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Preparation method for polyhedral submicron tungsten powder

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CN105798317A
CN105798317A CN 201610197358 CN201610197358A CN105798317A CN 105798317 A CN105798317 A CN 105798317A CN 201610197358 CN201610197358 CN 201610197358 CN 201610197358 A CN201610197358 A CN 201610197358A CN 105798317 A CN105798317 A CN 105798317A
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tungsten
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polyhedral
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CN105798317B (en )
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何爱山
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宇辰新能源材料科技无锡有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F1/00Special treatment of metallic powder, e.g. to facilitate working, to improve properties; Metallic powders per se, e.g. mixtures of particles of different composition
    • B22F1/0003Metallic powders per se; Mixtures of metallic powders; Metallic powders mixed with a lubricating or binding agent
    • B22F1/0007Metallic powder characterised by its shape or structure, e.g. fibre structure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds

Abstract

The invention belongs to the technical field of powder preparation, and particularly relates to a preparation method for polyhedral submicron tungsten powder. The preparation method includes the following steps that (1) soluble tungsten salt and a surface active agent are dissolved into water and stirred evenly, the pH is adjusted with acid to reach 2-4, then a solution A is obtained, and a reducing agent is dissolved in water to obtain a solution B; (2) after the solution A is heated to 50-90 DEG C, the solution B is poured in, a mixed solution with A and B is obtained, the volume ratio of the solution A to the solution B is 3:1-1:3, reaction is carried out for 1-6 h at the temperature kept at 50-90 DEG C, then the mixed solution is cooled to 10-30 DEG C, a tungsten oxide precursor filter cake is obtained after reaction products are subjected to solid-liquid separation, and impurities in the tungsten oxide precursor filter cake are removed through washing with water; tungsten oxide precursor powder is obtained after water in the washed filter cake is removed; and (3) the tungsten oxide precursor powder is subjected to heat treatment at a reducing atmosphere, and then the polyhedral submicron tungsten powder is obtained. The production process is simple, short, easy to control, small in equipment investment, and low in production cost. Prepared product particles are polyhedral, particle diameter distribution is narrow, and the degree of crystallinity is high.

Description

一种多面体亚微米钨粉的制备方法 Method for preparing submicron tungsten powder polyhedral

技术领域 FIELD

[0001]本发明属于粉末制备技术领域,尤其涉及一种多面体亚微米钨粉的制备方法。 [0001] The present invention belongs to the technical field powders prepared, in particular, it relates to a method for preparing submicron tungsten powder polyhedron.

背景技术 Background technique

[0002]钨是一种宝贵的稀有金属,广泛用作硬质合金、特种钢和各种钨制品。 [0002] Tungsten is a valuable rare, widely used as carbide, steel and various special tungsten products. 钨合金中最主要的原料是钨粉,其粒度的大小对合金的性能起关键性的作用。 Tungsten the most important starting material is tungsten powder, its particle size on the performance of the alloy play a crucial role. 含细颗粒的合金比含粗颗粒的合金性能明显的提尚,若合金含超细晶粒,则性能可广生质的飞跃,达到尚强度与尚硬度的统一,从而扩展其应用领域。 Alloy containing fine particles is significantly higher than the properties of alloys containing coarse particles still mention, if an alloy containing superfine grains, the performance can be qualitative leap Kwong Sang, yet achieve the strength and hardness unified yet, to extend its field of application. 同时,金属钨在这些领域中的应用还与其形貌、粒度的分布有着密切的关系。 Meanwhile, application of tungsten in these areas also its morphology, the particle size distribution is closely related.

[0003]目前超细和亚微米钨粉的制备方法主要有:(I)氧化钨还原法,该法是工业上常用方法,但缺点是产量低、成本高、周期长、工艺控制复杂;(2)高能球磨法,该方法具有成本低、产量高和工艺简单等优点,在一些对粉体的纯度和粒度要求不太高的场合应用很广,但将ΙΟμπι的物料粉磨至微米级甚至亚微米级超细粉体,球磨时间非常长,球耗、能耗等成本相应增加;(3)喷雾干燥法,即热化学合成法,该法制备的超细钨粉颗粒呈球壳状,比表面积较大,孔隙率高,有利于还原过程中氢气进入和水蒸气的排出,从而降低还原温度和缩短还原时间,易于制备超细钨粉,但是生产效率低,设备复杂,技术要求高,成本昂贵;(4)冷冻干燥法,具有生产效率低、设备复杂、成本昂贵等缺点,难以实现大规模生产;(5)溶胶凝胶法,可在低温下制备纯度高、粒径分 [0003] It was prepared and ultrafine submicron tungsten powder mainly: (I) tungsten oxide reduction method, which method is industrially common method, but the disadvantage is the low yield, high cost, long cycle, complicated process control; ( 2) high energy ball milling method, this method has a low cost, high throughput and simple process, etc., is widely in some of the purity and particle size of the powder less demanding occasions, but the grinding material to ΙΟμπι micron and even sub-micron ultra-fine powder, the milling time is very long, the ball consumption, the cost of a corresponding increase in energy consumption; (3) spray-drying method, i.e. a thermal chemical synthesis, the preparation of ultrafine fullerene particles are tungsten powder, large specific surface area, high porosity, facilitate reduction during discharge of hydrogen and water vapor to enter, thereby lowering the reduction temperature and reduction time shortened, easy to prepare ultra-fine tungsten powder, but the production efficiency is low, complicated equipment, high technical requirements, expensive; (4) freeze-drying process, low production efficiency, complicated equipment, costly and other shortcomings, it is difficult to achieve large-scale production; (5) a sol-gel method, can be prepared in high purity at a low temperature, the particle size fraction 均匀、化学活性高的超细粒子,但因其容易引入其他杂质元素,影响最终产品的性能而未得到广泛的应用;(6)熔盐电解法,这种方法制备的钨粉形状为非球形,制备的粉末团聚严重,且生产成本较高;(7)自蔓延高温合成法,又称燃烧合成,该方法原料便宜,来源广,生产工艺具有高效、节能等优点而引起世界各国的普遍重视,但在实际应用中还存在许多工艺技术等方面的难题,如燃烧速度和反应过程难以控制。 Uniform, high chemical activity of ultrafine particles, but because of its easy introduction of other impurity elements, influence the performance of the final product but have not been widely used; Preparation of (6) by molten salt electrolysis, this method is non-spherical shape of the tungsten powder , severely agglomerated powder produced, and the production cost is high; (7) SHS method, also known as combustion synthesis, the cheaper feedstock wide source, the production process with high efficiency, energy saving and caught the attention of the world , but in practice there are still many challenges and other aspects of the technology, such as combustion reaction and is difficult to control the speed.

[0004]上述方法制备的亚微米钨粉大多数呈类球型和不规则形状,且粒度分布大,颗粒均匀性和分散性不好。 [0004] submicron tungsten powder prepared as described above was most classes spherical and irregular shapes, and a large particle size distribution, particle uniformity and poor dispersion.

[0005]有鉴于上述的缺陷,本设计人,积极加以研究创新,以期创设一种多面体亚微米钨粉的制备方法,使其更具有产业上的利用价值。 [0005] In view of the above drawbacks, the present design people actively pursued research and innovation, to create a method of preparing one kind of polyhedron submicron tungsten powder to make it more industrial utility value.

发明内容 SUMMARY

[0006]为解决上述技术问题,本发明的目的是提供一种多面体亚微米钨粉的制备方法,其生产工艺简短易控,设备投资少,生产成本低,易于实现工业化生产的方法,且制备的产品粒子呈多面体形状,粒径分布窄、抗氧化性强、结晶度高。 [0006] In order to solve the above problems, an object of the present invention is to provide a polyhedron submicron tungsten powder preparation, short and easy to control its production process, less investment in equipment, low production cost, industrial production method is easy to implement, and may be prepared product particles were polyhedral shape, a narrow particle size distribution, strong antioxidant activity, high crystallinity.

[0007]本发明提出了一种多面体亚微米钨粉的制备方法,包括以下步骤: [0007] The present invention provides a method for preparing submicron tungsten powder polyhedron, comprising the steps of:

[0008] (I)将可溶性钨盐和表面活性剂溶于水中搅拌均匀,其中钨盐的浓度为0.1〜 [0008] (I) soluble tungsten salt and a surfactant are dissolved in water Stir, wherein the concentration of the tungsten salt is 0.1~

2.0moI/L,表面活性剂的浓度为1.0〜60.0g/L,用酸调节pH至2〜4得到A液;将还原剂溶于水得到B液,其中还原剂的浓度为0.4〜8.0mo I/L ; 2.0moI / L, the concentration of surfactant is 1.0~60.0g / L, pH was adjusted to ~ 4 with an acid to give solution A; the reducing agent is dissolved in water to give solution B, wherein the concentration of reducing agent is 0.4~8.0mo I / L;

[0009] (2)将A液加热至50〜90 °C后,倒入B液,得到A与B混合溶液,其中A液与B液的体积比为3:1〜1:3,保持温度在50〜90 0C反应I〜6h,然后冷却至1〜30 °C,反应产物经固液分离得到氧化钨前驱体滤饼,经水洗去除滤饼中的杂质;洗涤后的滤饼在100〜200 °C干燥I〜24小时除去水分得到氧化钨前驱体粉体; After [0009] (2) A was heated to 50~90 ° C, poured into solution B, A and B to give a mixed solution, wherein the volume ratio of A liquid and B liquid is 3: 1~1: 3, keeping the temperature in reaction I~6h 50~90 0C, and then cooled to 1~30 ° C, the reaction product by solid-liquid separation to obtain a tungsten oxide precursor cake, washing the filter cake by impurities removed; cake was washed 100~ drying 200 ° C I~24 hours to remove water to obtain a precursor of tungsten oxide powders;

[0010] (3)将氧化钨前驱体粉体在还原气氛下进行热处理,即得多面体亚微米钨粉。 [0010] (3) A tungsten oxide precursor powder was heat-treated in a reducing atmosphere, i.e., submicron tungsten powder to obtain a polyhedron.

[0011 ]进一步的,所述步骤(I)中,A液中钨盐的浓度为0.5〜1.5mol/L,表面活性剂的浓度为10.0〜40g/L,pH为2.5-3.5;B液中还原剂的浓度为I.0〜6.0mol/L;所述步骤(2)中A液与B液的体积比为2:1〜1:2。 [0011] Further, the step (I), the concentration of tungsten salt A solution of 0.5~1.5mol / L, the concentration of surfactant is 10.0~40g / L, pH of 2.5-3.5; B liquid the concentration of reducing agent is I.0~6.0mol / L; the volume ratio of the step (2) a liquid and B liquid was 2: 1~1: 2.

[0012]进一步的,所述步骤(I)中的可溶性钨盐包括钨酸钠、钨酸钾或偏钨酸铵中的一种或多种。 [0012] Further soluble tungsten salt, said step (I) comprises one or more of sodium tungstate, potassium tungstate or ammonium metatungstate in.

[0013]进一步的,所述步骤(I)中的表面活性剂包括聚乙烯吡咯烷酮、聚丙烯酸、油酸、聚乙二醇、聚乙烯醇中的一种或多种。 [0013] Further, the step (I) of the surfactants include polyvinyl pyrrolidone, polyacrylic acid, oleic acid, polyethylene glycol, polyvinyl alcohol is one or more.

[0014]进一步的,所述步骤(I)中的酸包括硫酸、盐酸或硝酸中的一种或多种。 [0014] Further, in the acid step (I) comprises one or more of sulfuric acid, hydrochloric acid or nitric acid.

[0015]进一步的,所述步骤(I)中的还原剂包括硼氢化钠与水合肼或乙二胺的混合物、硼氢化钾与水合肼或乙二胺的混合物中的一种。 [0015] Further, the step (I) is a mixture of reducing agents include sodium borohydride or hydrazine hydrate and ethylenediamine, potassium borohydride or hydrazine hydrate and ethylenediamine in.

[0016]进一步的,所述步骤(3)中还原气氛包括氢气、氢气与惰性气体的混合气体中的一种。 Restore [0016] Further, the step (3) comprises one atmosphere of hydrogen gas, a mixed gas of hydrogen and inert gas in.

[0017] 进一步的,所述步骤(3)热处理温度为500〜900°C,还原时间为I〜6小时,还原气体的流量为30〜300mL/min。 [0017] Further, the step (3) heat treatment temperature is 500~900 ° C, I~6 hours reduction time, flow rate of reducing gas is 30~300mL / min.

[0018]进一步的,所述步骤(2)中冷却的方法为向反应液中加水。 [0018] Further, the step (2) A method for cooling water was added to the reaction mixture.

[0019]进一步的,所述步骤(2)中产物的固液分离的方式包括真空过滤或离心中的一种。 Solid-liquid separation manner [0019] Further, the step (2) product comprises a centrifugal or vacuum filtration of.

[0020]借由上述方案,本发明至少具有以下优点:本发明提出的多面体亚微米钨粉的制备方法,其生产工艺简短易控,设备投资少,生产成本低,易于实现工业化生产的方法,且制备的产品粒子呈多面体形状,粒径分布窄、抗氧化性强、结晶度高。 [0020] by means of the above-described embodiment, the present invention has at least the following advantages: Preparation polyhedron submicron tungsten powder proposed by the present invention, its production process short and easy to control, less investment in equipment, low production cost and easy industrial production method, and products prepared particles were polyhedral shape, a narrow particle size distribution, oxidation resistance, high crystallinity.

[0021]上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,并可依照说明书的内容予以实施,以下以本发明的较佳实施例并配合附图详细说明如后。 [0021] The above description is only an overview of the technical solution of the present invention, in order to more fully understood from the present disclosure, may be implemented in accordance with the contents of the specification, the following preferred embodiments of the present invention to the detailed description and the accompanying drawings as Rear.

附图说明 BRIEF DESCRIPTION

[0022]图1是本发明实施例1制备的钨粉的SEM图; [0022] FIG. 1 is a SEM image of the tungsten powder prepared according to Example 1 of the present invention;

[0023]图2为本发明实施例4制备的钨粉的SEM图。 [0023] FIG. FIG. 2 SEM tungsten powder prepared in Example 4 of the present embodiment of the invention.

具体实施方式 detailed description

[0024]下面结合附图和实施例,对本发明的具体实施方式作进一步详细描述。 [0024] The following embodiments and the accompanying drawings, specific embodiments of the present invention will be further described in detail. 以下实施例用于说明本发明,但不用来限制本发明的范围。 The following examples serve to illustrate the present invention but are not intended to limit the scope of the present invention.

[0025] 实施例1 [0025] Example 1

[0026] 一种多面体亚微米钨粉的制备方法,包括以下步骤: [0026] A method for preparing a polyhedral submicron tungsten powder, comprising the steps of:

[0027] (I)将0.15mol钨酸钠和3.0g聚乙烯吡咯烷酮(PVP)溶于水中均匀混合并用稀盐酸调节为pH为3.0得到3OOmL A液;将0.25mo I水合肼和0.0 5mo I硼氢化钠混溶于水中得到3 O OmL B液; [0027] (I) and the sodium tungstate 3.0g 0.15mol polyvinyl pyrrolidone (PVP) dissolved in water were uniformly mixed and adjusted with dilute hydrochloric acid to a pH of 3.0 was obtained 3OOmL A; the 0.25mo I hydrazine hydrate and 0.0 5mo I B sodium hydride miscible in water to give liquid 3 O OmL B;

[0028] (2)A液加热至900C,把B液倾倒入A液,反应体系温度维持在90°C反应Ih,然后加入冷水冷却至室温(10〜30°C);将反应产物经离心分离,滤饼经水洗去除滤饼中的杂质,将废水集中处理;洗涤后的滤饼在150°C干燥10小时除去水分得到氧化钨前驱体粉体; [0028] (2) A was heated to 900C, the solution B was poured into solution A, the reaction system temperature was maintained at 90 ° C the reaction Ih is, then added to cold water cooled to room temperature (10~30 ° C); the reaction product by centrifugation separation, the filter cake is removed by washing the filter cake impurities, wastewater treatment concentrate; washed filter cake was dried at 150 ° C 10 hours to remove water to obtain a precursor of tungsten oxide powders;

[0029] (3)将得到的氧化钨前驱体粉体直接置于管式炉,然后通氢气进行还原,控制氢气的流量为30mL/min,热处理温度为500°C,时间为6小时,即得多面体亚微米钨粉。 [0029] (3) The tungsten oxide precursor powder obtained directly placed in a tubular furnace, then through hydrogen reduction, controlling the flow rate of hydrogen is 30mL / min, a heat treatment temperature of 500 ° C, time was 6 hours, i.e., submicron tungsten powder to obtain a polyhedron.

[0030]图1为本实施例中制备的钨粉的扫描电镜图,从图中可以看到,该钨粉的粒径为400nmo [0030] Figure 1 scanning electron micrograph of tungsten powder prepared in the present embodiment, can be seen from the figure, the tungsten powder particle size is 400nmo

[0031] 实施例2 [0031] Example 2

[0032] 一种多面体亚微米钨粉的制备方法,包括以下步骤: [0032] A method for preparing a polyhedral submicron tungsten powder, comprising the steps of:

[0033] (I)将0.25mol钨酸钾和5.0g聚乙烯醇(PVA)溶于水中均匀混合并用稀硫酸调节为pH为2.5得到250mL A液;将1.0mol乙二胺和0.1mol硼氢化钾混溶于水中得到350mL B液; [0033] (I) and the potassium tungstate 5.0g 0.25mol polyvinylalcohol (PVA) were uniformly mixed and dissolved in water with dilute sulfuric acid to adjust the pH to 2.5 to obtain 250mL A solution; ethylenediamine to 1.0mol and 0.1mol borohydride potassium miscible in water to give 350 mL of solution B;

[0034] (2)A液加热至60°C,把B液倾倒入A液,反应体系温度维持在60°C反应3h,然后加入冷水冷却至室温(10〜30°C);将反应产物经真空过滤,滤饼经水洗去除滤饼中的杂质,将废水集中处理;洗涤后的滤饼在100°C干燥24小时除去水分得到氧化钨前驱体粉体; [0034] (2) A was heated to 60 ° C, the solution B was poured into solution A, the reaction temperature in the system was maintained at 60 ° C the reaction 3h, cooled to room temperature and then added to cold water (10~30 ° C); the reaction product of by vacuum filtration, the filter cake was removed by washing the filter cake impurities, wastewater treatment concentrate; washed filter cake was dried for 24 hours to remove water to obtain a tungsten oxide precursor powders at 100 ° C;

[0035] (3)将得到的氧化钨前驱体粉体直接置于管式炉,然后通还原气体进行还原,还原气体中H2与N2体积比为3:1,控制气体流量为60mL/min,热处理温度为700°C,时间为5小时,即得多面体亚微米钨粉。 Tungsten oxide precursor powder [0035] (3) obtained directly on the tube furnace, and a reducing gas through the reduction, the reducing gas volume ratio of H2 to N2 is 3: 1, to control the gas flow 60mL / min, The heat treatment temperature of 700 ° C, for 5 hours to obtain the polyhedron submicron tungsten powder.

[0036] 实施例3 [0036] Example 3

[0037] 一种多面体亚微米钨粉的制备方法,包括以下步骤: [0037] A method for preparing a polyhedral submicron tungsten powder, comprising the steps of:

[0038] (I)将0.3mol钨酸钠和8.0g聚乙二醇(PEG)溶于水中均匀混合并用稀硝酸调节为pH为2.5得到200mL A液;将0.80mol水合肼和0.06mol硼氢化钠混溶于水中得到400mL B液; [0038] (I) and 8.0g of sodium tungstate to 0.3mol polyethylene glycol (PEG) were uniformly mixed and dissolved in water adjusted with dilute nitric acid to a pH of 2.5 was obtained 200mL A; 0.80mol hydrazine hydrate and the borohydride 0.06mol sodium miscible in water to give a solution 400mL B;

[0039] (2)A液加热至700C,把B液倾倒入A液,反应体系温度维持在70°C反应2h,然后加入冷水冷却至室温(10〜30°C);将反应产物经真空过滤,滤饼经水洗去除滤饼中的杂质,将废水集中处理;洗涤后的滤饼在120°C干燥15小时除去水分得到氧化钨前驱体粉体; [0039] (2) A was heated to 700C, the solution B was poured into solution A, the reaction system temperature was maintained at 70 ° C the reaction 2h, cooled to room temperature and then added to cold water (10~30 ° C); and the reaction product was vacuum the filter cake is removed by washing the filter cake impurities, wastewater treatment concentrate; washed filter cake was dried at 120 ° C 15 hours to remove water to obtain a precursor of tungsten oxide powders;

[0040] (3)将得到的氧化钨前驱体粉体直接置于管式炉,然后通还原气体进行还原,还原气体中H2和Ar的体积比为1:1,控制气体流量为100mL/min,热处理温度为800°C,时间为4小时,即得多面体亚微米钨粉。 Tungsten oxide precursor powder [0040] (3) obtained directly on the tube furnace, and a reducing gas through the reduction, the reducing gas of Ar and H2 volume ratio of 1: 1, the control of gas flow rate 100mL / min heat treatment temperature of 800 ° C, for 4 hours to obtain the polyhedron submicron tungsten powder.

[0041 ] 实施例4 [0041] Example 4

[0042] 一种多面体亚微米钨粉的制备方法,包括以下步骤: [0042] A method for preparing a polyhedral submicron tungsten powder, comprising the steps of:

[0043] (I)将0.3mol偏钨酸铵和6.0g聚乙烯吡咯烷酮(PVP)溶于水中均匀混合并用稀盐酸调节为pH为3.5得到400mL A液;将1.15mol乙二胺和0.05mol硼氢化钠混溶于水中得到 [0043] (I) The ammonium metatungstate and 0.3mol 6.0g polyvinylpyrrolidone (PVP) were uniformly mixed and dissolved in water with diluted hydrochloric acid to adjust the pH to 3.5 to obtain 400mL A solution; 1.15mol ethylenediamine and the boron 0.05mol of sodium hydride to obtain a water-miscible

2 O OmL B液; 2 O OmL B solution;

[0044] (2)A液加热至500C,把B液倾倒入A液,反应体系温度维持在50°C反应6h,然后加入冷水冷却至室温(10〜30°C);将反应产物经离心分离,滤饼经水洗去除滤饼中的杂质,将废水集中处理;洗涤后的滤饼在200°C干燥I小时除去水分得到氧化钨前驱体粉体; [0044] (2) A solution is heated to 500C, the solution A was poured into solution B, maintaining the temperature of the reaction system was 50 ° C and the reaction 6h, cooled to room temperature and then added to cold water (10~30 ° C); the reaction product by centrifugation separation, the filter cake is removed by washing the filter cake impurities, wastewater treatment concentrate; washed cake was dried to remove water to obtain a tungsten oxide precursor powder was dried at 200 ° C I h;

[0045] (3)将得到的氧化钨前驱体粉体直接置于管式炉,然后通氢气进行还原,控制氢气的流量为200mL/min,热处理温度为900°C,时间为I小时,即得多面体亚微米钨粉。 [0045] (3) The tungsten oxide precursor powder obtained directly placed in a tubular furnace, then through hydrogen reduction, hydrogen flow rate was controlled 200mL / min, the heat treatment temperature of 900 ° C, time of I hour, i.e., submicron tungsten powder to obtain a polyhedron.

[0046]图2是本实施中制备的钨粉的扫描电镜图,从图中可以看到,该钨粉的粒径为800nmo [0046] FIG. 2 is a scanning electron micrograph of tungsten powder was prepared according to the present embodiment in FIG can be seen from the figure, the tungsten powder particle size is 800nmo

[0047] 实施例5 [0047] Example 5

[0048] 一种多面体亚微米钨粉的制备方法,包括以下步骤: [0048] A method for preparing a polyhedral submicron tungsten powder, comprising the steps of:

[0049] (I)将0.45mol钨酸钠和10.5g聚丙烯酸(PAA)溶于水中均匀混合并用稀硝酸调节为pH值为3.0得到350mLA液;将1.0mol乙二胺和0.08mol硼氢化钾混溶于水中得到250mL B液; [0049] (I) and the sodium tungstate 10.5g 0.45mol polyacrylic acid (PAA) were uniformly mixed and dissolved in water adjusted with dilute nitric acid to a pH of 3.0 was obtained 350mLA; 1.0mol the ethylenediamine and potassium borohydride 0.08mol miscible in water to give a solution 250mL B;

[0050] (2)A液加热至80°C,把B液倾倒入A液,反应体系温度维持在80°C反应4h,然后加入冷水冷却至室温(10〜30°C);将反应产物经真空过滤,滤饼经水洗去除滤饼中的杂质,将废水集中处理;洗涤后的滤饼在180°C干燥4小时除去水分得到氧化钨前驱体粉体; [0050] (2) A was heated to 80 ° C, the solution B was poured into solution A, the reaction temperature of the system was maintained at 80 ° C the reaction 4h, cooled to room temperature and then added to cold water (10~30 ° C); the reaction product of by vacuum filtration, the filter cake was removed by washing the filter cake impurities, wastewater treatment concentrate; cake was washed with water to remove the tungsten oxide precursor powder obtained was dried at 180 ° C 4 hours;

[0051] (3)将得到的氧化钨前驱体粉体直接置于管式炉,然后通还原气体进行还原,还原气体中H2和N2的体积比为1:1,控制气体流量为300mL/min,热处理温度为600°C,时间为3小时,即得多面体亚微米钨粉。 Tungsten oxide precursor powder [0051] (3) placed directly obtained tube furnace, a reducing gas and then through the reduction, the reducing gas of N2 and H2 volume ratio of 1: 1, the control of gas flow rate 300mL / min heat treatment temperature of 600 ° C, for 3 hours, to obtain submicron tungsten powder polyhedron.

[0052]综上所述,本发明提出的多面体亚微米钨粉的制备方法,具有以下优点: [0052] In summary, the method for preparing submicron tungsten powder polyhedral proposed by the present invention has the following advantages:

[0053] (I)克服了现有技术的缺点,通过化学还原法制备氧化钨前驱体,然后直接还原气氛热处理氧化钨前驱体制得多面体亚微米钨粉,其生产工艺简短易控,设备投资少,生产成本低,易于实现工业化生产;通过调节钨盐的pH来实现钨粉形貌的可控生产;还采用倾倒法,该方法操作简便,采用倾倒法进行氧化还原反应,会使每个氧化钨前驱体颗粒成核与生长的时间保持一致,适合大规模工业生产; [0053] (I) overcomes the disadvantages of the prior art, by Chemical Reduction Method tungsten oxide precursor, and then directly reducing atmosphere heat treatment have a polyhedral tungsten oxide precursors submicron tungsten powder, which is easy to control the production process short, less investment in equipment , low production cost and easy industrial production; the production of tungsten powder to achieve a controlled morphology by adjusting the pH of the tungsten salt; pouring method also uses, this method is simple to operate, using the pouring method redox reaction, causes each oxide tungsten precursor particle nucleation growth consistent with the time for large-scale industrial production;

[0054] (2)采用水合肼或乙二胺作还原剂制备氧化钨前驱体反应速度慢,还原率低,而本发明中用还原性较强的硼氢化钠或硼氢化钾来替代部分水合肼或乙二胺,既明显提高了反应速率,又减低了还原剂的用量,提高了生产效率,降低了生产成本,而且所制备的钨粉纯度高,在工业领域中有广泛的应用前景; [0054] (2) using hydrazine hydrate or ethylenediamine tungsten oxide precursor prepared as a reducing agent is slow, the reduction rate is low, while reducing the present invention using sodium borohydride or potassium borohydride to replace stronger partially hydrated hydrazine or ethylenediamine, significantly increased both the reaction rate, but also reduced the amount of reducing agent, improve production efficiency, reduce production costs, and high-purity tungsten powder prepared with a wide range of applications in the industrial field;

[0055] (3)采用化学还原法制备氧化钨前驱体,不仅原料廉价易得,而且大大降低了制备温度,降低了原料成本和能耗。 [0055] (3) prepared by chemical reduction of tungsten oxide precursor not only cheap raw materials, but also greatly reduces the preparation temperature, reducing the cost of raw materials and energy.

[0056] (4)本发明制备的亚微米钨粉具有多面体结构,粒子表面光滑,粒径可控且粒径分布窄、抗氧化性强、分散性好、平均粒度为400〜SOOnm;该钨粉可广泛应用于硬质合金、航空航天、电子工业等领域。 [0056] (4) Preparation of submicron tungsten powder of the present invention has a polyhedral structure, smooth particle surface, a narrow particle size distribution and a controllable, high oxidation resistance, good dispersion, an average particle size of 400~SOOnm; the tungsten carbide powder can be widely used in aerospace, electronics industry and other fields.

[0057]以上所述仅是本发明的优选实施方式,并不用于限制本发明,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,这些改进和变型也应视为本发明的保护范围。 [0057] The above are only preferred embodiments of the present invention is not intended to limit the present invention, it should be noted that those of ordinary skill in the art, in the art without departing from the principles of the present invention is provided, may also be made a number of improvements and modifications, such modifications and variations shall also be considered in the scope of the invention.

Claims (10)

1.一种多面体亚微米钨粉的制备方法,其特征在于:包括以下步骤: (1)将可溶性钨盐和表面活性剂溶于水中搅拌均匀,其中钨盐的浓度为0.1〜2.0mol/L,表面活性剂的浓度为1.0〜60.0g/L,用酸调节pH至2〜4得到A液;将还原剂溶于水得到B液,其中还原剂的浓度为0.4〜8.0mo I/L; (2)将A液加热至50〜90 0C后,倒入B液,得到A与B混合溶液,其中A液与B液的体积比为3:1〜1:3,保持温度在50〜90°C反应I〜6h,然后冷却至10〜30°C,反应产物经固液分离得到氧化钨前驱体滤饼,经水洗去除滤饼中的杂质;洗涤后的滤饼在100〜200°C干燥I〜24小时除去水分得到氧化钨前驱体粉体; (3)将氧化钨前驱体粉体在还原气氛下进行热处理,即得多面体亚微米钨粉。 1. A method for the preparation of polyhedral submicron tungsten powder, characterized by: comprising the steps of: (1) the soluble tungsten salt and a surfactant are dissolved in water Stir, wherein the concentration of the tungsten salt is 0.1~2.0mol / L the concentration of the surface active agent is 1.0~60.0g / L, pH was adjusted to ~ 4 with an acid to give solution a; the reducing agent is dissolved in water to give solution B, wherein the concentration of reducing agent is 0.4~8.0mo I / L; (2) a solution was heated to 50~90 0C, poured into solution B, a and B to give a mixed solution, wherein the volume ratio of a liquid and B liquid is 3: 1~1: 3, maintaining the temperature at 50~90 ° C reaction I~6h, then cooled to 10~30 ° C, the reaction product by solid-liquid separation to obtain a tungsten oxide precursor cake was removed by washing the filter cake impurities; washed cake was dried at 100~200 ° C I~24 hours to remove water and dried to obtain a tungsten oxide precursor powder; (3) the tungsten oxide precursor powder was heat-treated in a reducing atmosphere, i.e., submicron tungsten powder to obtain a polyhedron.
2.根据权利要求1所述的多面体亚微米钨粉的制备方法,其特征在于:所述步骤(I)中,A液中钨盐的浓度为0.5〜1.5mol/L,表面活性剂的浓度为10.0〜40g/L,pH为2.5-3.5;B液中还原剂的浓度为1.0〜6.0mol/L;所述步骤(2)中A液与B液的体积比为2:1〜1:2。 The production method of claim 1 polyhedron submicron tungsten powder as claimed in claim wherein: said step (I), the concentration of A solution of a tungsten salt, the concentration of the surfactant 0.5~1.5mol / L is 10.0~40g / L, pH of 2.5-3.5; B concentration of the reducing agent solution 1.0~6.0mol / L; step (2) a volume of liquid and the B liquid ratio of 2: 1~1: 2.
3.根据权利要求1所述的多面体亚微米钨粉的制备方法,其特征在于:所述步骤(I)中的可溶性钨盐包括钨酸钠、钨酸钾或偏钨酸铵中的一种或多种。 The production method of claim 1 polyhedron submicron tungsten powder as claimed in claim wherein: said step a soluble tungsten salt (I) comprises one kind of sodium tungstate, potassium tungstate or ammonium metatungstate in or more.
4.根据权利要求1所述的多面体亚微米钨粉的制备方法,其特征在于:所述步骤(I)中的表面活性剂包括聚乙烯吡咯烷酮、聚丙烯酸、油酸、聚乙二醇、聚乙烯醇中的一种或多种。 The method of preparing submicron tungsten powder polyhedron claim, wherein: said step (I) of the surfactants include polyvinyl pyrrolidone, polyacrylic acid, oleic acid, polyethylene glycol, polypropylene one or more vinyl alcohol.
5.根据权利要求1所述的多面体亚微米钨粉的制备方法,其特征在于:所述步骤(I)中的酸包括硫酸、盐酸或硝酸中的一种或多种。 The preparation of polyhedral submicron tungsten powder as claimed in claim 1, wherein: said step (I) in one or more of the acid include sulfuric acid, hydrochloric acid or nitric acid.
6.根据权利要求1所述的多面体亚微米钨粉的制备方法,其特征在于:所述步骤(I)中的还原剂包括硼氢化钠与水合肼或乙二胺的混合物、硼氢化钾与水合肼或乙二胺的混合物中的一种。 6. The method of claim 1 prepared polyhedron submicron tungsten powder as claimed in claim wherein: said step (I) is a mixture of reducing agents include sodium borohydride or hydrazine hydrate and ethylenediamine, potassium borohydride and hydrazine hydrate or a mixture of ethylene diamine in.
7.根据权利要求1所述的多面体亚微米钨粉的制备方法,其特征在于:所述步骤(3)中还原气氛包括氢气、氢气与惰性气体的混合气体中的一种。 The preparation of polyhedral submicron tungsten powder according to claim 1, wherein: said step (3) the reducing atmosphere comprises a mixture of hydrogen gas, hydrogen and inert gas in.
8.根据权利要求1所述的多面体亚微米钨粉的制备方法,其特征在于:所述步骤(3)热处理温度为500〜900°C,还原时间为I〜6小时,还原气体的流量为30〜300mL/min。 8. The method of preparing submicron tungsten powder polyhedron claim, wherein: said step (3) heat treatment temperature is 500~900 ° C, I~6 hours reduction time, flow rate of reducing gas is 30~300mL / min.
9.根据权利要求1所述的多面体亚微米钨粉的制备方法,其特征在于:所述步骤(2)中冷却的方法为向反应液中加水。 Preparation polyhedron submicron tungsten powder according to claim 1, wherein: said step (2) A method for cooling water was added to the reaction mixture.
10.根据权利要求1所述的多面体亚微米钨粉的制备方法,其特征在于:所述步骤(2)中产物的固液分离的方式包括真空过滤或离心中的一种。 Preparation polyhedron submicron tungsten powder according to claim 1, wherein: said solid-liquid step (2) separating the product comprises one embodiment of a vacuum filtration or centrifugation.
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