CN101569929A - Method for preparing nano aluminum oxide coated tungsten powder - Google Patents
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 71
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 51
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- 239000007921 spray Substances 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 20
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- 239000011812 mixed powder Substances 0.000 claims description 14
- 229910052721 tungsten Inorganic materials 0.000 claims description 14
- 239000010937 tungsten Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000011946 reduction process Methods 0.000 claims description 2
- 208000032544 Cicatrix Diseases 0.000 claims 2
- 239000008187 granular material Substances 0.000 claims 2
- 231100000241 scar Toxicity 0.000 claims 2
- 230000037387 scars Effects 0.000 claims 2
- 230000011218 segmentation Effects 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000007710 freezing Methods 0.000 abstract description 2
- 230000008014 freezing Effects 0.000 abstract description 2
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000005352 clarification Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000011109 contamination Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 description 17
- 229910052573 porcelain Inorganic materials 0.000 description 16
- 239000000463 material Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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Abstract
本发明涉及一种纳米氧化铝包覆钨粉的制备方法，属于粉末冶金制备领域。目前制备纳米氧化铝包覆钨粉存在的问题有粒度不均匀、达不到纳米级、易受污染、粉体存在团聚等。本发明包覆粉的特征为：纳米氧化铝包覆在微米级钨粉的表面，氧化铝的摩尔含量为10～30％。该包覆粉体的制备方法特征为：将偏钨酸铵粉末与硫酸铝粉末共溶于蒸馏水中，待澄清，使用氮气喷枪将其分散在液氮中预冻，将预冻物置于冻干机中进行真空干燥得到冻干粉末；在氢气气氛下对冻干粉末进行分段煅烧还原，即可得到纳米氧化铝包覆钨粉的复合粉体。本发明优势在于制备过程步骤少、操作简单，原料便宜易得，且无需提前添加基体相颗粒。The invention relates to a preparation method of nano-alumina-coated tungsten powder, which belongs to the field of powder metallurgy preparation. At present, the problems in the preparation of nano-alumina-coated tungsten powder include uneven particle size, failure to reach the nanometer level, easy contamination, and agglomeration of the powder. The coating powder of the present invention is characterized in that: nano-alumina is coated on the surface of the micron-sized tungsten powder, and the molar content of the alumina is 10-30%. The preparation method of the coated powder is characterized by: dissolving ammonium metatungstate powder and aluminum sulfate powder in distilled water, and after clarification, use a nitrogen spray gun to disperse it in liquid nitrogen for pre-freezing, and place the pre-frozen product in freeze-dry The freeze-dried powder is obtained by vacuum drying in the machine; the freeze-dried powder is calcined and reduced in stages under a hydrogen atmosphere to obtain a composite powder of nano-alumina-coated tungsten powder. The invention has the advantages of fewer steps in the preparation process, simple operation, cheap and easy-to-obtain raw materials, and no need to add matrix phase particles in advance.
Description
技术领域： Technical field:
本发明涉及一种纳米氧化铝包覆钨粉体的制备方法，特别是一种在钨粉表面包覆纳米氧化铝的复合粉制备方法，属于粉末冶金中包覆粉体制备领域。The invention relates to a preparation method of nano-alumina-coated tungsten powder, in particular to a preparation method of a composite powder in which nano-alumina is coated on the surface of tungsten powder, and belongs to the field of powder metallurgy preparation of coated powder.
背景技术： Background technique:
纳米陶瓷粉体均匀掺杂金属基颗粒得到的复合粉体制备的复合材料，不仅具有金属的优良韧性、导热导电性等，又具有陶瓷的耐高温、耐磨损和耐腐蚀以及高硬度、高化学稳定性等特性，引起了广泛的重视。为保证复合粒子的分散均匀性，以最大幅地提高材料的性能，往往要求将掺杂相粒子包覆在基体颗粒表面，形成包覆层，达到最佳混合度。纳米氧化铝粉体包覆钨粉制备的复合材料有着单相氧化物或金属不可比拟的优势。目前，纳米氧化铝包覆钨粉的制备多采用固相球磨和液相法，大都面临一些共性的问题：The composite material prepared by the composite powder obtained by uniformly doping metal-based particles with nano-ceramic powder not only has the excellent toughness and thermal conductivity of metal, but also has the high temperature resistance, wear resistance and corrosion resistance of ceramics, as well as high hardness and high Chemical stability and other characteristics have attracted extensive attention. In order to ensure the dispersion uniformity of the composite particles and maximize the performance of the material, it is often required to coat the dopant phase particles on the surface of the matrix particles to form a coating layer to achieve the best mixing degree. The composite material prepared by nano-alumina powder coated tungsten powder has incomparable advantages over single-phase oxide or metal. At present, the preparation of nano-alumina-coated tungsten powder mostly adopts solid-phase ball milling and liquid-phase methods, and most of them face some common problems:
(1)通过球磨得到的氧化铝包覆钨粉的粒度不均匀，且包覆层的氧化铝达不到纳米级，包覆粉体易受污染；(1) The particle size of the alumina-coated tungsten powder obtained by ball milling is uneven, and the alumina of the coating layer cannot reach the nanometer level, and the coated powder is easily polluted;
(2)液相法选用原料昂贵，制备条件苛刻，难以控制，且由于液相的存在使得最终包覆粉体存在团聚。(2) The raw materials used in the liquid phase method are expensive, the preparation conditions are harsh, and it is difficult to control, and the final coated powder is agglomerated due to the existence of the liquid phase.
这些问题的存在限制了纳米氧化铝包覆钨粉复合材料的发展和应用。The existence of these problems limits the development and application of nano-alumina-coated tungsten powder composites.
发明内容： Invention content:
针对现有技术存在的以上问题，本发明提供了一种纳米氧化铝包覆钨粉的制备方法。Aiming at the above problems in the prior art, the present invention provides a preparation method of nano-alumina-coated tungsten powder.
本发明所提供的一种纳米氧化铝包覆钨粉的制备方法，其特征在于，它包括以下步骤：A method for preparing nano-alumina-coated tungsten powder provided by the present invention is characterized in that it comprises the following steps:
(1)分别按目标复合粉体中氧化铝与钨的摩尔比为氧化铝∶钨＝1∶9～3∶7，称量偏钨酸铵[(NH4)6H2W12O40·14H2O]白色晶体粉末和硫酸铝[Al2(SO4)3·18H2O]晶体粉末，并将二者共溶于蒸馏水中，待澄清；(1) According to the molar ratio of alumina to tungsten in the target composite powder, alumina: tungsten = 1:9~3:7, weigh ammonium metatungstate [(NH 4 ) 6 H 2 W 12 O 40 · 14H 2 O] white crystal powder and aluminum sulfate [Al 2 (SO 4 ) 3 ·18H 2 O] crystal powder, and the two were co-dissolved in distilled water, to be clarified;
(2)使用通用氮气喷枪，将澄清的混合溶液分散在通用的液氮中预冻，得到冻结物，喷枪压力为1.5～3.5个大气压；(2) Use a general-purpose nitrogen spray gun to disperse the clarified mixed solution in general-purpose liquid nitrogen for pre-freezing to obtain a frozen product, and the spray gun pressure is 1.5 to 3.5 atmospheres;
(3)将使用液氮预冻的冻结物置于冻干机中进行真空干燥，得到冻干的混合粉末；(3) Place the frozen material pre-frozen with liquid nitrogen in a lyophilizer for vacuum drying to obtain a lyophilized mixed powder;
(4)将步骤(3)得到的冻干的混合粉末实行分段煅烧还原，气氛为氢气气氛，流量为0.1～0.5m3/h；得到纳米氧化铝包覆钨粉的复合粉体，氧化铝粒度约20nm左右，钨粉粒度约1μm左右。(4) The freeze-dried mixed powder obtained in step (3) is subjected to segmental calcination and reduction, the atmosphere is a hydrogen atmosphere, and the flow rate is 0.1 to 0.5m 3 /h; the composite powder of nano-alumina-coated tungsten powder is obtained, oxidized The aluminum particle size is about 20nm, and the tungsten powder particle size is about 1μm.
其中，步骤(2)中所述的氮气喷枪的压力为1.5～3.5个大气压。Wherein, the pressure of the nitrogen spray gun described in step (2) is 1.5 to 3.5 atmospheres.
步骤(3)所述的冻干机的执行程序为：在0～2400分钟内的工作压力为250～350毫托、温度为-28～-24℃；在2400～3800分钟内的工作压力为120～180毫托、温度为-15～-12℃；在3800～4600分钟内的工作压力为50～100毫托、温度为-3～2℃；在4600～4800分钟内的工作压力为0～20毫托、温度为15～25℃。The execution program of the freeze dryer described in step (3) is: the working pressure within 0～2400 minutes is 250～350 millitorr, the temperature is-28～-24 ℃; the working pressure within 2400～3800 minutes is 120~180 mtorr, temperature -15~-12°C; working pressure within 3800~4600 minutes,
步骤(4)中所述的分段煅烧还原，包括两段过程：第一段为还原过程，还原温度为650～850℃，保温120～240分钟，偏钨酸铵经热分解、氢还原变成金属钨；第二段为煅烧分解过程，分解温度为900～1100℃，保温120～360分钟，硫酸铝经热分解变成氧化铝，包覆在钨粉表面。The segmental calcination reduction described in step (4) includes two stages of process: the first stage is the reduction process, the reduction temperature is 650-850°C, and the heat preservation is 120-240 minutes. Ammonium metatungstate is transformed into into metal tungsten; the second stage is the calcination decomposition process, the decomposition temperature is 900-1100 ℃, and the temperature is kept for 120-360 minutes. Aluminum sulfate is thermally decomposed into alumina, which is coated on the surface of tungsten powder.
本发明采用液氮预冻-冷冻干燥法，通过低温低压干燥，制得非晶态冻干粉末，可以有效防止单相颗粒偏聚。再通过分段煅烧还原，得到纳米氧化铝包覆钨粉的复合粉体。本发明优势在于制备过程步骤少、操作简单，原料便宜易得，且无需提前添加基体相颗粒。The invention adopts a liquid nitrogen prefreezing-freeze drying method to obtain an amorphous freeze-dried powder through low-temperature and low-pressure drying, which can effectively prevent the segregation of single-phase particles. Then, the composite powder of nano-alumina-coated tungsten powder is obtained through segmental calcination and reduction. The invention has the advantages of fewer steps in the preparation process, simple operation, cheap and easy-to-obtain raw materials, and no need to add matrix phase particles in advance.
附图说明： Description of drawings:
图1：实施例2的冻干混合粉末X射线衍射图谱Fig. 1: X-ray diffraction pattern of freeze-dried mixed powder of embodiment 2
图2：实施例3的纳米氧化铝包覆钨粉X射线衍射图谱Figure 2: X-ray diffraction pattern of nano-alumina-coated tungsten powder in Example 3
图3：实施例4的纳米氧化铝包覆钨粉SEM像Figure 3: SEM image of nano-alumina-coated tungsten powder in Example 4
以下结合附图和具体实施方式对本发明作进一步描述。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.
具体实施方式：Detailed ways:
实施例中所使用的冻干机为FTS公司的FTD Dura-stop MP型冻干机。The freeze-drying machine used in the embodiment is the FTD Dura-stop MP type freeze-drying machine of FTS company.
实施例1：Example 1:
(1)按最终氧化铝与钨粉的摩尔比为2∶8，分别称量3.567克偏钨酸铵白色晶体粉末和2.222克硫酸铝白色晶体粉末，将二者共溶于250毫升蒸馏水，待澄清；(1) According to the final molar ratio of alumina and tungsten powder is 2: 8, weigh 3.567 grams of ammonium metatungstate white crystal powder and 2.222 grams of aluminum sulfate white crystal powder respectively, dissolve the two in 250 milliliters of distilled water, wait clarify;
(2)使用氮气喷枪，将澄清的混合溶液分散在液氮中得到冻结物，喷枪压力为1.5个大气压；(2) Use a nitrogen spray gun to disperse the clarified mixed solution in liquid nitrogen to obtain a frozen substance, and the spray gun pressure is 1.5 atmospheres;
(3)再将冻结物置于冻干机中进行真空干燥，冻干机的执行程序为：在0～2400分钟内的工作压力为250毫托、温度为-24℃；在2400～3800分钟内的工作压力为150毫托、温度为-14℃；在3800～4600分钟内的工作压力为80毫托、温度为-1℃；在4600～4800分钟内的工作压力为0毫托、温度为20℃；(3) Place the frozen material in a freeze dryer for vacuum drying. The execution procedure of the freeze dryer is as follows: the working pressure is 250 millitorr and the temperature is -24°C within 0 to 2400 minutes; The working pressure is 150 millitorr and the temperature is -14°C; the working pressure is 80 millitorr and the temperature is -1°C within 3800 to 4600 minutes; the working pressure is 0 millitorr and the temperature is 4600 to 4800
(4)将冷冻干燥后的混合粉末装入瓷舟，将瓷舟推入管式炉中，通氢气进行分段煅烧还原，氢气流量为0.1m3/h；第一段温度为650℃，保温240分钟，偏钨酸铵经热分解、氢还原变成金属钨；第二段温度为900℃，保温360分钟，硫酸铝经热分解变成氧化铝，包覆在钨粉表面，得到纳米氧化铝包覆钨粉的复合粉体，氧化铝粒度为32nm，钨粉粒度为1.17μm。(4) Put the freeze-dried mixed powder into a porcelain boat, push the porcelain boat into a tube furnace, and carry out staged calcination and reduction with hydrogen gas flow rate of 0.1m 3 /h; the temperature of the first stage is 650°C, After heat preservation for 240 minutes, ammonium metatungstate becomes metal tungsten through thermal decomposition and hydrogen reduction; the second stage temperature is 900°C, heat preservation is 360 minutes, aluminum sulfate is heat decomposed into alumina, coated on the surface of tungsten powder, and nano Alumina-coated tungsten powder composite powder, alumina particle size is 32nm, tungsten powder particle size is 1.17μm.
实施例2：Example 2:
(1)按最终氧化铝与钨粉的摩尔比为2∶8，分别称量4.28克偏钨酸铵白色晶体粉末和2.666克硫酸铝白色晶体粉末，将二者共溶于300毫升蒸馏水，待澄清；(1) According to the final molar ratio of alumina and tungsten powder is 2: 8, weigh 4.28 grams of ammonium metatungstate white crystal powder and 2.666 grams of aluminum sulfate white crystal powder respectively, dissolve the two in 300 milliliters of distilled water, wait clarify;
(2)使用氮气喷枪，将澄清的混合溶液分散在液氮中得到冻结物，喷枪压力为2个大气压；(2) Use a nitrogen spray gun to disperse the clarified mixed solution in liquid nitrogen to obtain a frozen substance, and the spray gun pressure is 2 atmospheres;
(3)再将冻结物置于冻干机中进行真空干燥，冻干机的执行程序为：在0～2400分钟内的工作压力为300毫托、温度为-26℃；在2400～3800分钟内的工作压力为160毫托、温度为-13℃；在3800～4600分钟内的工作压力为50毫托、温度为0℃；在4600～4800分钟内的工作压力为0毫托、温度为25℃；(3) Place the frozen material in a freeze dryer for vacuum drying. The execution procedure of the freeze dryer is as follows: the working pressure is 300 millitorr and the temperature is -26°C within 0 to 2400 minutes; The working pressure is 160 millitorr and the temperature is -13°C; the working pressure is 50 millitorr and the temperature is 0°C within 3800 to 4600 minutes; the working pressure is 0 millitorr and the temperature is 25 within 4600 to 4800 minutes ℃;
(4)将冷冻干燥后的混合粉末装入瓷舟，将瓷舟推入管式炉中，通氢气进行分段煅烧还原，氢气流量为0.2m3/h，第一段温度为700℃，保温240分钟，偏钨酸铵经热分解、氢还原变成金属钨；第二段温度为1000℃，保温240分钟，硫酸铝经热分解变成氧化铝，包覆在钨粉表面，得到纳米氧化铝包覆钨粉的复合粉体，氧化铝粒度为28nm，钨粉粒度为0.86μm。(4) Put the freeze-dried mixed powder into a porcelain boat, push the porcelain boat into a tube furnace, and carry out staged calcination and reduction with hydrogen gas flow rate of 0.2m 3 /h, and the temperature of the first stage is 700°C. After heat preservation for 240 minutes, ammonium metatungstate becomes metal tungsten through thermal decomposition and hydrogen reduction; the second stage temperature is 1000°C, heat preservation for 240 minutes, aluminum sulfate is heat decomposed into alumina, coated on the surface of tungsten powder, and nano Alumina-coated tungsten powder composite powder, the alumina particle size is 28nm, and the tungsten powder particle size is 0.86μm.
图1为本实施例步骤(3)所得冻干混合粉末的X射线衍射图谱，从图中可以看出，冻干粉末为非晶态粉末。Fig. 1 is the X-ray diffraction spectrum of the freeze-dried mixed powder obtained in step (3) of this embodiment, as can be seen from the figure, the freeze-dried powder is an amorphous powder.
实施例3：Example 3:
(1)按最终氧化铝与钨粉的摩尔比为2∶8，分别称量5.35克偏钨酸铵白色晶体粉末和3.332克硫酸铝白色晶体粉末，将二者共溶于400毫升蒸馏水，待澄清；(1) According to the molar ratio of final alumina and tungsten powder is 2: 8, weigh 5.35 grams of ammonium metatungstate white crystal powder and 3.332 grams of aluminum sulfate white crystal powder respectively, dissolve the two in 400 milliliters of distilled water, wait clarify;
(2)使用氮气喷枪，将澄清的混合溶液分散在液氮中得到冻结物，喷枪压力为2.5个大气压；(2) Use a nitrogen spray gun to disperse the clarified mixed solution in liquid nitrogen to obtain a frozen substance, and the spray gun pressure is 2.5 atmospheres;
(3)再将冻结物置于冻干机中进行真空干燥，冻干机的执行程序为：在0～2400分钟内的工作压力为350毫托、温度为-28℃；在2400～3800分钟内的工作压力为180毫托、温度为-15℃；在3800～4600分钟内的工作压力为100毫托、温度为-3℃；在4600～4800分钟内的工作压力为20毫托、温度为15℃；(3) Place the frozen material in a freeze dryer for vacuum drying. The execution procedure of the freeze dryer is as follows: the working pressure is 350 millitorr and the temperature is -28°C within 0 to 2400 minutes; The working pressure is 180 millitorr and the temperature is -15°C; the working pressure is 100 millitorr and the temperature is -3°C within 3800 to 4600 minutes; the working pressure is 20 millitorr and the temperature is 4600 to 4800 minutes 15°C;
(4)将冷冻干燥后的混合粉末装入瓷舟，将瓷舟推入管式炉中，通氢气进行分段煅烧还原，氢气流量为0.5m3/h，第一段温度为800℃，保温180分钟，偏钨酸铵经热分解、氢还原变成金属钨；第二段温度为1100℃，保温120分钟，硫酸铝经热分解变成氧化铝，包覆在钨粉表面，得到纳米氧化铝包覆钨粉的复合粉体，氧化铝粒度为30nm，钨粉粒度为0.98μm。(4) Put the freeze-dried mixed powder into a porcelain boat, push the porcelain boat into a tube furnace, and carry out staged calcination and reduction with hydrogen, the hydrogen flow rate is 0.5m 3 /h, and the temperature in the first stage is 800°C. After heat preservation for 180 minutes, ammonium metatungstate becomes metal tungsten through thermal decomposition and hydrogen reduction; the temperature of the second stage is 1100°C, heat preservation for 120 minutes, aluminum sulfate is thermally decomposed into alumina, and coated on the surface of tungsten powder to obtain nano The composite powder of alumina coated tungsten powder, the particle size of alumina is 30nm, and the particle size of tungsten powder is 0.98μm.
图2为本实施例得到的最终产物纳米氧化铝包覆钨粉的X射线衍射图谱。从图中可以看出，采用液氮预冻-冷冻干燥-分段煅烧还原的方法，煅烧还原后得到的最终粉末分别为钨和氧化铝，说明分解还原充分，得到了所需的物相组成。Fig. 2 is the X-ray diffraction spectrum of the final product nano-alumina-coated tungsten powder obtained in this embodiment. It can be seen from the figure that the final powders obtained after calcining and reducing are tungsten and alumina respectively by using the method of liquid nitrogen prefreezing-freeze drying-calcining and reducing, which shows that the decomposition and reduction are sufficient and the required phase composition is obtained. .
实施例4：Example 4:
(1)按最终氧化铝与钨粉的摩尔比为1∶9，分别称量12.038克偏钨酸铵白色晶体粉末和3.332克硫酸铝白色晶体粉末，将二者共溶于500毫升蒸馏水，待澄清；(1) According to the molar ratio of final alumina and tungsten powder being 1:9, weigh 12.038 grams of ammonium metatungstate white crystal powder and 3.332 grams of aluminum sulfate white crystal powder respectively, and dissolve the two in 500 milliliters of distilled water. clarify;
(2)使用氮气喷枪，将澄清的混合溶液分散在液氮中得到冻结物，喷枪压力为3个大气压；(2) Use a nitrogen spray gun to disperse the clarified mixed solution in liquid nitrogen to obtain a frozen substance, and the spray gun pressure is 3 atmospheres;
(3)再将冻结物置于冻干机中进行真空干燥，冻干机的执行程序为：在0～2400分钟内的工作压力为250毫托、温度为-24℃；在2400～3800分钟内的工作压力为120毫托、温度为-12℃；在3800～4600分钟内的工作压力为50毫托、温度为2℃；在4600～4800分钟内的工作压力为0毫托、温度为25℃；(3) Place the frozen material in a freeze dryer for vacuum drying. The execution procedure of the freeze dryer is as follows: the working pressure is 250 millitorr and the temperature is -24°C within 0 to 2400 minutes; The working pressure is 120 millitorr and the temperature is -12°C; the working pressure is 50 millitorr and the temperature is 2°C within 3800 to 4600 minutes; the working pressure is 0 millitorr and the temperature is 25 within 4600 to 4800 minutes ℃;
(4)将冷冻干燥后的混合粉末装入瓷舟，将瓷舟推入管式炉中，通氢气进行分段煅烧还原，氢气流量为0.4m3/h，第一段温度为850℃，保温120分钟，偏钨酸铵经热分解、氢还原变成金属钨；第二段温度为1050℃，保温300分钟，硫酸铝经热分解变成氧化铝，包覆在钨粉表面，得到纳米氧化铝包覆钨粉的复合粉体，氧化铝粒度为35nm，钨粉粒度为1.26μm。(4) Put the freeze-dried mixed powder into a porcelain boat, push the porcelain boat into a tube furnace, and carry out staged calcination and reduction with hydrogen flow, the hydrogen flow rate is 0.4m 3 /h, and the temperature in the first stage is 850°C. After heat preservation for 120 minutes, ammonium metatungstate becomes metal tungsten through thermal decomposition and hydrogen reduction; the temperature of the second stage is 1050°C, heat preservation for 300 minutes, aluminum sulfate is thermally decomposed into alumina, and coated on the surface of tungsten powder to obtain nano Alumina-coated tungsten powder composite powder, alumina particle size is 35nm, tungsten powder particle size is 1.26μm.
图3为本实施例得到的最终产物纳米氧化铝包覆钨粉的SEM像。从图中可以看出，采用液氮预冻-冷冻干燥-分段煅烧还原的方法获得的纳米氧化铝包覆钨粉的复合粉体，氧化铝粒径35nm，钨粉粒径1.26μm。Fig. 3 is the SEM image of the final product nano-alumina-coated tungsten powder obtained in this embodiment. It can be seen from the figure that the composite powder of nano-alumina-coated tungsten powder obtained by liquid nitrogen pre-freezing-freeze drying-segmented calcining reduction method has a particle size of alumina of 35nm and a particle size of tungsten powder of 1.26μm.
实施例5：Example 5:
(1)按最终氧化铝与钨粉的摩尔比为1∶9，分别称量8.025克偏钨酸铵白色晶体粉末和2.222克硫酸铝白色晶体粉末，将二者共溶于500毫升蒸馏水，待澄清；(1) According to the molar ratio of final alumina and tungsten powder being 1:9, weigh 8.025 grams of ammonium metatungstate white crystal powder and 2.222 grams of aluminum sulfate white crystal powder respectively, and dissolve the two in 500 milliliters of distilled water. clarify;
(2)使用氮气喷枪，将澄清的混合溶液分散在液氮中得到冻结物，喷枪压力为3.5个大气压；(2) Use a nitrogen spray gun to disperse the clarified mixed solution in liquid nitrogen to obtain a frozen substance, and the spray gun pressure is 3.5 atmospheres;
(3)再将冻结物置于冻干机中进行真空干燥，冻干机的执行程序为：在0～2400分钟内的工作压力为280毫托、温度为-25℃；在2400～3800分钟内的工作压力为140毫托、温度为-12℃；在3800～4600分钟内的工作压力为50毫托、温度为1℃；在4600～4800分钟内的工作压力为10毫托、温度为22℃；(3) Place the frozen material in a freeze dryer for vacuum drying. The execution procedure of the freeze dryer is as follows: the working pressure is 280 millitorr and the temperature is -25°C within 0 to 2400 minutes; The working pressure is 140 millitorr and the temperature is -12°C; the working pressure is 50 millitorr and the temperature is 1°C within 3800 to 4600 minutes; the working pressure is 10 millitorr and the temperature is 22 within 4600 to 4800 minutes ℃;
(4)将冷冻干燥后的混合粉末装入瓷舟，将瓷舟推入管式炉中，通氢气进行分段煅烧还原，氢气流量为0.3m3/h，第一段温度为750℃，保温240分钟，偏钨酸铵经热分解、氢还原变成金属钨；第二段温度为1100℃，保温120分钟，硫酸铝经热分解变成氧化铝，包覆在钨粉表面，得到纳米氧化铝包覆钨粉的复合粉体，氧化铝粒度为36nm，钨粉粒度为1.13μm。(4) Put the freeze-dried mixed powder into a porcelain boat, push the porcelain boat into a tube furnace, and carry out staged calcination and reduction with hydrogen gas flow rate of 0.3m 3 /h, and the temperature of the first stage is 750°C. After heat preservation for 240 minutes, ammonium metatungstate becomes metallic tungsten through thermal decomposition and hydrogen reduction; the temperature of the second stage is 1100°C, heat preservation for 120 minutes, aluminum sulfate is thermally decomposed into alumina, and coated on the surface of tungsten powder to obtain nano Alumina-coated tungsten powder composite powder, the alumina particle size is 36nm, and the tungsten powder particle size is 1.13μm.
实施例6：Embodiment 6:
(1)按最终氧化铝与钨粉的摩尔比为3∶7，分别称量3.746克偏钨酸铵白色晶体粉末和3.998克硫酸铝白色晶体粉末，将二者共溶于250毫升蒸馏水，待澄清；(1) According to the mol ratio of final alumina and tungsten powder is 3: 7, respectively weigh 3.746 grams of ammonium metatungstate white crystal powder and 3.998 grams of aluminum sulfate white crystal powder, the two are dissolved in 250 milliliters of distilled water, wait clarify;
(2)使用氮气喷枪，将澄清的混合溶液分散在液氮中得到冻结物，喷枪压力为1.8个大气压；(2) Use a nitrogen spray gun to disperse the clarified mixed solution in liquid nitrogen to obtain a frozen substance, and the spray gun pressure is 1.8 atmospheres;
(3)再将冻结物置于冻干机中进行真空干燥，冻干机的执行程序为：在0～2400分钟内的工作压力为320毫托、温度为-26℃；在2400～3800分钟内的工作压力为160毫托、温度为-13℃；在3800～4600分钟内的工作压力为80毫托、温度为0℃；在4600～4800分钟内的工作压力为0毫托、温度为20℃；(3) Place the frozen material in a freeze dryer for vacuum drying. The execution procedure of the freeze dryer is as follows: the working pressure is 320 millitorr and the temperature is -26°C within 0 to 2400 minutes; The working pressure is 160 millitorr and the temperature is -13°C; the working pressure is 80 millitorr and the temperature is 0°C within 3800 to 4600 minutes; the working pressure is 0 millitorr and the temperature is 20 within 4600 to 4800 minutes ℃;
(4)将冷冻干燥后的混合粉末装入瓷舟，将瓷舟推入管式炉中，通氢气进行分段煅烧还原，氢气流量为0.1m3/h，第一段温度为850℃，保温240分钟，偏钨酸铵经热分解、氢还原变成金属钨；第二段温度为900℃，保温360分钟，硫酸铝经热分解变成氧化铝，包覆在钨粉表面，得到纳米氧化铝包覆钨粉的复合粉体，氧化铝粒度为32nm，钨粉粒度为1.21μm。(4) Put the freeze-dried mixed powder into a porcelain boat, push the porcelain boat into a tube furnace, and carry out staged calcination and reduction with hydrogen gas flow rate of 0.1m 3 /h, and the temperature of the first stage is 850°C. After heat preservation for 240 minutes, ammonium metatungstate becomes metal tungsten through thermal decomposition and hydrogen reduction; the second stage temperature is 900°C, heat preservation is 360 minutes, aluminum sulfate is heat decomposed into alumina, coated on the surface of tungsten powder, and nano Alumina-coated tungsten powder composite powder, the alumina particle size is 32nm, and the tungsten powder particle size is 1.21μm.
实施例7：Embodiment 7:
(1)按最终氧化铝与钨粉的摩尔比为3∶7，分别称量5.619克偏钨酸铵白色晶体粉末和5.998克硫酸铝白色晶体粉末，将二者共溶于xx毫升蒸馏水，待澄清；(1) According to the final molar ratio of alumina and tungsten powder of 3:7, weigh 5.619 grams of ammonium metatungstate white crystal powder and 5.998 grams of aluminum sulfate white crystal powder respectively, and dissolve the two in xx milliliters of distilled water. clarify;
(2)使用氮气喷枪，将澄清的混合溶液分散在液氮中得到冻结物，喷枪压力为2.8个大气压；(2) Use a nitrogen spray gun to disperse the clarified mixed solution in liquid nitrogen to obtain a frozen substance, and the spray gun pressure is 2.8 atmospheres;
(3)再将冻结物置于冻干机中进行真空干燥，冻干机的执行程序为：在0～2400分钟内的工作压力为300毫托、温度为-26℃；在2400～3800分钟内的工作压力为150毫托、温度为-13℃；在3800～4600分钟内的工作压力为60毫托、温度为0℃；在4600～4800分钟内的工作压力为0毫托、温度为20℃；(3) Place the frozen material in a freeze dryer for vacuum drying. The execution procedure of the freeze dryer is as follows: the working pressure is 300 millitorr and the temperature is -26°C within 0 to 2400 minutes; The working pressure is 150 millitorr and the temperature is -13°C; the working pressure is 60 millitorr and the temperature is 0°C within 3800 to 4600 minutes; the working pressure is 0 millitorr and the temperature is 20 within 4600 to 4800 minutes ℃;
(4)将冷冻干燥后的混合粉末装入瓷舟，将瓷舟推入管式炉中，通氢气进行分段煅烧还原，氢气流量为0.5m3/h，第一段温度为750℃，保温240分钟，偏钨酸铵经热分解、氢还原变成金属钨；第二段温度为1000℃，保温240分钟，硫酸铝经热分解变成氧化铝，包覆在钨粉表面，得到纳米氧化铝包覆钨粉的复合粉体，氧化铝粒度为25nm，钨粉粒度为0.95μm。(4) Put the freeze-dried mixed powder into a porcelain boat, push the porcelain boat into a tube furnace, and carry out staged calcination and reduction with hydrogen, the hydrogen flow rate is 0.5m 3 /h, and the temperature of the first stage is 750°C. After heat preservation for 240 minutes, ammonium metatungstate becomes metal tungsten through thermal decomposition and hydrogen reduction; the second stage temperature is 1000°C, heat preservation for 240 minutes, aluminum sulfate is heat decomposed into alumina, coated on the surface of tungsten powder, and nano The composite powder of alumina coated tungsten powder, the particle size of alumina is 25nm, and the particle size of tungsten powder is 0.95μm.
实施例8：Embodiment 8:
(1)按最终氧化铝与钨粉的摩尔比为3∶7，分别称量7.492克偏钨酸铵白色晶体粉末和7.996克硫酸铝白色晶体粉末，将二者共溶于500毫升蒸馏水，待澄清；(1) According to the mol ratio of final alumina and tungsten powder is 3: 7, weigh 7.492 grams of ammonium metatungstate white crystal powder and 7.996 grams of aluminum sulfate white crystal powder respectively, dissolve the two in 500 milliliters of distilled water, wait clarify;
(2)使用氮气喷枪压，将澄清的混合溶液分散在液氮中得到冻结物，喷枪压力为3.2个大气：(2) Use the nitrogen spray gun pressure to disperse the clarified mixed solution in liquid nitrogen to obtain the frozen product, and the spray gun pressure is 3.2 atmospheres:
(3)再将冻结物置于冻干机中进行真空干燥，冻干机的执行程序为：在0～2400分钟内的工作压力为300毫托、温度为-30℃；在2400～3800分钟内的工作压力为120毫托、温度为-15℃；在3800～4600分钟内的工作压力为80毫托、温度为0℃；在4600～4800分钟内的工作压力为0毫托、温度为15℃；(3) Place the frozen material in a freeze dryer for vacuum drying. The execution procedure of the freeze dryer is as follows: the working pressure is 300 millitorr and the temperature is -30°C within 0 to 2400 minutes; The working pressure is 120 millitorr and the temperature is -15°C; the working pressure is 80 millitorr and the temperature is 0°C within 3800 to 4600 minutes; the working pressure is 0 millitorr and the temperature is 15 within 4600 to 4800 minutes ℃;
(4)将冷冻干燥后的混合粉末装入瓷舟，将瓷舟推入管式炉中，通氢气进行分段煅烧还原，氢气流量为0.3m3/h，第一段温度为650℃，保温240分钟，偏钨酸铵经热分解、氢还原变成金属钨；第二段温度为1100℃，保温240分钟，硫酸铝经热分解变成氧化铝，包覆在钨粉表面，得到纳米氧化铝包覆钨粉的复合粉体，氧化铝粒度为31nm，钨粉粒度为1.08μm。(4) Put the freeze-dried mixed powder into a porcelain boat, push the porcelain boat into a tube furnace, and carry out staged calcination and reduction with hydrogen gas flow rate of 0.3m 3 /h, and the temperature of the first stage is 650°C. After heat preservation for 240 minutes, ammonium metatungstate becomes metallic tungsten through thermal decomposition and hydrogen reduction; the temperature of the second stage is 1100°C, and heat preservation for 240 minutes, aluminum sulfate is thermally decomposed into alumina, which is coated on the surface of tungsten powder to obtain nano Alumina-coated tungsten powder composite powder, the alumina particle size is 31nm, and the tungsten powder particle size is 1.08μm.
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| TWI416056B (en) * | 2012-12-14 | 2013-11-21 | ||
| CN105397102A (en) * | 2015-12-30 | 2016-03-16 | 河南科技大学 | Preparation method aluminum oxide coating tungsten powder |
| CN107008917A (en) * | 2017-04-17 | 2017-08-04 | 河南科技大学 | A kind of nanometer Al2O3/WO3Composite granule and preparation method thereof, Al2O3/ W alloy powder |
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| JP3977226B2 (en) * | 2002-10-25 | 2007-09-19 | 大日本インキ化学工業株式会社 | Method of surface treatment of metal powder for forming sintered body and metal powder for forming sintered body |
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| TWI416056B (en) * | 2012-12-14 | 2013-11-21 | ||
| CN105397102A (en) * | 2015-12-30 | 2016-03-16 | 河南科技大学 | Preparation method aluminum oxide coating tungsten powder |
| CN107008917A (en) * | 2017-04-17 | 2017-08-04 | 河南科技大学 | A kind of nanometer Al2O3/WO3Composite granule and preparation method thereof, Al2O3/ W alloy powder |
| CN108723382A (en) * | 2018-06-25 | 2018-11-02 | 天津大学 | A kind of freeze drying process of preparing same of ultrafine yttria doping tungsten composite powder |
| CN116021020A (en) * | 2022-12-16 | 2023-04-28 | 辽宁省轻工科学研究院有限公司 | Thermal spraying sealing powder and preparation method thereof |
| CN116021020B (en) * | 2022-12-16 | 2024-09-06 | 辽宁省轻工科学研究院有限公司 | Thermal spraying sealing powder and preparation method thereof |
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