纳米W粉阶段碳化制备纳米WC粉的工艺及机制研究

以平均粒径40 nm的W粉为原料,采用"预碳化+二段碳化"的阶段碳化工艺制备出平均粒径为82 nm的近球形WC粉。利用X射线衍射(XRD)、场发射扫描电镜(FE-SEM)、BET比表面积分析仪等测试方法,分别对碳化产物的物相组成、形貌和粒径大小进行表征。研究了不同预碳化温度和二段碳化温度对WC粉粒径和形貌的影响,并对阶段碳化的机制进行了讨论。结果表明,在800~1000℃范围内,WC粉的平均粒径随预碳化温度升高呈先减小后增大的变化趋势,在900℃达到最小值。WC粉的平均粒径随二段碳化温度升高而增大,当二段碳化温度高于1250℃时,WC粉的平均粒径显著增大。碳化过程中WC颗粒的长大主要是由碳化初期纳米W颗粒的烧结合并引起的。低温预碳化能够在W粉颗粒表面形成一定厚度的WC层,阻碍W粉颗粒发生烧结合并,从而有效抑制WC粉的长大。阶段碳化制备纳米WC粉的最佳工艺为:预碳化温度900℃,二段碳化温度1150~1200℃。     

纳米钨粉的微波碳化

超细晶硬质合金具有优异的性能,而纳米级碳化钨是其制备的直接原料.采用酚醛树脂作为供碳源,研究了微波加热对纳米钨粉碳化过程的作用.研究发现,在微波碳化时只依靠钨粉自身发热不能完成碳化过程,而采用加入微波吸收物质的混合加热方式能提供足够的热量得到完全的碳化钨相;微波碳化时间很短,能有效防止碳化钨的过分长大.平均粒度50 nm的钨粉经过微波加热碳化得到平均粒度为84 nm的碳化钨粉末.     

H2O2氧化水热晶化法制备超细钨粉

通过H2O2氧化工业级钨粉颗粒制备出纳米级WO3粉体,采用两段还原法对所得的产物进行氢还原后得到超细钨粉。用XRD、SEM、BET等对所得产物进行了一系列的表征。结果表明:工业级钨粉经氧化水热晶化处理后所得产物为单斜相WO3,平均粒径约为60 nm;将制得的WO3在氢气氛下还原,800℃下保温45 min后得到颗粒分布较窄、平均粒径约150 nm的立方相钨粉。当还原温度升高至900℃时,所得的钨粉颗粒明显长大,部分粒径长大至2~3μm,但颗粒的球形度更好。     

纳米钨粉形貌结构对碳化钨粉末性能的影响

采用球磨破碎分级的氧化钨为原料,氢还原制备出平均粒度为30 nm的纳米钨粉,并分别以干磨搅拌和添加适量分散剂的湿式球磨的方式配碳,然后置于通氢钼丝碳化炉中在1180℃长时间碳化,得到了粒度分别为109和148 nm的碳化钨粉末,继而于低压真空烧结炉中,在1360℃的温度下烧结制备出WC-7%Co(质量分数)烧结体,研究了纳米钨粉形貌结构对纳米碳化钨粉末及其超细晶硬质合金性能的影响。通过比表面测定仪和费氏粒度仪测定了粉体的比表面和粒度,采用X射线衍射(XRD)分析了碳化产物的相成分,用扫描电镜(SEM)观察了粉末的形貌和烧结体的显微组织结构,按硬质合金性能测试标准对WC-Co烧结体的物理和力学性能进行了测定。结果表明,湿磨配碳强制破坏了纳米钨颗粒,呈其氧化钨前驱体的团聚状的形貌结构,可以改善纳米钨粉和碳粉弥散分布的均匀性,更有利于获得颗粒细小、均匀,分散性好的优质纳米碳化钨粉,其所制备的超细晶WC-7%Co硬质合金,显微组织均匀,综合性能优,硬度和抗弯强度分别为HRA 93.7和4450 MPa。     

喷雾转化法纳米WC/6Co复合粉形貌研究

纳米碳化钨钴复合粉体具有重要的工程应用和市场发展潜力。针对纳米碳化钨钴复合粉形貌难以精确控制这一问题,本文以偏钨酸铵(AMT)、可溶性钴盐、有机碳源为原材料,以蒸馏水为溶剂,不添加WC晶粒长大抑制剂,制备钨钴碳混合溶液,再采用喷雾转化(SCP)和连续低温还原碳化法制备了纳米碳化钨钴复合粉;研究了喷雾转化过程中溶液浓度、进料速度、离心转速和转化温度4个关键因素对纳米碳化钨钴复合粉松装密度、WC晶粒度及微观形貌的影响。研究表明:通过喷雾转化法制备的纳米碳化钨钴复合粉呈空壳球形结构,Co相发生熔化使大多WC被粘结在一起,WC颗粒之间存在明显的烧结颈,颗粒表面存在大量孔隙,部分颗粒存在破裂现象;WC平均晶粒度小于200 nm;离心转速是影响粉末松装密度、WC晶粒度及颗粒形貌的最主要因素;离心转速越大,复合粉末颗粒越小,松装密度越大;同时转化温度越高,WC晶粒度越小,复合粉末颗粒越易破裂。     

高温中颗粒WC粉及其WC-6Co合金的组织和性能

采用高温氢还原工艺制备中颗粒钨粉,经添加适量炭黑球磨混合后,分别置于管式石墨通氢碳化炉中于1950和1680℃长时间碳化获得高温中颗粒WC粉和普通中颗粒WC粉末,继而在H2保护气氛下于1470℃的温度下烧结制备出WC-6%Co(质量分数)烧结体。通过费氏粒度仪和马尔文粒度分布仪分别测定了WC粉体的平均粒度和粒度分布,采用X射线衍射(XRD)分析了碳化产物的相成分。用扫描电镜(SEM)观察了粉末的形貌和烧结体的显微组织结构,按硬质合金性能测试标准对WC-6%Co烧结体的物理和力学性能进行了测定;研究了高温WC粉对低钴硬质合金性能的影响,并与普通工艺生产的YG6合金的性能进行了对比分析。结果表明,高温氢还原工艺制备的中颗粒钨粉粒度均匀,经高温碳化后所获WC粉粒度粗化,颗粒尺寸均匀,且颗粒表面光滑、发育完整、亚晶粗大、晶格缺陷少、碳化完全、纯度较高。高温WC粉制备的WC-6%Co合金的显微组织均匀,且WC硬质相晶形完整,平均晶粒度2.0～2.5μm,硬度和抗弯强度分别为HRA90.0和3000 MPa,综合性能优于YG6牌号合金性能,因而在地矿工具、切削刀具,冲压模具等领域有较高的应用价值。     

兰钨球磨对纳米钨粉团聚的影响

采用超声喷雾干燥制备的前驱体为原料,经过两阶段低温还原和球磨工艺的结合使用制备了纳米钨粉.通过还原前后粉末形貌的对比,分析了钨粉还原过程中的形貌特征.采用第一段低温还原后得到的兰钨为原料,对比了在不同阶段球磨对还原后钨粉团聚状态的影响.对所制备的纳米钨粉进行了SAXS粒度表征.结果表明:钨粉的形貌和结构具有"遗传性";兰钨阶段的球磨有效地打碎了颗粒之间的团聚,有利于颗粒之间的分散;钨粉的球磨不能打碎纳米颗粒之间的硬团聚.SAXS检测结果表明,使用两阶段还原和球磨相结合的工艺制备的纳米钨粉平均粒径为35nm.     

喷雾干燥-直接碳化法制备WC-Co复合粉末

在高性能WC-Co的制备中,WC与Co均匀混合和C含量的严格控制具有重要意义。以偏钨酸铵、乙酸钴、重铬酸铵和炭黑为原料,通过喷雾干燥和直接还原碳化法制备WC-Co复合粉末,然后在钼丝炉中通入氢气对前驱体进行还原碳化制备WC-Co复合粉末。对制备好的WC-Co进行总碳含量测定,用X射线衍射进行相分析。研究了喷雾法制备WC复合粉末形貌粒度及碳化温度、碳化时间、配碳量对WC-Co粉末总碳量的影响。结果表明:WC复合粉末为球形粉末,平均颗粒度为50μm;当碳化温度在950℃、碳化时间为3.5h、配碳量为9%时,所得WC-Co复合粉末中WC与Co达到均匀的分布,且其实际总碳含量达到理论总碳量5.79%。     

共沉淀-直接碳化原位合成WC-Co复合粉的研究

以偏钨酸铵、硝酸钴、氨水、炭黑为原材料,采用共沉淀-直接碳化原位合成法制备了WC-Co复合粉。研究了前驱体的制备过程,考察了还原碳化工艺参数对所得产物物相的影响。利用SEM、XRD分析方法对粉末样品的微观形貌和物相组成进行了表征,并对还原碳化过程进行了探讨。结果表明:采用共沉淀法制备的前驱体粉末为许多小颗粒团聚而成的大颗粒,小颗粒均匀细小,粒径在500 nm左右,前驱体粉末经1 000℃还原碳化可以得到物相纯净的WC-Co复合粉,WC-Co复合粉分散性好,粒度分布均匀。     

碳化钒对超细WC粒度和物相的影响

为了研究在超细WC粉的制备过程中,碳化钒(VC)添加对超细碳化钨(WC)粉末粒度和相形成的影响,对不同VC添加量和不同碳化温度下制备的超细WC粉末的粒度、相成分和微观形貌进行了分析。研究结果表明:在1 400℃碳化时,当碳化钒的添加量由0%增加到10%时,WC的BET粒度由0.274μm降到0.159μm,WC粉末单颗粒粒度在逐渐减小,WC粉末颗粒的聚集程度增加。随着碳化钒的添加量的增加,碳化钒相衍射峰强度增大,WC的衍射强度降低。此外,碳化温度提高到1 600℃时,WC粉末的BET粒度增大,VC晶粒结晶更完整。     

China's Major Non-ferrous Metals Imports & Exports

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Zinc Production by Province in 2014

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80% of Chinese Firms Purchasing Overseas Mines Ended up in the Red

<正>Minmetals Resources acquired the world’s largest copper mine under construction for USD5.85 billion.One after another,listed companies Jien Nickle,China Molybdenum and Chihong Zinc and Germanium raised money to get involved in overseas mining projects…SOEs and private enterprises are engaged in a frenzy of overseas mine purchasing.A reporter with Economic     

Copper Processing Profit Dropped Sharply,Copper Consumption Will Face Impact in the Second Half of the Year

正Judging from China’s copper consumption field,the biggest consumption unit is electric power,which accounts for 47%of total consumption;it is followed by light industry sector,including household electrical appliance,machinery,durable goods and hardware etc,which accounts for 22%of total consumption;followed by transportation field,     

Central Geological Prospecting Fund Newly Added 16.47 Million Tonnes of Bauxite in 2013

正In 2013,the Central Geological Prospecting Fund(CGPF)Project newly discovered 15 ore fields,including 3 large above ore fields,and 5medium sized ore fields.The reporter learned from the recently published"Annual Report of Central Geological Prospecting Fund Project(2013)"that,from 2006 to 2013 the CGPF     

Manufacturers of Copper Tube for Central Air Conditioner Use Face Mounting Pressure in the Final Quarter of the Year

正This year,the investment growth rate of real estate industry continued to slow down,sold area of commercial housing also dropped significantly,which brought huge pressure to the domestic air conditioning manufactures.In the first half of the year,by relying on high growth in national financial expenditure,along with investment in public infrastructure     

Xinjiang Ranks No.1 in Production of Primary Aluminum in China

正Kang Yi,Honorary Chairman of China Nonferrous Metals Industry Association,said recently at the Forum on Development of the Non-ferrous Metals Industry in Central and Western China held in Zhengzhou that,as more and more electrolytic aluminum factories in Xinjiang came into operation,the electrolytic aluminum output of Xinjiang had reached2,275,000 tons in the first 7 months this year,     

Shenhuo Coal Industry and Electricity Power Completed800,000 t/a Aluminum Project in Xinjiang

正"Xinjiang project has been completed according to schedule,but total completion and total start of production are two different concepts,after completion it still needs a gradual process of reaching production target."On the morning of November 3,Shenhuo Coal Industry and Electricity Power told investors the above statement on the investor interaction platform.     

Guangdong Metal Transaction Center has Become the Second Largest Precious Metal Transaction Platform Nationwide

正The reporter learned from Guangdong Province Precious Metal Transaction Center that in 2013the Center maintained healthy development momentum,and had become the second largest precious metal transaction platform in China in terms of market size;currently Guangdong is quickening steps of financial innovation for the Center,aiming to build a transaction center with international core competitiveness.     

Seven Rare Earth Projects Involving Close to 3 Billion Yuan Investment Landed In the HighTech Zone

正On May 22,Baotou Rare Earth Industry Cooperation Consultation MeetingProject Agreement-signing Ceremony was held in Ningbo,nearly 40 enterprises from Ningbo,Guangdong,Hunan,and Shanxi participated in project consultation.After multi-lateral communication,agreements were signed for a total of 7 rare earth projects successfully.