CN107723511B - 一种激光增材制造准晶-纳米晶改性梯度复合材料的方法 - Google Patents
一种激光增材制造准晶-纳米晶改性梯度复合材料的方法 Download PDFInfo
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Abstract
本发明公开了一种用激光3D打印技术制备准晶‑纳米晶改性梯度复合材料的方法。用同轴送法将Stellite 12‑B4C‑Y2O3混合粉末激光合金化于TA15合金表面形成组织较为组大的下层；后将Stellite 12‑B4C‑Cu‑Y2O3混合粉末激光沉积于下层表面形成组织较为致密的上层，上层与下层之间呈良好的冶金结合，且都具有较好的耐磨性。实验结果表明，随着Cu的加入产生了许多超细纳米晶及准晶相，改变了激光增材制造梯度复合层的结构并提高了其力学性能。本发明能够获得组织结构致密且具有极高耐磨性的梯度复合材料。
Description
技术领域
本发明涉及一种激光增材制造准晶-纳米晶改性梯度复合材料的方法，属于增材制造技术领域。特别涉及一种在钛合金表面用Stellite 12-B4C-Cu-Y2O3混合粉末通过激光加工技术来制备准晶-纳米晶改性复合材料的方法。
背景技术
增材制造（3D打印）正强劲地驱动新兴产业技术群快速崛起，顺应了新技术革命大趋势，即由传统大规模、批量生产模式向个性化、订制化、小批量生产模式转型。激光合金化技术是增材制造的一个重要分枝，可实现工件微结构纳米化，具有效率高、速度快及绿色环保等特点。梯度复合材料既能较好地克服单一材料性能上的局限，又能充分发挥不同材料的特殊性能，满足现代高科技领域对新型材料的要求。将不同成分金属陶瓷混合粉末分层激光熔化沉积所形成的结构会产生许多界面，这些界面可钉扎缺陷得到比单一结构材料综合力学性能更强的梯度复合材料。利用纳米准晶化技术改变金属材料的组织结构进而提高性能、拓展其使用范围是新材料研究与开发的热点。准晶体的结构与晶体及非晶体有本质区别，准晶具有许多理想特性，如硬度高、摩擦系数低及抗高温氧化性好等，准晶材料在耐磨涂层研究领域有较大的应用潜力。而纳米材料基于其高韧性、高强度、高硬度等特性在增材制造领域具有非常巨大的应用潜力。
基于上述科学原理，并依据激光辐射于金属表面所形成高温熔池的快速冷凝特性，本发明提出了一种能够降低生产成本，通过激光加工技术制备准晶-纳米晶改性梯度复合材料的方法。激光所形成熔池具有急冷特性，利于纳米晶与准晶相产生。采用同轴送粉法在氩气环境中将Stellite 12-B4C-Y2O3混合粉末激光合金化于TA15钛合金表面形成组织较为粗大的下层；后将Stellite 12-B4C-Cu-Y2O3 混合粉末激光沉积于下层之上形成组织结构较为致密的上层。上层与下层之间呈良好的冶金结合且都具有较好的耐磨性。试验结果表明，Cu的加入可催生出许多AlCu2Ti超细纳米晶。该类超细纳米晶的生成有利于涂层组织结构细化并提高其力学性能。所制备准晶-纳米晶改性梯度复合材料的组织结构见图1。
所制备梯度复合材料中Stellite 12-B4C-Cu-Y2O3上层中的准晶相形貌见图2，由于激光熔池的急冷作用，许多晶体还未得到充分时间长大就已凝固，所以在准晶中呈纳米结构。
用HV-1000型显微硬度计测试所制备梯度复合材料的硬度，加载时间5 s；用WMM-W1盘式磨损试验机测定梯度复合材料的耐磨性，选用烧结硬度为1800 HV 的Al2O3作为磨轮材料，载荷98 N，转速465 rpm。磨损体积测定：磨损试验中每隔15分钟测量一次磨痕宽度或磨损失重；磨痕宽度采用体积显微镜测定，经过多点测定后取平均值作为测量结果。利用如下公式近似计算磨损体积。
V=l{r 2arcsin-
}
式中：V磨损体积，单位mm3；
l磨痕长度（即试样宽度），单位mm；
b磨痕宽度，单位mm；
r磨轮半径，单位mm。
图3显示了梯度复合材料的显微硬度分布。Stellite 12-B4C-Cu-Y2O3上层显微硬度分布范围1500～1600 HV0.2；由于基材对下层的稀释作用及欠缺Cu作用的原因，下层显微硬度较上层偏低，分布范围700～1200 HV0.2。
所制备梯度复合材料具有较高的硬度与较好的耐磨性及组织结构，磨损体积随测试时间的延长呈明显上升趋势，这表明上层的耐磨性明显高于下层（见图4）。
发明内容
本发明采用激光增材制造技术，针对钛合金表面耐磨性较差的缺陷，先采用激光合金化技术制备Stellite 12-B4C-Y2O3下层；后在其表面激光熔化沉积Stellite 12-B4C-Cu-Y2O3混合粉末制备准晶-纳米化复合材料，形成梯度复合材料。该项技术可应用于飞机零件制造中以及航空领域部件修复等诸多方面。具体步骤如下：
1）将一定质量比例Stellite 12、B4C、Y2O3的混合粉末以同轴送粉方式激光合金化于钛合金表面形成下层；再将一定质量比例的Stellite 12、B4C、Cu及Y2O3的混合粉末以同样方式激光熔化沉积于下层表面形成上层。所述Stellite 12 粉末尺寸50~150 μm，B4C粉末尺寸75~250 μm，Cu粉末尺寸1~30 μm，Y2O3粉末尺寸10~200 nm；
2）在上、下层的成形过程中，激光束垂直扫描并同轴吹送氩气保护熔池及镜筒，工艺参数：激光功率0.6～2.8 kW，激光束扫描速度 2～12 mm/s，送粉速率15～35 g/min，光斑直径4 mm，氩气流速10～40 L/min，焊道搭接率30%。上层与下层的工艺方法与参数完全相同。
步骤1）所述钛合金为TA15牌号；混合粉末各成分及质量分数： B4C 7～29%，Y2O3 1～3%，余量 Stellite 12下层；B4C 7～29%， Cu 3～7%，Y2O3 1～3%，余量 Stellite 12上层。Stellite 12中各化学元素质量分数: C1.40%，Cr 29.50%， Si1.45%，W8.25%，Fe3.00%，Mo1.00%，Ni3.00%，Mn1.00%，余量Co。
本发明是在氩气环境中钛合金试样表面发生激光合金化。在激光处理过程中，激光束扫描速度保持不变。试样表面被完全激光合金化后将激光关闭，两秒钟后关闭保护气体，原因是使保护气对试样表面进行充分保护。本发明能够获得具有立体形态且较强耐磨性的梯度复合材料，具有工艺简单方便、适用性强、便于推广应用等优点。
附图说明
图1是梯度复合材料SEM形貌。
图1中(a) 是下层， 图中(b) 是上层，图中(c)上层中纳米晶聚集态，图中(d)是纳米晶。
图2 梯度复合材料上层中准晶及其中的纳米晶。
图3 TA15合金梯度复合材料显微硬度分布。
图4 TA15合金梯度复合材料磨损体积随时间延长变化图。
具体实施方式
实例1:
将TA15钛合金切成长度30 mm、宽度10 mm、厚度10 mm的长方体。进行激光加工之前清理钛合金表面，并拭净、吹干。将质量分数为89%Stellite 12、10%B4C、1%Y2O3的混合粉末激光合金化于钛合金的30 mm×10 mm面表面形成下层；后将质量分数为84%Stellite12、10%B4C、5%Cu及1%Y2O3的混合粉末激光熔化沉积于下层之上，形成上层。具体工艺步骤如下：
(1) 在激光合金化之前，用240号砂纸打磨已切好的TA15钛合金待激光处理表面，使其表面粗糙度达Ra 2.5 μm；而后，先用清水冲洗，再用酒精将待熔表面擦拭干净后吹干；
(2) 用天平分别称取Stellite 12粉末89 g、B4C粉末10 g、Y2O3粉末1 g，放入1号烧杯；用天平再称取Stellite 12粉末84g、B4C粉末10 g、Cu粉末5 g、Y2O3 粉末1g，放入2号烧杯。其中Stellite 12粉末尺寸100 μm，、B4C粉末尺寸100 μm、Cu粉末尺寸15 μm、Y2O3 粉末尺寸20 nm；将两个烧杯中的混合粉末通过机械混粉器充分混合并分别用烘干机烘干；
(3) 用同轴送粉器直接将1号烧杯中的混合粉末吹向试样待处理表面进行激光熔化沉积处理，形成下层。工艺参数：激光功率1.10 kW，激光束扫描速度 2.5 mm/s，送粉速率25 g/min，光斑直径4 mm，焊道搭接率30%，氩气流速20 L/min
(4) 再用同轴送粉器将烧杯2中的混合粉末吹向下层表面进行激光熔化沉积处理，形成上层。本次工艺参数与之前制备上层相同，也采用氩气作为保护气体。
Claims (1)
1.一种激光增材制造准晶-纳米晶改性梯度复合材料的方法，其特征是：
（1）将一定质量比例Stellite 12、B4C、Y2O3混合粉末通过机械混粉器充分混合并用烘干机烘干，用同轴送粉器将Stellite 12、B4C、Y2O3混合粉末吹向TA15钛合金待处理表面进行激光合金化处理形成下层，过程采用激光束垂直扫描并同轴吹送氩气保护熔池及镜筒，工艺参数：激光功率0.6～2.8 kW，扫描速度 2～12 mm/s，送粉速率15～35 g/min，光斑直径4 mm，氩气流速10～40 L/min，焊道搭接率30%；混合粉末成分及质量分数：B4C 7～29%，Y2O3 1～3%，余量 Stellite 12；Stellite 12中各化学元素质量分数：C1.40%，Cr 29.50%，Si1.45%，W8.25%，Fe3.00%，Mo1.00%，Ni3.00%，Mn1.00%，余量Co；
（2）将一定质量比例Stellite 12、B4C、Cu、Y2O3混合粉末通过机械混粉器充分混合并用烘干机烘干，用同轴送粉器将Stellite 12、B4C、Cu、Y2O3混合粉末吹向下层表面进行激光熔化沉积处理形成上层，激光束垂直扫描并同轴吹送氩气保护熔池及镜筒，工艺参数：激光功率0.6～2.8 kW，扫描速度 2～12 mm/s，送粉速率15～35 g/min，光斑直径4 mm，氩气流10～40 L/min，焊道搭接率30%，混合粉末各成分及质量分数：B4C 7～29%， Cu 3～7%，Y2O3 1～3%，余量 Stellite 12。
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