CN107385364A - 一种热喷涂用非晶涂层粉末 - Google Patents
一种热喷涂用非晶涂层粉末 Download PDFInfo
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Abstract
本发明涉及一种形成涂层的防腐耐磨合金粉末及一种喷涂有该粉末的高硬耐磨材料，所述热喷涂用非晶涂层粉末按原子百分比计算，有以下成分组成：Cr 14％‑18％，Fe 2％‑8％，C≤2％，Co 5％‑10％，B 5％‑8％，0＜Y≤3％，Mo 12％‑16％，余量为Ni。将该粉末可喷涂于哈氏合金C276，致密度高，气孔率低，结合强度高，表面硬度高，耐磨性好，耐腐蚀性强等特点。
Description
技术领域
本发明涉及高温环境中构件表面防护技术领域，特别涉及一种用于制备耐高温且防腐防磨的热喷涂防护涂层的粉末材料及含有该粉末形成涂层的制品。
背景技术
结构件表面由于长时间磨损造成结构件损伤甚至失效，因此会在结构件表面涂覆高硬耐磨材料。热喷涂是一种表面强化技术，指将熔融状态的喷涂材料，通过高速气流使其雾化喷射在零件表面上，迅速冷却形成喷涂层的一种金属表面加工方法。热喷涂作为一种广泛应用的工业技术，成功应用于航空、航天、冶金、能源、交通、石油化工、机械、轻纺等工业部门,成效十分显著。碳化钨是热喷涂领域制备高耐磨层的重要原料粉末，碳化钨硬度高，与Fe、Ni基体润湿性好，因此常被用作热喷涂耐磨涂层使用。然而，热喷涂碳化钨涂层的主要缺点是抗高温氧化能力差，在500-800℃空气中操守严重氧化，即所谓“失碳”，此外，热喷涂碳化钨涂层形成表面空隙，造成致密度下降，从而耐腐蚀性也会降低。
非晶态合金简称非晶合金，又称为金属玻璃，具有长程无序、短程有序的亚稳态结构特征。与传统的晶态合金相比，非晶合金具备很多优异的性能，如高强度、高硬度、耐磨和耐腐蚀等，引起材料学界广泛的关注。非晶合金材料存在的问题是其制备工艺过程难以控制，在实际中很难制备大块非晶材料难以作为结构材料使用，而非晶材料形成涂层喷涂于金属材料表面可以发挥良好的耐磨、耐腐蚀性能。
非晶合金涂层是指通过表面工程技术在传统材料表面获得的一层非晶涂层，该涂层的应用可以大大提高传统表面硬度、耐蚀及耐磨性能，在材料表面改性领域具有十分巨大的潜在应用价值，尤其是成本相对低廉的铁基非晶合金涂层，具有优异的物理和化学性能，如超高的硬度和极佳的耐磨抗腐性能，因此在表面工程领域有广阔的应用前景。
热喷涂非晶涂层的核心技术难点在于热喷涂过程中，熔融的粉末不能被氧化，也不能超过晶化转变温度以上，而非晶粉末一般来说其中含有大量的易氧化的微量元素，申请号为201410406600.8的中国申请公布了一种表面改性的非晶合金粉末，其通过粉末表面改性的方法在非晶合金粉末表面包覆一层抗氧化的金属镀层，从而降低非晶合金粉末在热喷涂过程中的氧化程度，解决目前非晶合金粉末由于高温喷涂过程的氧化而导致的涂层性能降低的问题。申请号为201510566809.5的中国申请公布了一种用于锅炉炉内受热面的热喷涂非晶合金涂层方法，其中描述的主要为电弧喷涂所用的非晶涂层丝材，但是鉴于电弧喷涂所用的涂层致密度不高，其孔隙率约为5％，抗腐蚀效果有限。
发明内容
本发明所要解决的技术问题是克服现有技术的不足，提供一种新的热喷涂用非晶涂层粉末，可以兼顾热喷涂过程中元素氧化烧损和涂层致密度不够问题。
为解决以上技术问题，本发明所采用如下技术方案：
一种防腐耐磨合金粉末，该粉末用于实施在基体上形成防护涂层，所述防腐耐磨合金粉末由非晶合金组成，以原子百分比计，所述非晶合金的组分为：Cr 14at％-18at％，Fe 2at％-8at％，C≤2at％，Co 5at％-10at％，B 5at％-8at％，0＜Y≤3at％，Mo 12at％-16at％，余量为Ni。
进一步优选地，所述的防腐耐磨合金粉末粒度均低于150μm。
进一步优选地，所述的防腐耐磨合金粉末以原子百分比计，所述粉末的组分为：Cr15％-17％，Fe 3％-7％，C≤2％，Co 5％-8％，B 6％-8％，0＜Y≤3％，Mo 12％-15％，余量为Ni。
进一步优选地，所述的防腐耐磨合金粉末以原子百分比计，所述粉末的组分为：Cr14％-18％，Fe 3％-6％，C 0.5-1.8％，Co 6％-9％，B 6％-7.5％，Y 1-3％，Mo 12％-14％，余量为Ni。
进一步优选地，所述的防腐耐磨合金粉末以原子百分比计，所述粉末的组分为：Cr16％，Fe 6％，C≤1％，Co 7％，B 6％，0＜Y≤3％，Mo 14％，余量为Ni。
一种制备如上所述的防腐耐磨合金粉末的方法，采用高能机械球磨工艺制备，具体包括以下步骤：
(1)混粉：首先将Ni粉、Cr粉、Fe粉、Mo粉、Co粉、C粉、B粉和Y粉按相应的原子百分比进行配料，然后将粉末在混粉机中干混至均匀；
(2)高能球磨制备：Ni-Cr-Fe-Mo-Co系镍基非晶态合金粉末采用行星式高能球磨机完成非晶态合金粉末的制备，球磨罐反复抽真空后充入氩气以防氧化，球磨用不锈钢球或刚玉球，球磨机转速为300-500r/min，球粉质量比为20:1，球磨时间为35～45h；球磨过程中，正反交替运行时间为0.5-2h，交替运行间隔时间为0.2-0.4h。
所述的制备方法制得的热喷涂应用于喷涂镍基或铁基合金，例如不锈钢或哈氏合金。
一种包含防腐耐磨涂层的制品，其特征在于，该涂层由将上述防腐耐磨合金粉末喷涂或熔敷于镍基或铁基合金表面而形成，涂层厚度20μm-2mm，喷涂后涂层非晶比例达到90％以上。
进一步优选地，镍基合金为哈氏合金C276。
进一步优选地，喷涂方式采用等离子喷涂或激光熔敷或超声速火焰喷涂。
本发明相比于现有技术，具备以下优点：
(1)本发明形成的Ni-Cr-Fe-Mo-Co系镍基非晶态合金粉末热喷涂与铁基和镍基合金表面，形成的涂层非晶率高，结合强度高，硬度高，相比于碳化钨涂层，高温环境下氧化程度低，失炭烧少；涂层气孔率不足1％，致密度高，耐腐蚀性好。
附图说明
图1本发明非晶喷涂粉末喷涂于哈氏合金C276基体与传统碳化钨喷涂于SUS304不锈钢基体在FeCl3环境腐蚀72小时后形态对比图。
图2本发明非晶喷涂粉末喷涂于基体表面硬度测试图。
具体实施方式
下面结合实施例，对本发明的具体实施方式作进一步详细的描述。
本发明的热喷涂用防腐耐磨合金粉末，该粉末可通过热喷涂方法实施在基体上形成防护涂层，所述防腐耐磨合金粉末由非晶合金组成，以原子百分比计，所述非晶合金的组分为：Cr 14at％-18at％，Fe 2at％-8at％，C≤2at％，Co 5at％-10at％，B 5at％-8at％，0＜Y≤3at％，Mo 12at％-16at％，余量为Ni。
对于粉末的颗粒限定在200μm以下，优选150μm以下。喷涂采用的方式没有特别限定，可选但不局限于等离子喷涂或激光熔敷或超声速火焰喷涂以及爆炸熔敷，对于涂层的厚度可实现2mm厚，对于基体合金可以为铁基、钴基、镍基合金，其中以镍基合金效果为最优。
实施例1
制备本申请非晶态的防腐耐磨合金粉末的方法，采用高能机械球磨工艺制备，具体包括以下步骤：
(1)混粉：首先将Ni粉、Cr粉、Fe粉、Mo粉、Co粉、C粉、B粉和Y粉按相应的原子百分比为Cr 14at％-18at％，Fe 2at％-8at％，C≤2at％，Co 5at％-10at％，B 5at％-8at％，0＜Y≤3at％，Mo 12at％-16at％，余量为Ni进行配料，然后将粉末在混粉机中干混至均匀；
(2)高能球磨制备：Ni-Cr-Fe-Mo-Co系镍基非晶态合金粉末采用行星式高能球磨机完成非晶态合金粉末的制备，球磨罐反复抽真空后充入氩气以防氧化，球磨用不锈钢球或刚玉球，球磨机转速为300-500r/min，球粉质量比为20:1，球磨时间为35～45h；球磨过程中，正反交替运行时间为0.5-2h，交替运行间隔时间为0.2-0.4h。
实施例2
选择以原子百分比计，所述粉末的组分为：Cr 16％，Fe 6％，C0.5％，Co 7％，B6％，Y 2％，Mo 14％，余量为Ni的热喷涂用防腐耐磨合金粉末，粒度控制在30-100μm。将热喷涂用防腐耐磨合金粉末通过超音速火焰喷涂装置，喷涂于C276合金表面，涂层厚度300μm，表面气孔率0.58％，表面结合强度59MPa。
实施例3
选择以原子百分比计，所述粉末的组分为：Cr 14％，Fe 7％，C 2％，Co 8％，B7％，Y 3％，Mo 13％，余量为Ni的热喷涂用防腐耐磨合金粉末，粒度控制在100-150μm。将热喷涂用防腐耐磨合金粉末通过等离子喷涂装置，喷涂于SUS304合金表面，涂层厚度600μm,表面气孔率0.65％，表面结合强度58MPa。
实施例4
选择以原子百分比计，所述粉末的组分为：Cr 15％，Fe 3％，C 2％，Co 5％，B8％，Y 0.8％，Mo 15％，余量为Ni的热喷涂用防腐耐磨合金粉末，粒度控制在60-120μm。将热喷涂用防腐耐磨合金粉末通过激光熔敷装置，熔敷于Inconel600合金表面，涂层厚度2mm,表面气孔率0.69％，表面结合强度55.6MPa。
比较例1
对SUS304不锈钢表面采用超音速火焰装置喷涂碳化钨，涂层厚度400μm。
耐腐蚀性比较：
将实施例2中的喷涂有本申请的防腐耐磨合金粉末的C276合金与比较例1中喷涂碳化钨的SUS304不锈钢，分别放置于FeCl3溶液中72小时后，表面形态如图1所示。其中(A)为喷涂碳化钨的SUS304不锈钢，(B)为喷涂有本申请的防腐耐磨合金粉末的C276合金，从形态上可以明显看出，喷涂有本申请的防腐耐磨合金粉末的C276合金表面完整致密，被腐蚀较小，而喷涂碳化钨的SUS304不锈钢表面被腐蚀严重。可见，相比于碳化钨涂层，本申请的涂层便显出有优异的耐腐蚀性。
表面显微硬度测试：
对实施例4中通过激光熔敷涂层进行表面显微硬度，测试得到涂层表面洛式硬度分布如图2所示，涂层制品从上向下分为熔敷层、热影响区和基体。在熔敷层靠近上表面区域具有最高的强度，可以达到56HRC，能够较好地满足高强耐磨的需要。
最后应说明的是：以上实施例仅用以说明本发明而并非限制本发明所描述的技术方案，因此，尽管本说明书参照上述的各个实施例对本发明已进行了详细的说明，但是，本领域的普通技术人员应当理解，仍然可以对本发明进行修改或等同替换，而一切不脱离本发明的精神和范围的技术方案及其改进，其均应涵盖在本发明的权利要求范围中。
Claims (9)
1.一种防腐耐磨合金粉末，该粉末用于实施在基体上形成防护涂层，其特征在于：所述防腐耐磨合金粉末由非晶合金组成，以原子百分比计，所述非晶合金的组分为：Cr 14at％-18at％，Fe 2at％-8at％，C≤2at％，Co 5at％-10at％，B 5at％-8at％，0＜Y≤3at％，Mo12at％-16at％，余量为Ni。
2.根据权利要求1所述的防腐耐磨合金粉末，其特征在于：所述的防腐耐磨合金粉末粒度均低于150μm。
3.根据权利要求1或2所述的防腐耐磨合金粉末，其特征在于：以原子百分比计，所述粉末的组分为：Cr 15％-17％，Fe 3％-7％，C≤2％，Co 5％-8％，B 6％-8％，0＜Y≤3％，Mo12％-15％，余量为Ni。
4.根据权利要求1或2所述的防腐耐磨合金粉末，其特征在于：以原子百分比计，所述粉末的组分为：Cr 14％-18％，Fe 3％-6％，C 0.5-1.8％，Co 6％-9％，B 6％-7.5％，Y 1-3％，Mo 12％-14％，余量为Ni。
5.根据权利要求1或2所述的防腐耐磨合金粉末，其特征在于：以原子百分比计，所述粉末的组分为：Cr 16％，Fe 6％，C≤1％，Co 7％，B 6％，0＜Y≤3％，Mo 14％，余量为Ni。
6.一种制备权利要求1-5中任一项所述的防腐耐磨合金粉末的方法，其特征在于包括以下步骤：
(1)混粉：首先将Ni粉、Cr粉、Fe粉、Mo粉、Co粉、C粉、B粉和Y粉按相应的原子百分比进行配料，然后将粉末在混粉机中干混至均匀；
(2)高能球磨制备：Ni-Cr-Fe-Mo-Co系镍基非晶态合金粉末采用行星式高能球磨机完成非晶态合金粉末的制备，球磨罐反复抽真空后充入氩气以防氧化，球磨用不锈钢球或刚玉球，球磨机转速为300-500r/min，球粉质量比为20:1，球磨时间为35～45h；球磨过程中，正反交替运行时间为0.5-2h，交替运行间隔时间为0.2-0.4h。
7.一种包含防腐耐磨涂层的制品，其特征在于，该涂层由将权利要求1-5任一项所述的防腐耐磨合金粉末喷涂或熔敷于镍基或铁基合金表面而形成，涂层厚度20μm-2mm，喷涂后涂层非晶比例达到90％以上。
8.根据权利要求8所述的制品，其特征在于，镍基合金为哈氏合金C276。
9.根据权利要求8或9所述的制品，其特征在于，喷涂方式采用等离子喷涂或激光熔敷或超声速火焰喷涂。
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