CN115448731B - 一种钒氮合金用石墨坩埚涂层的制备方法 - Google Patents
一种钒氮合金用石墨坩埚涂层的制备方法 Download PDFInfo
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- 239000010439 graphite Substances 0.000 title claims abstract description 98
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- 238000000576 coating method Methods 0.000 title claims abstract description 58
- 229910001199 N alloy Inorganic materials 0.000 title claims abstract description 45
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 title claims abstract description 45
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- 238000010304 firing Methods 0.000 claims abstract description 25
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 21
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical group C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical group CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 18
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种钒氮合金用石墨坩埚涂层的制备方法，该制备方法包括以下步骤：1)浆料制备：将单晶硅粉体、二氧化硅粉体以及粘结剂混合制成浆料；2)涂覆涂层：将料浆喷涂到未经烧制的石墨坩埚表面形成厚度为3～10mm的料浆层；3)干燥：在惰性气体保护下干燥涂覆涂层后的石墨坩埚；4)烧成：将干燥后的石墨坩埚高温氮气气氛进行烧制，烧制制得表面包覆氮化硅涂层的石墨坩埚。本发明的钒氮合金用石墨坩埚涂层的制备方法所用二氧化硅，与直接使用氮化硅相比价格更加低廉，且可利用钒氮合金生产过程保护气体氮气反应制备氮化硅，成本更低。
Description
技术领域
本发明属于钒冶金技术领域，尤其涉及一种钒氮合金用石墨坩埚涂层的制备方法。
背景技术
钒作为一种高熔点稀有金属，战略地位十分重要，主要用来生产微合金钢，也被广泛应用于制备航空航天钒钛合金材料、化工催化剂等领域。在材料制备方面有着广泛的应用，被称为“现代工业的味精”。钒可以增加钢的强度、塑性和韧性，是钢中重要的微合金元素。当以钒氮合金形式加入到钢中时，可以对钢起到同时增钒和增氮的效果。由于合金钢达到同样强度所需的钒氮合金含钒量远小于钒铁含钒量，因此，相对于钒铁合金，使用钒氮合金可以有效降低钒的用量，且不改变合金钢的强度，大大地降低了钢铁企业的生产成本。
坩埚是钒氮合金生产的必需装置。目前，钒氮合金生产主要是采用石墨坩埚，这是因为石墨具有来源丰富、化学性质稳定以及耐高温的特性。石墨坩埚适合工业化生产钒氮合金，但是其存在的缺陷在于重复使用时易出现粉化的问题，降低使用寿命。原因在于钒氮合金制备原料在高温加热过程中，释放出钾、钠蒸汽，石墨坩埚吸附钾、钠蒸汽后造成体积膨胀使石墨粉化；钒氮合金制备过程需通入大量氮气作为反应气，高温氮气冲刷也加剧会石墨粉化。
为了减少石墨坩埚在使用过程中逐渐粉化，可以在坩埚表面施用保护涂层，由此阻止钾钠蒸汽吸附和提高石墨坩埚抗热冲击性。现有技术采用介质熔炼、喷涂等方法制备涂层。
例如在高温条件下，将金属硅在石墨坩埚中熔化，利用石墨与硅之间发生化学反应所生成的碳化硅(SiC)对石墨坩埚内表面起到保护作用，延长石墨坩埚的使用寿命。
例如通过将高温抗氧化的Al4SiC4陶瓷弥散到以再生石墨粉为原料的石墨坩埚中，在高温氧化性气氛中，石墨坩埚表面的非氧化物Al4SiC4陶瓷颗粒被氧化，在1300℃时生成氧化物Al2O3薄膜、在1600℃时生成氧化物Al2O3和铝硅酸盐SiO2-Al2O3薄膜，薄膜覆盖在石墨坩埚的表面，与此同时，非氧化物Al4SiC4陶瓷颗粒被氧化时产生的体积膨胀，可以填充和封闭材料中的气体通道，通过薄膜的隔绝及气体通道的封闭使石墨坩埚材料被有效保护，从而使石墨坩埚实现了自愈合抗氧化的技术效果。
上述方法虽然能够减少石墨坩埚粉化的问题，但是此方法所需设备价格较为昂贵且操作复杂，亟需开发一种高效、低成本制备石墨坩埚涂层的方法。
发明内容
基于此，有必要针对上述技术问题，采用以下技术方案：
本发明提供一种钒氮合金用石墨坩埚涂层的制备方法，包括以下步骤：
浆料制备：将单晶硅粉体、二氧化硅粉体以及粘结剂混合制成浆料；
涂覆涂层：将料浆喷涂到未经烧制的石墨坩埚表面形成厚度为3～10mm的料浆层；
干燥：在惰性气体保护下干燥涂覆涂层后的石墨坩埚；
烧成：将干燥后的石墨坩埚高温氮气气氛进行烧制，烧制制得表面包覆氮化硅涂层的石墨坩埚。
进一步地，所述单晶硅粉体的粒度为38～74um；所述二氧化硅粉体的粒度为38～74um。
进一步地，单晶硅粉体、二氧化硅粉体和粘接剂的重量比为(20～50):(10～20):(30～70)。
进一步地，所述粘接剂选自有机硅烷、硅酸、多元醇、聚乙烯醇和丙烯酸酯。
进一步地，在惰性气体保护下干燥涂覆涂层后的石墨坩埚2～8h，所述惰性气体选自氩气、氦气、氩-氦混合气。
进一步地，干燥过程中的干燥温度为100～300℃。
进一步地，在烧成步骤中，将干燥后的石墨坩埚送入钒氮合金冶炼用推板窑，在温度为800～1500℃氮气气氛条件下烧制0.5～48小时。优选地，烧制温度为1100℃～1500℃。优选地，烧制时间为2-48小时。
进一步地，有机硅烷选自四甲基硅烷和甲基硅油。
进一步地，多元醇选自乙二醇和丙二醇。
进一步地，丙烯酸酯为甲基丙烯酸酯。
本发明具有以下有益技术效果：
在钒氮合金生产成本中，石墨坩埚成本约占总成本的1/6。为了降低钒氮合金生产成本，本发明的钒氮合金用石墨坩埚涂层的制备方法通过将单晶硅粉、二氧化硅粉、粘接剂混合制成浆料涂覆于石墨坩埚外表面，料浆干燥后送入推板窑，料浆在推板窑氮气气氛下与石墨坩埚反应形成氮化硅涂层，提升石墨坩埚的使用寿命，减缓石墨坩埚消耗速率，降低生产成本。
本发明的钒氮合金用石墨坩埚涂层的制备方法所用二氧化硅，与直接使用氮化硅相比价格更加低廉，且可利用钒氮合金生产过程保护气体氮气反应制备氮化硅，成本更低。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白，以下结合具体实施例，对本发明实施例进一步详细说明。
针对钒氮合金冶炼时石墨坩埚易粉化的问题，本发明提供的一种钒氮合金用石墨坩埚涂层的制备方法，包括以下步骤：
浆料制备：将单晶硅粉体、二氧化硅粉体以及粘结剂混合制成浆料；
涂覆涂层：将料浆喷涂到未经烧制的石墨坩埚表面形成厚度为3～10mm的料浆层；
干燥：在惰性气体保护下干燥涂覆涂层后的石墨坩埚；
烧成：将干燥后的石墨坩埚高温氮气气氛进行烧制，烧制制得表面包覆氮化硅涂层的石墨坩埚。
氮气流量无明确要求，但要求炉内氮气压力维持微正压。
石墨坩埚的主要化学成分为碳单质。具体的单晶硅粉体、二氧化硅粉体与石墨坩埚形成氮化硅涂层的原理在于：
1)单质硅和氮气直接进行化合反应得到氮化硅：
3Si(s)+2N2(g)→Si3N4(s)
2)二氧化硅在氮气气氛下与碳发生碳热还原反应得到氮化硅：
3SiO2(s)+6C(s)+2N2(g)→Si3N4(s)+6CO(g)
浆料里面的硅或二氧化硅与石墨坩埚表面的碳反应，在石墨坩埚表面生成碳化硅是形成涂层的主要原因，粘结剂的加入是为了使硅或二氧化硅可以很好地附着于石墨坩埚表面，从而进行反应。
本发明选用的单晶硅粉体的粒度为38～74um；二氧化硅粉体的粒度为38～74um。在此粒度范围的粉体能够更好的进行氮化硅的合成反应。
本发明控制单晶硅粉体、二氧化硅粉体和粘接剂的重量比为(20～50):(10～20):(30～70)。通过控制粘结剂的含量能够使得单晶硅粉体、二氧化硅粉体更好的粘附到石墨坩埚表面。单晶硅粉体、二氧化硅粉体和粘接剂的重量比不在上述范围时，会对产生涂层的质量产生不好的影响。例如当单晶硅粉体、二氧化硅粉体低于上述范围，那么，会使得反应物含量过低，难以在石墨坩埚表面形成致密的氧化硅涂层。
粘接剂选自有机硅烷、硅酸、多元醇、聚乙烯醇和丙烯酸酯。有机硅烷选自四甲基硅烷和甲基硅油。多元醇选自乙二醇和丙二醇。丙烯酸酯为丙烯酸甲酯。
优选地，在惰性气体保护下干燥涂覆涂层后的石墨坩埚2～8h，所述惰性气体选自氩气、氦气、氩-氦混合气。
优选地，干燥过程中的干燥温度为100～300℃。
优选地，在烧成步骤中，将干燥后的石墨坩埚送入钒氮合金冶炼用推板窑，在温度为800～1500℃氮气气氛条件下烧制0.5～48小时。通过将料浆干燥后送入推板窑，料浆在推板窑氮气气氛下与石墨坩埚反应形成氮化硅涂层，没有使用额外的设备且操作简单，降低生产成本。
在另一个优选的实施例中，烧制温度为1100℃～1500℃。
在另一个优选的实施例中，烧制时间为2-48小时。
本发明的钒氮合金用石墨坩埚涂层的制备方法所用二氧化硅，与直接使用氮化硅相比价格更加低廉，且可利用钒氮合金生产过程保护气体氮气反应制备氮化硅，成本更低。
为了进一步理解本发明，下面结合实施例对本发明提供的钒氮合金用石墨坩埚涂层及其制备方法进行描述，本发明的保护范围不受以下实施例的限制。
实施例1
本实施例的钒氮合金用石墨坩埚涂层的制备方法，包括以下步骤：
浆料制备：将粒度为38～44μm的单晶硅粉、38～44μm二氧化硅粉和有机硅烷按重量比30:20:50混合形成料浆。
浆料制备：将混合料浆喷涂到未经烧制的石墨坩埚外表面，形成厚度为3～5mm的涂层。
干燥：在惰性气体保护下，涂覆涂层后的石墨坩埚在120℃的温度下干燥4h。
烧成：将干燥后的石墨坩埚送入钒氮合金冶炼用推板窑，在温度为1000～1300℃氮气气氛条件下烧制8h小时，烧制制得表面包覆氮化硅涂层的石墨坩埚。
实施例2
本实施例的钒氮合金用石墨坩埚涂层的制备方法，包括以下步骤：
浆料制备：将粒度为44～61μm的单晶硅粉、44～61μm二氧化硅粉和多元醇按重量比20:15:65混合形成料浆。
涂覆涂层：将混合料浆喷涂到未经烧制的石墨坩埚外表面，形成厚度为2～4mm的涂层。
干燥：在惰性气体保护下，涂覆涂层后的石墨坩埚在160℃的温度下干燥3h。
烧成：将干燥后的石墨坩埚送入钒氮合金冶炼用推板窑，在温度为1100～1400℃氮气气氛条件下烧制16h小时，烧制制得表面包覆氮化硅涂层的石墨坩埚。
实施例3
本实施例的钒氮合金用石墨坩埚涂层的制备方法，包括以下步骤：
浆料制备：将粒度为61～74μm的单晶硅粉、61～74μm二氧化硅粉和丙烯酸酯按重量比35:10:55混合形成料浆。
浆料制备：将混合料浆喷涂到未经烧制的石墨坩埚外表面，形成厚度为5～7mm的涂层。
干燥：在惰性气体保护下，涂覆涂层后的石墨坩埚在180℃的温度下干燥6h。
烧成：将干燥后的石墨坩埚送入钒氮合金冶炼用推板窑，在温度为900～1200℃氮气气氛条件下烧制24h小时，烧制制得表面包覆氮化硅涂层的石墨坩埚。
实施例4
本实施例的钒氮合金用石墨坩埚涂层的制备方法，包括以下步骤：
浆料制备：将粒度为38～44μm的单晶硅粉、38～44μm二氧化硅粉和丙烯酸酯按重量比50:20:70混合形成料浆。
涂覆涂层：将混合料浆喷涂到未经烧制的石墨坩埚外表面，形成厚度为8～10mm的涂层。
干燥：在惰性气体保护下，涂覆涂层后的石墨坩埚在300℃的温度下干燥2h。
烧成：将干燥后的石墨坩埚送入钒氮合金冶炼用推板窑，在温度为800～1100℃氮气气氛条件下烧制48h小时，烧制制得表面包覆氮化硅涂层的石墨坩埚。
实施例5
本实施例的钒氮合金用石墨坩埚涂层的制备方法，包括以下步骤：
浆料制备：将粒度为38～44μm的单晶硅粉、38～44μm二氧化硅粉和丙烯酸酯按重量比20:10:30混合形成料浆。
涂覆涂层：将混合料浆喷涂到未经烧制的石墨坩埚外表面，形成厚度为3～4mm的涂层。
干燥：在惰性气体保护下，涂覆涂层后的石墨坩埚在100℃的温度下干燥8h。
烧成：将干燥后的石墨坩埚送入钒氮合金冶炼用推板窑，在温度为1200～1500℃氮气气氛条件下烧制14h小时，烧制制得表面包覆氮化硅涂层的石墨坩埚。
以上是本发明公开的示例性实施例，但是应当注意，在不背离权利要求限定的本发明实施例公开的范围的前提下，可以进行多种改变和修改。尽管本发明实施例公开的元素可以以个体形式描述或要求，但除非明确限制为单数，也可以理解为多个。
所属领域的普通技术人员应当理解：以上任何实施例的讨论仅为示例性的，并非旨在暗示本发明实施例公开的范围(包括权利要求)被限于这些例子；在本发明实施例的思路下，以上实施例或者不同实施例中的技术特征之间也可以进行组合，并存在如上本发明实施例的不同方面的许多其它变化，为了简明它们没有在细节中提供。因此，凡在本发明实施例的精神和原则之内，所做的任何省略、修改、等同替换、改进等，均应包含在本发明实施例的保护范围之内。
Claims (7)
1.一种钒氮合金用石墨坩埚涂层的制备方法，其特征在于，包括以下步骤：
浆料制备：将单晶硅粉体、二氧化硅粉体以及粘结剂混合制成浆料，单晶硅粉体、二氧化硅粉体和粘接剂的重量比为（20~50）:（10~20）:（30~70）；所述粘接剂选自有机硅烷、硅酸、多元醇、聚乙烯醇和丙烯酸酯，所述单晶硅粉体的粒度为38~74μm；所述二氧化硅粉体的粒度为38~74μm；
涂覆涂层：将料浆喷涂到未经烧制的石墨坩埚表面形成厚度为 3~10mm的料浆层；
干燥：在惰性气体保护下干燥涂覆涂层后的石墨坩埚；
烧成：将干燥后的石墨坩埚高温氮气气氛进行烧制，烧制制得表面包覆氮化硅涂层的石墨坩埚。
2.根据权利要求1所述的钒氮合金用石墨坩埚涂层的制备方法，其特征在于，在惰性气体保护下干燥涂覆涂层后的石墨坩埚2~8h，所述惰性气体选自氩气、氦气、氩-氦混合气。
3.根据权利要求2所述的钒氮合金用石墨坩埚涂层的制备方法，其特征在于，干燥过程中的干燥温度为100~300℃。
4.根据权利要求1所述的钒氮合金用石墨坩埚涂层的制备方法，其特征在于，在烧成步骤中，将干燥后的石墨坩埚送入钒氮合金冶炼用推板窑，在温度为800~1500℃氮气气氛条件下烧制0.5~48小时。
5.根据权利要求1所述的钒氮合金用石墨坩埚涂层的制备方法，其特征在于，有机硅烷选自四甲基硅烷和甲基硅油。
6.根据权利要求1所述的钒氮合金用石墨坩埚涂层的制备方法，其特征在于，多元醇选自乙二醇和丙二醇。
7.根据权利要求1所述的钒氮合金用石墨坩埚涂层的制备方法，其特征在于，丙烯酸酯为甲基丙烯酸酯。
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