别适用于钨、钼等难熔金属复合硼粉的制备。硼颗粒表面包覆的金属,能够在硼粉燃烧时起到促进燃烧的作用,尤其适用于含硼燃料领域。The metal composite boron powder of the invention has good dispersibility, uniform composite and excellent combustion performance, and the composite process can be carried out continuously, and is especially suitable for the preparation of refractory metal composite boron powders such as tungsten and molybdenum. The metal coated on the surface of the boron particles can promote combustion when the boron powder is burned, and is especially suitable for the field of boron-containing fuels.
附图说明Description of drawings
为了更清楚地说明本发明实施例的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,应当理解,以下附图仅示出了本发明的某些实施例,因此不应被看作是对范围的限定,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他相关的附图。In order to illustrate the technical solutions of the embodiments of the present invention more clearly, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention, and thus It should be regarded as a limitation on the scope, and those skilled in the art can also obtain other related drawings based on these drawings without creative work.
图1是本发明实施例1的钼复合硼粉在放大20000倍下的电镜图。Fig. 1 is an electron micrograph of the molybdenum composite boron powder in Example 1 of the present invention under a magnification of 20,000 times.
图2是本发明实施例1的钼复合硼粉在放大1000倍下的SEM面扫描整体图。Fig. 2 is an overall view of the SEM surface scanning of the molybdenum composite boron powder in Example 1 of the present invention under a magnification of 1000 times.
图3是本发明实施例1的钼复合硼粉在放大1000倍下的SEM面扫描Mo分布图,灰色部分为Mo。Fig. 3 is a SEM surface scanning Mo distribution diagram of the molybdenum composite boron powder in Example 1 of the present invention under a magnification of 1000 times, and the gray part is Mo.
图4是本发明实施例1的钼复合硼粉在放大1000倍下的SEM面扫描B分布图,灰色部分为B。Fig. 4 is a SEM surface scanning B distribution diagram of the molybdenum composite boron powder in Example 1 of the present invention under magnification of 1000 times, and the gray part is B.
具体实施方式Detailed ways
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.
本发明中,球料比是以质量计。所述送至等离子体火焰最底部的下方10-30cm处是指位于等离子体火焰最底部的正下方的以等离子体火焰的最低点起计的10-30cm处的位置。In the present invention, the ball-to-material ratio is based on mass. The 10-30 cm below the bottom of the plasma flame refers to the position at 10-30 cm from the lowest point of the plasma flame directly below the bottom of the plasma flame.
第一方面,本发明提供了一种制备金属复合硼粉的方法,包括以下步骤:In a first aspect, the present invention provides a method for preparing metal composite boron powder, comprising the following steps:
(1)将硼粉和金属氧化物粉末进行球磨混合,得到混合粉末;(1) Ball milling and mixing boron powder and metal oxide powder to obtain mixed powder;
(2)再将所述混合粉末经可选的真空烘干后,经载气携带被送至等离子体火焰最底部的下方10-30cm处,且控制等离子功率为20-30kw,使得金属氧化物气化并与氢气反应生成金属颗粒,金属颗粒分布于硼颗粒表面,得到金属复合硼粉。(2) After the mixed powder is optionally vacuum dried, it is carried by the carrier gas and sent to the bottom 10-30cm of the plasma flame, and the plasma power is controlled at 20-30kw, so that the metal oxide Gasify and react with hydrogen to form metal particles, which are distributed on the surface of boron particles to obtain metal composite boron powder.
本发明将混合粉末送至等离子体火焰最底部的下方10-30cm处,使得混合粉末中金属氧化物和等离子体火焰气源中的氢气在温度为1200-2000℃的低温区仅发生还原反应生成极其细小的纳米级金属颗粒,而不与硼粉发生反应生成硼化物;同时由于在反应之前,金属氧化物气化,在等离子体热扰动气体的影响下,金属氧化物和反应气体氢气混合后均匀分散在硼颗粒表面,达到还原反应温度后,气气反应瞬间进行,生成的金属纳米颗粒就会均匀的分散在硼颗粒的表面,得到金属复合硼粉。在硼颗粒燃烧过程中,包覆在表面的纳米金属颗粒可以对硼粉的燃烧起到高效的促进作用,促进其完成燃烧,释放足够能量。In the present invention, the mixed powder is sent to 10-30 cm below the bottom of the plasma flame, so that the metal oxide in the mixed powder and the hydrogen in the gas source of the plasma flame only undergo a reduction reaction in a low temperature zone with a temperature of 1200-2000 ° C. Extremely fine nanoscale metal particles do not react with boron powder to form borides; at the same time, due to the gasification of metal oxides before the reaction, under the influence of plasma thermal disturbance gas, the metal oxides and reaction gas hydrogen are mixed Evenly disperse on the surface of boron particles. After reaching the reduction reaction temperature, the gas-gas reaction proceeds instantly, and the generated metal nanoparticles will be evenly dispersed on the surface of boron particles to obtain metal composite boron powder. During the combustion process of boron particles, the nano-metal particles coated on the surface can effectively promote the combustion of boron powder, promote its completion of combustion, and release sufficient energy.
本发明将混合粉末送至等离子体火焰最底部的下方10-30cm处,例如具体可以为10、11、12、13、15、18、20、23、25、28、30cm处等。In the present invention, the mixed powder is sent to 10-30 cm below the bottom of the plasma flame, for example, it can be 10, 11, 12, 13, 15, 18, 20, 23, 25, 28, 30 cm, etc.
优选情况下,所述混合粉末经可选的真空烘干后,经载气携带被送至等离子体火焰最底部的下方10-25cm处。该优选方案下,更利于提升所得金属复合硼粉的燃烧性能。Preferably, after the optional vacuum drying, the mixed powder is carried by the carrier gas and sent to the place 10-25 cm below the bottom of the plasma flame. Under this preferred scheme, it is more beneficial to improve the combustion performance of the obtained metal composite boron powder.
所述混合粉末的送入速率为10-30g/min,例如具体可以为10、11、12、13、15、18、20、23、25、28、30g/min等。The feeding rate of the mixed powder is 10-30 g/min, for example, specifically 10, 11, 12, 13, 15, 18, 20, 23, 25, 28, 30 g/min, etc.
在一些优选实施方式中,步骤(2)中,所述混合粉末的送入速率为10-20g/min。该优选方案下,混合粉末的送入量适宜,更利于金属氧化物的及时快速气化并参与与氢气的反应,从而进一步促进纳米颗粒的均匀、快速生成,且在硼颗粒表面弥散分布的更均匀;从而进一步提升金属复合硼粉的燃烧性能。In some preferred embodiments, in step (2), the feeding rate of the mixed powder is 10-20 g/min. Under this preferred scheme, the feeding amount of the mixed powder is appropriate, which is more conducive to the timely and rapid gasification of metal oxides and participation in the reaction with hydrogen, thereby further promoting the uniform and rapid generation of nanoparticles, and a more dispersed distribution on the surface of boron particles Uniform; thereby further improving the combustion performance of metal composite boron powder.
可以理解的是,所述载气的流量只要满足上述混合粉末的送入速率即可。所述载气优选为氩气。It can be understood that the flow rate of the carrier gas only needs to meet the feeding rate of the mixed powder mentioned above. The carrier gas is preferably argon.
在一些优选实施方式中,所述等离子体的气源包括氩气和氢气,该氢气的通入流量不大于100L/min,其中该氩气与该氢气的流量比为1-3:1。In some preferred embodiments, the plasma gas source includes argon and hydrogen, the flow rate of the hydrogen gas is not more than 100 L/min, and the flow ratio of the argon gas to the hydrogen gas is 1-3:1.
在一些优选实施方式中,所述混合粉末的粒度在0.3-45μm。更优选地,混合粉末中硼粉的粒度在0.3-6μm,金属氧化物粉末的粒度在5-45μm。该优选方案下,更利于在步骤(2)中生成粒度主要集中在30-80nm之间的金属颗粒,其以单质的形式大量吸附在硼颗粒表面,其比表面积大,表面能高,利于促进硼粉的快速燃烧。In some preferred embodiments, the particle size of the mixed powder is 0.3-45 μm. More preferably, the particle size of the boron powder in the mixed powder is 0.3-6 μm, and the particle size of the metal oxide powder is 5-45 μm. Under this preferred scheme, it is more conducive to the generation of metal particles with a particle size mainly concentrated between 30-80nm in step (2), which is adsorbed on the surface of boron particles in a large amount in the form of simple substance, and has a large specific surface area and high surface energy, which is conducive to promoting Rapid combustion of boron powder.
在一些优选实施方式中,步骤(2)中,所述真空烘干的条件包括:真空度≤-0.09MPa,烘干温度≥90℃,烘干时间≥10h。该优选方案下,能够降低粉体中残余水分对反应的影响,更利于促进还原反应。In some preferred embodiments, in step (2), the vacuum drying conditions include: vacuum degree ≤ -0.09MPa, drying temperature ≥ 90°C, and drying time ≥ 10h. Under this preferred solution, the influence of residual moisture in the powder on the reaction can be reduced, which is more conducive to promoting the reduction reaction.
所述金属氧化物的种类只要能够在前述等离子体火焰环境下气化并与氢气反应生成金属颗粒,进而对硼颗粒进行包覆即可,本领域技术人员可以根据需求选择。在一些优选实施方式中,步骤(1)中,所述金属氧化物包括氧化钼和/或氧化钨。The type of the metal oxide only needs to be gasified in the aforementioned plasma flame environment and react with hydrogen to form metal particles, and then coat the boron particles, and those skilled in the art can choose according to requirements. In some preferred embodiments, in step (1), the metal oxide includes molybdenum oxide and/or tungsten oxide.
本领域技术人员可以根据需求选择原料比例。在一些优选实施方式中,步骤(1)中,所述金属氧化物和硼粉的质量比为1:4-45。Those skilled in the art can select the proportion of raw materials according to requirements. In some preferred embodiments, in step (1), the mass ratio of the metal oxide to boron powder is 1:4-45.
在一些优选实施方式中,步骤(1)中,所述球磨混合的条件包括:球料比为5-8:1,频率为15-25Hz,时间为30-240min。该优选方案下,能够使得原料混合更均匀,更利于后续生成的金属纳米颗粒均匀分散在硼颗粒表面。In some preferred embodiments, in step (1), the conditions of the ball mill mixing include: a ball-to-material ratio of 5-8:1, a frequency of 15-25 Hz, and a time of 30-240 min. Under this preferred solution, the mixing of the raw materials can be made more uniform, which is more conducive to the uniform dispersion of the subsequently generated metal nanoparticles on the surface of the boron particles.
所述球磨混合的方式可以为滚筒球磨等方式,本领域技术人员可以根据需求选择。The way of ball milling and mixing can be roller milling, etc., and those skilled in the art can choose according to requirements.
在一些优选实施方式中,步骤(1)中,还包括:在所述球磨混合之前先对硼粉进行球磨预分散处理。该优选方案下,将硼粉先进行球磨预分散处理,能够使得后续即便对于较小粒度的硼粉,也能实现金属颗粒的均匀包覆。In some preferred embodiments, step (1) further includes: performing ball milling pre-dispersion treatment on the boron powder before the ball milling. Under this preferred solution, the boron powder is pre-dispersed by ball milling, so that even for boron powder with a smaller particle size, uniform coating of metal particles can be achieved.
更优选地,所述球磨预分散处理的条件包括:球料比为10-15:1,频率为10-30Hz,时间为60-300min。More preferably, the conditions of the ball milling pre-dispersion treatment include: a ball-to-material ratio of 10-15:1, a frequency of 10-30 Hz, and a time of 60-300 min.
所述球磨预分散处理的方式可以为滚筒球磨或行星球磨,本领域技术人员可以根据需求选择。The method of ball milling pre-dispersion treatment can be roller ball milling or planetary ball milling, which can be selected by those skilled in the art according to requirements.
第二方面,本发明提供一种金属复合硼粉,其通过第一方面所述的方法制备得到,所述金属复合硼粉包括微米级硼颗粒和分散在硼颗粒表面的纳米级金属颗粒,所述金属复合硼粉中金属质量含量在2-15%,且所述金属复合硼粉的激光粒度满足:D50<1μm,D[4,3]<1μm。In a second aspect, the present invention provides a metal composite boron powder prepared by the method described in the first aspect, the metal composite boron powder includes micron-sized boron particles and nano-sized metal particles dispersed on the surface of the boron particles, the The mass content of metal in the metal composite boron powder is 2-15%, and the laser particle size of the metal composite boron powder satisfies: D 50 <1 μm, D[4,3] <1 μm.
优选地,所述金属复合硼粉中硼颗粒的粒度在0.2-3μm,金属颗粒的粒度在100nm以下。Preferably, the particle size of the boron particles in the metal composite boron powder is 0.2-3 μm, and the particle size of the metal particles is below 100 nm.
下面结合具体实例对本发明进行进一步详细的阐述。其中,实例中等离子体的气源为氩气和氢气,该氢气的通入流量为90L/min,其中氩气与该氢气的流量比为2:1。The present invention will be further described in detail below in conjunction with specific examples. Wherein, the gas sources of the plasma in the example are argon and hydrogen, the flow rate of the hydrogen is 90 L/min, and the flow ratio of the argon to the hydrogen is 2:1.
实施例1Example 1
一种制备金属复合硼粉的方法,步骤如下:A method for preparing metal composite boron powder, the steps are as follows:
(1)先对硼粉进行球磨预分散处理,球磨预分散处理的条件包括:球料比为12:1,频率为15Hz,时间为150min;(1) Pre-disperse the boron powder by ball milling. The conditions for ball milling pre-dispersion include: the ratio of ball to material is 12:1, the frequency is 15Hz, and the time is 150min;
再将氧化钼和所得硼粉粉末以质量比1:15进行球磨混合,得到粒度为0.3-45μm的混合粉末,所述混合粉末中硼粉的粒度在0.3-6μm,金属氧化物粉末的粒度在5-45μm;其中球磨混合的条件包括:球料比为6:1,频率为20Hz,时间为180min;Then molybdenum oxide and the obtained boron powder powder are ball milled and mixed at a mass ratio of 1:15 to obtain a mixed powder with a particle size of 0.3-45 μm, the particle size of the boron powder in the mixed powder is 0.3-6 μm, and the particle size of the metal oxide powder is 5-45μm; the mixing conditions of the ball mill include: the ratio of ball to material is 6:1, the frequency is 20Hz, and the time is 180min;
(2)再将所述混合粉末进行真空烘干,控制真空度≤-0.09MPa,烘干温度≥100℃,烘干时间≥15h;(2) Then vacuum-dry the mixed powder, control the vacuum degree ≤ -0.09MPa, the drying temperature ≥ 100°C, and the drying time ≥ 15h;
然后,将其与氩气载气混合送至等离子体火焰最底部的下方10cm处,混合粉末的送入速率为10g/min,且控制等离子功率为30kw,使得氧化钼气化并与氢气反应生成纳米钼颗粒,钼颗粒弥散分布于硼颗粒表面,得到钼复合硼粉。其中,硼颗粒的粒度在0.2-3μm,钼颗粒的粒度在100nm以下。Then, mix it with argon carrier gas and send it to the place 10cm below the bottom of the plasma flame. The feeding rate of the mixed powder is 10g/min, and the plasma power is controlled at 30kw, so that molybdenum oxide is vaporized and reacts with hydrogen to form Nano-molybdenum particles, the molybdenum particles are dispersed on the surface of the boron particles to obtain molybdenum composite boron powder. Wherein, the particle size of the boron particle is 0.2-3 μm, and the particle size of the molybdenum particle is below 100 nm.
所得钼复合硼粉中金属质量含量在5.42%,且激光粒度满足:D50=0.587μm,D[4,3]=0.797μm。钼复合硼粉的电镜图如图1所示,SEM面扫描如图2、图3、图4所示,结合其透镜图可以看出,所得复合物中吸附界面两侧分布以Mo和B单质的形式存在,且Mo以极小纳米颗粒弥散均匀分散在硼颗粒表面。The metal mass content in the obtained molybdenum composite boron powder is 5.42%, and the laser particle size meets: D 50 =0.587μm, D[4,3]=0.797μm. The electron microscope picture of molybdenum composite boron powder is shown in Figure 1, and the SEM surface scans are shown in Figure 2, Figure 3, and Figure 4. It can be seen from the lens diagram that Mo and B are distributed on both sides of the adsorption interface in the obtained composite. Exists in the form of Mo, and Mo is uniformly dispersed on the surface of boron particles in the form of extremely small nanoparticles.
实施例2Example 2
按照实施例1的方法进行,不同的是,送料位置不同,具体地,将其与氩气载气混合送至等离子体火焰最底部的下方30cm处。Carry out according to the method of Example 1, the difference is that the feeding position is different, specifically, it is mixed with argon carrier gas and sent to the place 30 cm below the bottom of the plasma flame.
所得钼复合硼粉中金属质量含量在5.15%,且激光粒度满足:D50=0.671μm,D[4,3]=0.873μm。钼复合硼粉中钼、硼均以单质形式存在,且钼以极小纳米颗粒弥散均匀分散在硼颗粒表面。The metal mass content in the obtained molybdenum composite boron powder is 5.15%, and the laser particle size meets: D 50 =0.671 μm, D[4,3]=0.873 μm. Both molybdenum and boron in molybdenum composite boron powder exist in the form of simple substance, and molybdenum is uniformly dispersed on the surface of boron particles in the form of extremely small nanoparticles.
实施例3Example 3
按照实施例1的方法进行,不同的是,混合粉末的送入速率为30g/min。Carry out according to the method of embodiment 1, difference is, the feeding rate of mixed powder is 30g/min.
所得钼复合硼粉中金属质量含量在5.29%,且激光粒度满足:D50=0.662μm,D[4,3]=0.891μm。钼复合硼粉中钼、硼均以单质形式存在,且钼以极小纳米颗粒弥散均匀分散在硼颗粒表面。The metal mass content in the obtained molybdenum composite boron powder is 5.29%, and the laser particle size meets: D 50 =0.662μm, D[4,3]=0.891μm. Both molybdenum and boron in molybdenum composite boron powder exist in the form of simple substance, and molybdenum is uniformly dispersed on the surface of boron particles in the form of extremely small nanoparticles.
对比例1Comparative example 1
按照实施例1的方法进行,不同的是,送料位置不同,具体地,将其与氩气载气混合送至等离子体火焰最底部的下方35cm处。Carry out according to the method of Example 1, the difference is that the feeding position is different, specifically, it is mixed with argon carrier gas and sent to the place 35 cm below the bottom of the plasma flame.
其送料位置温度较低,经分析产物为硼复合硼粉和氧化钼的混合物,主要是因为该位置温度较低,部分氧化钼未与氢气发生反应,冷却后又形成氧化钼粉体,混入生成的钼复合硼粉内。The temperature at the feeding position is low, and the analyzed product is a mixture of boron composite boron powder and molybdenum oxide, mainly because the temperature at this position is low, and part of the molybdenum oxide does not react with hydrogen, and forms molybdenum oxide powder after cooling, which is mixed to form molybdenum complex boron powder.
对比例2Comparative example 2
按照实施例1的方法进行,不同的是,送料位置不同,具体地,将其与氩气载气混合送至等离子体火焰最底部的下方5cm处。Carry out according to the method of Example 1, the difference is that the feeding position is different, specifically, it is mixed with argon carrier gas and sent to the place 5 cm below the bottom of the plasma flame.
其送料位置过高,反应温度较高,硼粉有气化可能,并与生成的钼金属反应,生成硼化物,导致金属复合硼粉制备失败。The feeding position is too high, the reaction temperature is high, the boron powder may be gasified, and react with the generated molybdenum metal to form borides, resulting in the failure of the preparation of the metal composite boron powder.
对比例3Comparative example 3
通过常规球磨工艺(硼粉500g,钼粉25g,进行混合球磨,球料比5:1,球磨频率40Hz,球磨时间240min)制备钼复合硼粉,复合后出现钼金属沉积情况,复合失败。Molybdenum composite boron powder was prepared by conventional ball milling process (boron powder 500g, molybdenum powder 25g, mixed ball milling, ball to material ratio 5:1, ball milling frequency 40Hz, ball milling time 240min). Molybdenum metal deposition occurred after compounding, and compounding failed.
测试例test case
将上述实施例和对比例获得的产物进行性能测试:使用氧弹量热仪对其燃烧热值进行测试,燃烧热值的高低直接反应了硼粉经钼复合改性后燃烧性能的变化情况。测试结果如下表1所示。Performance tests were performed on the products obtained in the above examples and comparative examples: the combustion calorific value was tested with an oxygen bomb calorimeter, and the combustion calorific value directly reflected the change of the combustion performance of the boron powder modified by molybdenum compounding. The test results are shown in Table 1 below.
表1Table 1
通过上述结果可知,采用本发明的实施例方案,能够获得特定结构的金属复合硼粉,其中金属单质以极小纳米颗粒弥散均匀分散在硼颗粒表面,显著提高了金属复合硼粉的燃烧性能。而不在本发明范围的对比例1-2,或者采用常规球磨工艺的对比例3,其燃烧性能明显低于本发明实施例。From the above results, it can be known that the metal composite boron powder with a specific structure can be obtained by using the embodiments of the present invention, in which the metal element is uniformly dispersed on the surface of the boron particles with extremely small nanoparticles, which significantly improves the combustion performance of the metal composite boron powder. The combustion performance of Comparative Example 1-2, which is not within the scope of the present invention, or Comparative Example 3, which adopts a conventional ball milling process, is significantly lower than that of the examples of the present invention.
进一步的,根据本发明实施例1和实施例2可知,采用本发明优选的方案,所得金属复合硼粉的燃烧性能更优。Further, according to Example 1 and Example 2 of the present invention, it can be seen that the combustion performance of the obtained metal composite boron powder is better by adopting the preferred scheme of the present invention.
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the content disclosed in the present invention. All belong to the protection scope of the present invention.
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US4755221A (en) * | 1986-03-24 | 1988-07-05 | Gte Products Corporation | Aluminum based composite powders and process for producing same |
US7285329B2 (en) * | 2004-02-18 | 2007-10-23 | Hitachi Metals, Ltd. | Fine composite metal particles and their production method, micro-bodies, and magnetic beads |
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CN112028083B (en) * | 2020-09-15 | 2021-05-18 | 湖南澎越新材料有限公司 | Preparation method of rare metal boride |
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