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通讯作者:

李文亚(1976—),男(汉),教授,博士;研究方向:冷喷涂与摩擦焊接;E-mail:liwy@nwpu.edu.cn

中图分类号:TG174.442

文献标识码:A

文章编号:1007-9289(2020)04-0082-20

DOI:10.11933/j.issn.1007-9289.20200529001

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目录contents

    摘要

    冷喷涂技术因其固态沉积特性及突出的冶金优势,在金属或金属基复合材料涂层制备、增材制造与修复再制造等领域获得了国内外研究者的广泛关注。 近十年来,国内外对冷喷涂技术的基础理论研究也取得了重要进展。 冷喷涂粒子加速加热行为是结合机理研究的先决条件。 因此,文中结合作者多年的研究经验,对冷喷涂过程中气固两相流动行为及喷涂工艺优化的最新进展进行了综述。 首先,分析了冷喷涂喷嘴内外的气体流动特性;其次,讨论了冷喷涂粒子的加速与加热行为;然后,阐述了冷喷涂过程中工艺参数优化的策略;最后,给出了相关研究的发展方向。

    Abstract

    Cold spray has been applied in producing metals or metal matrix composites coatings, additive manufacturing and repairing of components due to its solid-state deposition nature and prominent metallurgical advantages and has been attracting more and more scholars and entrepreneurs around the world in recent years. In the last ten years, great progess has been made on the theoretical study of bonding mechanisms in cold spray. The acceleration behavior of particles during cold spray is an important prerequisite for understanding the bonding mechanisms. Therefore, in this paper, the state-of-the-art of gas-solid twophase flow behavior during cold spray and process parameters optimization were summarized by referring to the relevant research results in recent ten years and the experience of the authors. Firstly, the aerodynamic characteristics inside and outside the cold spray nozzle were analyzed. Secondly, the acceleration and heating behaviors of cold spray particles were discussed. And then, the optimization strategy of process parameters in cold spray was introduced. Finally, the research perspective was given.

  • 0 引言

  • 冷喷涂技术是20 世纪80 年代中期由前苏联科学院理论与应用力学研究所(西伯利亚) Alkhimov等发明, 开始叫冷气动力喷涂( Cold gas-dynamic spray,CGDS),后来逐渐被认可为冷喷涂(Cold spray或Cold spraying,CS);以1990 年发表的论文[1] 为起点,开启了冷喷涂研究的大门;2001 年A.N.Papyrin对冷喷涂方法进行了详细的阐述,并正式提出了临界速度(Critival velocity)的概念[2]。作为一种新型的固态涂层制备方法,冷喷涂具有突出的冶金优势,因此在高质量腐蚀防护[3-4] 与耐磨损[5-7] 金属涂层、复合材料涂层[8-9]等方面获得了重要应用。近几年的大量研究结果表明,冷喷涂技术完全可以用于金属材料增材制造(3D打印)与修复[10-15],并正在获得越来越多的关注,因此,在航空、航天、航海、能源、化工、生物等重点行业有着巨大的应用潜力及价值[16-20]。目前,欧美发达国家正在不断加大对冷喷涂领域的研发投入,每年有大量的科研项目立项,大量的技术专利申请,科技论文数量逐年上升,图1 所示为近10 年冷喷涂相关科研论文的数量统计,与10 年前相比[21-22],数量大大增加,也侧面反映了冷喷涂的“热”。

  • 图1 近10 年冷喷涂相关科研论文的数量统计(WoS) [21-22]

  • Fig.1 Number of research publications on cold spray in recent ten years(WoS) [21-22]

  • 与传统的“高温”热喷涂技术、激光熔覆/增材制造技术等相比,冷喷涂具有很多优点[3-23], 这里不再赘述,但冷喷涂颗粒的高速碰撞过程与累加沉积过程使得涂层内扁平颗粒间界面结合相对较弱,需要进一步提升与改善,根据现有的研究报道,分为喷涂前处理、喷涂过程中处理与喷后处理3 种渠道。喷涂前处理主要包括粉末设计[9-10]。喷涂过程中改善涂层特性的处理方法主要包括原位喷丸[4,10,23]、激光在线辅助[10,23-24]等。喷后处理主要包括热处理[10,23,25]、激光重熔[10,23,26]、搅拌摩擦加工[10,23,27]等。

  • 除此之外,近年来的研究也表明,冷喷涂也可以用于辅助其他加工工艺[23],比如,用作钎焊中间层[28]、改善搅拌摩擦焊接接头组织与力学性能[29]、改善熔焊接头残余应力分布[30],甚至直接实现Al-Cu异种材料连接[31]

  • 针对冷喷涂粒子结合机理的基础研究,2000 年后也获得了国内外学者的广泛关注[32-34]。对于冷喷涂粒子结合机理的理解可以分为3 个层次:(1)粒子加速加热行为研究,以获得高于临界速度的合适工艺参数与沉积窗口;(2)粒子碰撞行为研究,以获得粒子结合机制、临界沉积条件及影响因素以及界面组织演变分析等;(3)涂层组织性能特征及调控。鉴于篇幅所限,文中重点对粒子加速加热行为进行综述,后面两个方面也会陆续给出。作者根据多年来的研究经验以及近年来国际上相关的研究进展,从冷喷涂喷嘴内外气体动力学特性、粒子加速加热行为和工艺参数优化等方面进行综述,为冷喷涂技术研究者与从业者提供参考。

  • 1 冷喷涂喷嘴内外气体动力学特性

  • 冷喷涂喷嘴内的高压气体在喷嘴的喉部由亚音速变为超音速。当气体到达扩张段时,气流速度持续增加,直到接近喷嘴的出口,在出口位置由于要适应环境压力,因此可能会产生复杂的冲击波结构。图2 所示为喷嘴扩张段内部和外部气体的3 种典型流动形式(由速度等值线表示),即欠膨胀、理想膨胀和过膨胀[35]。图2(a) 所示为欠膨胀气流,由于喷嘴出口压力高于环境压力,首先出现的结构是膨胀波;而随着在射流边界处多次反射而形成激波,这两种波随后在射流中呈现周期性,导致气体速度呈周期性波动, 具体表现为先急剧上升, 然后迅速下降。图2(c)所示的过膨胀气流则表现出了相反的波结构。图2( b) 所示为接近理想流动状态下的流场,喷嘴出口处的压力与环境压力并没有显著差异。无论在喷嘴出口处形成哪种流动波结构,当超音速气体射流最终撞击到基体时,都会在基体表面产生高密度、低速区的弓形激波,在弓形激波中,气流速度会突然从超音速降至零。

  • 图2 环境压强为0.1 MPa时,喷嘴扩张段内部和外部气体速度分布计算流体动力学数值模拟结果[35]

  • Fig.2 Computational fluid dynamics modeling result of gas velocity contour inside nozzle divergent section and outside nozzle without substrate at ambient pressure of 0.1 MPa [35]

  • 1.1 工作气体条件对气体流速的影响

  • 计算流体动力学(Computational fluid dynamics,CFD)是研究冷喷涂载气条件(压力、温度和气体种类)对气体流动特性影响的重要工具。对于气体总压,由一维等熵理论可知喷嘴中的气体速度与总压无关。然而,在实际的工作中,喷嘴出口处的气流速度随着总压的增加而增加,并逐渐趋于平稳[36]。产生这种差异的原因是一维等熵理论没有考虑环境压力的影响。实际上,由于环境压力作用,总压会对喷嘴内的气流产生较大的影响[36-38]。图3 所示为气流通过收缩-扩张型(de-Laval) 喷嘴后的流动示意图[39]。一般冷喷涂系统中的环境压力是恒定的,并且与大气压力相等。当总压过低时,不能满足喷嘴喉部达到声速的临界条件,那么整个喷嘴(AB)中的气流速度将保持在亚音速。当临界条件已得到满足(C),气体在喷嘴喉部达到音速,但随后又在喷嘴的发散段降为亚音速。 ABC 这3 种情况不会在实际冷喷涂过程中发生。随着总压的逐渐增大(DEF),气体在喷嘴扩张段开始以超音速流动,但由于喷嘴内扩张段激波的产生,导致气体速度从超音速突然降低到亚音速。随着气体总压的进一步增大,喷嘴内的激波消失,气体在喷嘴扩张段保持超音速,直到喷嘴出口产生斜激波和膨胀波(GHI)。最后,当总压继续增大时,外部射流保持膨胀状态( I),在这种情况下,环境压力不再影响喷嘴内气体流动,此时可近似认为总压与喷嘴内气体流动特性之间的关系基本遵循一维等熵理论,因此喷嘴出口处的气流速度将保持恒定。总之,当总压相对较低时, 会影响喷嘴内的气流速度,但当总压足够高时, 这种影响可以忽略不计。随着总压的进一步增大,喷嘴外部欠膨胀射流的强度将增大,此时喷嘴外的气流速度将可能持续增加。除此之外,一维等熵理论及数值模拟结果都表明,增加总温或者采用分子量更低的氦气均可提高喷嘴内的气体速度[40-42]

  • 图3 气流通过de-Laval喷嘴后的流动示意图[39]

  • Fig.3 Schematic picture of flow through a de-Laval nozzle [39]

  • 现有研究还发现,除气体条件外,基体(喷涂距离、基体形状和基体角度)也会对气体的流动特性产生影响,特别是喷嘴外部射流和弓形激波。压缩弓形激波中的气体压力随着喷涂距离的增加而变化[43-44]。但是弓形激波的尺寸在宽度和高度方向上均呈下降趋势,如图4 所示,这主要是由于外部射流超音速核心区缩短[45]。另外,基体的形状、角度对冲击射流也会产生影响。圆柱以及呈一定角度放置的基体上弓形激波的强度及形状与正常垂直平放的基体不同。圆柱基体上的弓形激波强度更小,因为流体未被基体完全阻挡[46];而呈一定角度放置的基体由于没有对称放置, 导致不规则形状的弓形激波的产生[47]

  • 图4 不同喷涂距离下采用气体密度表征的基体表面冲击射流和弓形激波的数值模拟结果[45]

  • Fig.4 Modeling result of impinging jet and bow shock of substrate surface represented by gas density at different standoff distances [45]

  • 送粉条件是影响气体流动特性的另一重要因素。由于低温送粉气体和高温工作气体(主气)之间的热交换,喷嘴内的气体速度和温度随着送粉压力的升高而降低[48-49]。相反,提高送粉气体温度有利于提高喷嘴内主气的速度和温度, 因为主气获得了送粉气体的额外能量输入[50]。与空气和氮气相比,使用氦气作为送粉气体可以在喷嘴内部和外部产生更高的气体速度[51]。另外,在许多数值模拟工作中,送粉率对气体的影响往往被忽略。一些研究表明,提高送粉率可以降低气体动量,当送粉率较高时,会减弱激波、膨胀波和弓形激波[44,52]。随着送粉率的增加,喷嘴内部气体的流动速度也会下降。这说明当送粉率较高时,必须考虑气相和固相之间的相互作用。

  • 1.2 喷嘴形状对气体流动特性的影响

  • 喷嘴的扩张比(又称膨胀比,出口截面积与喉部截面积之比)是冷喷涂喷嘴设计的一个重要因素。理论上,扩张比越高则气体的马赫数及速度越高。但是在实际情况中,气体总压对喷嘴内外的流动具有显著影响,只有当总压足够高,环境压力不再影响喷嘴内的流动,喷嘴出口处的马赫数和气体速度才会随着扩张比的增大而增大[37-38]。这说明尽管扩张比高的喷嘴能够产生较高的气流速度,但同时需要足够高的总压。此外,喷嘴扩张段的长度也会影响气体速度[37]。扩张段越长,则会导致更大的壁面能量耗散,因此, 喷嘴出口处的马赫数会随着扩张比的增加而逐渐减小。

  • 针对内孔类零部件内表面强化改性或修复再制造的需求,研究人员提出利用冷喷涂技术来实现这一目标,并对喷嘴结构进行了改进[53-54]。图5 为气流在改进后的喷嘴中的流动情况。由图可知,气流在喷嘴径向截面入口处加速到超音速,在转向处先远离喷嘴壁,随后又重新附着并先后产生两次激波。由此可见,射流在距离喷嘴出口一定范围内具有不稳定性,并且会产生弯曲振荡。

  • 图5 气体流场计算结果[53]

  • Fig.5 Calculation results of gas flow field [53]

  • 1.3 冷喷涂气体流动特性的实验观察

  • 气体流动实验观测对于深入理解气体动力学和粒子加速行为以及验证模拟结果至关重要。气体通常是无色的,因此难以对其进行观测,而气体可视化是分析气体流动特征的一种有效方法。目前,纹影摄影技术是实现气体流动可视化最常用的方法,它能够捕捉气体密度梯度引起的折射率变化,并将其转换成人眼和摄像机可以观察到的不同光强。图6 所示为利用该技术实现的冷喷涂喷嘴出口下游超音速射流的可视化以及与数值模拟结果的对比。对于喷嘴内部的气体流动,由于喷嘴通常由不透明材料制成,用光学技术测量流动特性非常困难。 KATANODA H等[55] 曾尝试用透明玻璃作为喷嘴材料来观察低压冷喷涂喷嘴内的气体流动,如图7 所示,可以清楚的观察到喷嘴内复杂的激波。该研究为传统高压冷喷涂喷嘴内部气体流动的可视化提供了参考。尽管通过纹影照相成功实现了冷喷涂流场结构(密度梯度)的可视化,但该技术无法定量地记录速度和温度等重要参数。因此,在大多数情况下,纹影摄影技术仅用于验证CFD模型的计算精度。

  • 图6 冷喷涂喷嘴外部冲击射流数值模拟结果与相同工况下实验纹影照片对比[52]

  • Fig.6 Comparison of impinging jet outside the nozzle in cold spray between CFD modeling result and experimental Schlieren photograph at the same working condition [52]

  • 图7 不同入口压力下低压冷喷涂喷嘴内部和外部超音速气流的纹影图像[55]

  • Fig.7 Schilieren image of supersonic gas flow pattern inside and outside a low-pressure cold spray nozzle with different inlet pressures [55]

  • 2 冷喷涂粒子加速加热行为

  • 2.1 喷涂条件对粒子速度的影响

  • 首先是气体条件。冷喷涂粒子的加速行为主要取决于气体的流动特性。一般而言,气体速度较高,颗粒的加速效果则越好,从而可以获得较高的颗粒速度。现有的大量研究发现,冷喷涂粒子速度会随着气体总压、总温的增加及分子量的减小而增加[40-42,47,56-61],增加总温比增加总压的影响更显著。该发现已被广泛应用于实际的冷喷涂过程中,用于提高颗粒速度和改善涂层的结合性能。图8 所示为数值模拟得到的气体速度与总温、总压及载气种类的关系曲线[60,62]。需要注意的是,气体温度过高可能会导致涂层及基体产生由热效应引起的缺陷,而使用氦气喷涂则会显著增加经济成本。此外,送粉气体的压力、温度和气体种类也会对粒子的速度产生影响,较低的送粉压力、较高的送粉温度或使用氦气作为送粉气体均有助于提高混合气体(载气和主气) 的速度,从而提高粒子的撞击速度[49-51]

  • 图8 喷嘴出口30 mm处粒子速度随总压、总温和气体种类的变化[60,62]

  • Fig.8 Modeling result of particle velocity at the location 30 mm away from nozzle exit as a function of gas stagnation pressure, temperature and species [60,62]

  • 其次,喷涂距离是影响粒子碰撞速度及涂层沉积效率的另一个重要参数。一般认为,弓形激波区内的压力随着喷涂距离的增加而变化,由于弓形激波区域的压力决定了粒子的减速行为,因此基体应放在激波压力最小的位置,从而削弱粒子在穿过弓形激波时的减速效果。另一方面,基体的几何形状和放置角度同样会影响粒子速度, 决定沉积效率的法向速度对涂层性能的影响更为重要[43,47]

  • 最后,粒子本身特性也会对粒子速度产生重要影响。质量较小的粒子更容易受到超音速气流的影响,喷嘴出口处的粒子速度随着粒子尺寸(或密度)的增加而降低。尽管粒子在喷嘴出口处获得了很高的速度,但当这些粒子进入弓形激波区时,粒子的速度会明显下降。而对于较重的粒子,尽管喷嘴出口处的速度很小,但这些粒子在弓形激波处的减速不明显[39,41,67,49-50,57,61,63-66]。图9 为通过CFD计算得到的Cu颗粒尺寸与撞击基体时速度的关系[64]。由于尺寸较小的粒子在弓形激波后速度会明显下降,而尺寸较大的粒子在喷嘴内又无法获得足够大的加速,因此,随着粒子直径的增大,会存在一个最佳粒径以保证粒子在撞击基体时获得最大速度,在此基础上粒径增大或减小都将导致其速度相应减小,如图9 所示。另外,形状不规则的粒子受到的气体拖曳力更大, 因此,与球形粒子相比,形状不规则的粒子加速效果反而更好。因此,在相同的当量尺寸下,形状不规则的粒子可以获得更高的撞击速度[68]

  • 图9 采用CFD模拟计算得到的Cu颗粒尺寸与撞击速度的关系[64]

  • Fig.9 Impact velocity as function of copper particle size predicted by CFD modeling [64]

  • 最近的研究发现,当送粉率处在较低范围时, 随着送粉率的增加,粒子速度略有下降[40,69],此时,气-固两相之间的动量交换可以忽略不计。但当送粉率较高时,这种影响将更加显著,并且随着送粉率的增加,粒子速度明显下降[44,52,70-71]

  • 2.2 喷嘴形状对粒子速度的影响

  • 喷嘴的扩张比对粒子速度具有显著影响。当喷嘴扩张比较高时,可以获得更高的粒子速度,但同时也需要较高的总压。在总压固定的情况下,存在一个最优的喷嘴扩张比,以获得最大的粒子速度[37,58,72-73],在此基础上减小膨胀比会导致气体流速下降,而增大则会导致喷嘴内气体流动受到环境压力的影响,两种情况都会导致粒子速度下降。此外,喷嘴扩张段长度对粒子的撞击速度也具有显著影响[37,58]。图10 所示为粒子碰撞速度随喷嘴扩张段长度变化的模拟结果[37]。从图中可以看到,随着扩张段长度的增加,粒子速度呈现出先增大再减小的趋势。还有研究表明,对于矩形截面的喷嘴,喉部宽度与扩张段长度的比值对喷嘴扩张段的粘性边界层和恒定扩张比下的粒子加速具有重要影响[74]。在设计矩形喷嘴时,不建议喷嘴出口宽长比低于0.02,因为较强的边界层效应导致喷嘴内粒子速度下降[74-75]。目前为止还没有对圆形喷嘴进行过类似的研究。此外,数值模拟结果表明,与相同扩张比的锥形喷嘴相比,使用钟形喷嘴可以获得更高的粒子速度[76]

  • 图10 粒子碰撞速度随喷嘴扩张段长度变化的模拟结果[37]

  • Fig.10 Modeling result of impact velocity of particle as a function of nozzle divergent length with different particle sizes and expansion ratios [37]

  • 粉末的送入位置对粒子的加速行为也有影响。由于粒子加速主要发生在喷嘴的扩张段,当在喷嘴的收缩段添加粉末粒子时,送粉位置对粒子的速度影响则相对较小。但是,当送粉位置位于喷嘴扩张段时,送粉位置越靠近出口,则粒子在喷嘴中的加速时间越短,粒子的撞击速度也越小[77]。在某些情况下,送粉口位于喷嘴入口前段的混合腔,粒子有更长的加热时间,因此,粒子温度会相对较高[48,78];粒子速度也会随着预热腔长度的增加而增加。

  • 2.3 粒子轨迹和落点位置

  • 冷喷涂粒子在喷嘴内外以及基体表面的分布是目前的研究重点之一。 Karimi等[46] 基于非轴向送粉的喷嘴模型,率先研究了粒子在气流中的轨迹和分布。图11 所示为直径 Φ5~Φ60 μm的粒子在基体表面的分布情况。结果表明,由于非轴向送粉,粒径较大的粒子主要集中在中心底部区域,而粒径较小的粒子由于受气流的影响分散更为严重。近年来,相关研究主要侧重于径向送粉的喷嘴模型。对于广泛使用的轴向送粉方式,粒子在注入位置的下游或喷嘴的收缩段会出现明显的发散现象,发散导致粒子与喷嘴内壁之间发生碰撞, 从而增加喷嘴堵塞的风险[49,78-80]。图12 所示为采用CFD计算模拟得到的Ti粒子在喷嘴内外的射流轨迹[79]。从图中可以明显观察到粒子与喷嘴内壁发生了碰撞,这增加了喷嘴堵塞的潜在风险。另外,较高的送粉压力会导致颗粒在喷嘴收缩段产生更严重的分散现象及颗粒-内壁碰撞行为[49]。 OZDEMIR O C等[81]的研究还发现送粉管的直径对粒子-内壁的碰撞也会产生明显的影响。对于直径较大的送粉喷管,在喷嘴扩张段更容易造成粒子与喷嘴内壁碰撞,如果送粉方向与中心轴线稍有偏差,将导致粒子与喷嘴内壁发生剧烈碰撞。 LIEBERSBACH P等[82] 通过在Ansys-Fluent中建立的自定义方程(User-difined fanction,UDF) 来记录粒子与喷嘴内壁碰撞时的速度,并与临界速度进行比较,以分析喷嘴堵塞的原因。结果表明,在稳态条件下,粒子几乎不会和喷嘴内壁发生碰撞,而提高送粉压力会导致粒子与内壁发生碰撞,并可能导致喷嘴堵塞。除空间分布的研究外,大量的数值模拟研究还表明粒子速度在喷嘴外及基体表面的分布呈现出中心向外部沿径向逐渐减小的分布规律[40,49,80,83-84]。基于CFD预测的粒子位置及速度的空间分布情况,ZHU W等[85]建立了冷喷涂涂层在基体表面的轮廓形貌,成功将CFD结果与实际的涂层相关联。

  • 图11 采用 Φ5~Φ60 μm粉末时距喷嘴出口10 mm基体表面的粒子分布情况[43

  • Fig.11 Footprints for the particles ranging between Φ5 and Φ60 μm on a flat substrate10 mm away from nozzle exit [43]

  • 图12 采用CFD计算模拟得到的喷嘴内部和外部钛粒子射流轨迹(1.4 MPa,550℃) [79]

  • Fig.12 Trajectories of titanium particle stream colored by velocity magnitude at the stagnation pressure and temperature of 1.4 MPa and 550℃ [79]

  • 2.4 粒子温度特征

  • 冷喷涂粒子温度也是影响涂层性能的重要因素,较高的粒子温度会使临界速度降低,进而有助于涂层沉积[64-65,86]。由于技术上的限制,目前很难在实验中测量粒子的温度,现有的研究方法主要是采用CFD数值模拟方法以及理论分析。提高载气的总温能够向粒子输入更多的热能,从而也能够提高粒子在撞击基体时的温度[57,59]。依据气体流动的能量守恒(气体速度升高意味着气体温度下降),提高粒子温度必须要牺牲粒子的速度。因此,在没有额外装置的前提下,无法满足粒子温度与速度的同步提高。为了同时获得高的粒子速度和粒子温度,通常在喷嘴前段加装预热装置[78-79,87]。总而言之,增加气体总温、采用预热腔对粒子预热是同时提高粒子速度和温度的两种有效方法。

  • 2.5 粒子速度的实验测量

  • 为了阐明粒子在冷喷涂过程中的运动行为和临界速度,相关学者采用多种实验方法对粒子的速度进行了测量。目前常用的测量粒子飞行速度的方法有3 种:激光双聚焦(L2F)、多普勒图像测速(Drppier picture vebcimetry,DPV) 以及粒子图像测速(Particle image velocimetry,PIV)。早期的研究主要采用L2F技术测量冷喷涂的粒子速度[67,88],该技术可以测量有限体积内单个粒子的飞行速度,但其空间分辨率相对较低,后续应用较少。采用DPV方法可得到某一横截面的速度分布图,但测量精度相对较低且需要较长的测量和分析时间。 PIV是一种更先进及灵活的测量技术,它能以更高的空间分辨率来记录瞬时速度分布,不仅大大提高了测量精度,而且还缩短了实验时间。图13 是分别采用DPV和PIV测量的横截面和纵截面处的典型粒子速度分布图[83,89]。近年来, 诞生了一种改进的PIV方法———粒子跟踪测速法(Particle tracking velocimetry,PTV),研究人员将其应用于冷喷涂粒子的速度测量。与PIV相比,PTV在单相机曝光期间使用多脉冲激光照明,因此PTV可以跟踪图像中特定粒子飞行的轨迹。图14 所示为典型的通过PTV技术测量的图像[90]。此外,红外摄像技术也被应用于粒子加速行为的表征。采用红外摄像技术,可以直观地观测到粒子在喷嘴外的扩散RAOELISON R N等[92-93]也使用过与PIV类似的行为,但该技术无法获得粒子的速度[91]。装置来表征粒子扩散行为。根据目前所有粒子测速相关的研究以及主要结论,通过实验观测得到的结果与理论计算和CFD数值模拟结果基本保持一致。值得一提的是,KOIVULUOTO H等[90] 的最新研究首次基于PIV技术同时对冷喷涂粒子的速度和粒径进行了测量,结果表明,粒子速度随着粒子直径的增大而减小。 MEYER M等[94] 的最新研究使用透明石英作为喷嘴壁材料,测量了冷喷涂喷嘴内的粒子速度。图15 显示了随着压力的增加,Stellite-21 粉末在透明喷嘴内粒子速度的变化,在喷嘴内可以清楚地看到粒子的加速过程。

  • 图13 采用DPV和PIV测量的横截面和纵截面处的典型粒子速度分布图[83,89]

  • Fig.13 Particle velocity distribution at cross-section measured by DPV and longitudinal section measured by PIV [83,89]

  • 图14 典型的PTV图像[90]

  • Fig.14 Typical PTV images [90]

  • 图15 Stellite-21 粒子速度随喷嘴内压力升高的变化[94]

  • Fig.15 Spatial evolution of particle velocity for Stellite-21 with increasing pressure within nozzle [94]

  • 3 冷喷涂过程工艺参数优化

  • 工艺参数的选择对冷喷涂起着至关重要的作用。图16 所示为冷喷涂过程中典型的工艺参数,包括:气体参数(压力、温度、种类等)、送粉参数(送粉率等)以及喷嘴参数(喷嘴移动速度、扫描间距、喷涂距离、喷涂角度、喷涂路径等) [13]

  • 图16 冷喷涂过程中典型的工艺参数示意图[10,13]

  • Fig.16 Schematic of typical manufacturing parameters used in cold spray [10,13]

  • 3.1 气体参数

  • 加速气体是冷喷涂过程中最重要的工艺参数,因为它直接决定了粒子的碰撞速度,进而对沉积涂层的性能产生影响。通常而言,冷喷涂常使用的气体包括氦气、氮气和空气。气体压力通常为0.5~7.0 MPa, 气体温度通常为室温至1000℃。适当增加气体压力、提高气体温度或选择分子量较小的气体可以获得更高的粒子碰撞速度,如图8 所示[60,62]。使用氦气来替代氮气和空气是提高粒子碰撞速度最有效的方法,但是使用氦气会导致成本大大增加。此外,与增加气体压力相比,通过提高气体温度来增加粒子的碰撞速度效果更好。

  • 迄今为止,冷喷涂领域的学者普遍认为,提高粒子的碰撞速度可以改善涂层的性能。大量实验结果表明,提高粒子的碰撞速度能够显著提高沉积效率、涂层致密度、涂层强度(结合强度或拉伸强度)和粘结强度(涂层与基体之间),这主要是因为涂层的固有缺陷减少,金属键合作用增强[11,95]。图17 为粒子碰撞速度(或气体参数)对冷喷涂Ti涂层沉积效率、涂层孔隙率、涂层强度和粘结强度的影响[96-98]。粒子碰撞速度增加,加工硬化作用增强,导致涂层的硬度升高。此外,提高粒子的碰撞速度会导致冷喷涂涂层的残余应力增加,这是由于粒子的塑性变形增加导致的[99-102]。然而,较高的气体温度可以在基体表面起到原位退火的作用,从而释放涂层内部的残余应力,因此,提高气体温度不会使残余应力显著增加[103-105]

  • 图17 粒子碰撞速度(或气体参数)对冷喷涂Ti涂层孔隙率[96]、涂层沉积效率[96]、涂层强度[97]和粘结强度[98]的影响

  • Fig.17 Effect of particle impact velocity( or gas parameters) on deposition porosity [96], deposition efficiency [96], deposit strength [97] and deposit adhesion strength [98] of CSAM titanium deposits

  • 3.2 喷嘴参数

  • 3.2.1 喷嘴移动速度

  • 喷嘴移动速度决定了喷涂持续的时间和单位时间内撞击基体的粉末数量,从而直接影响到单道次喷涂沉积物的厚度和截面形貌[71,106-112]。一般而言,如果喷嘴的移动速度较低,单道次喷涂的沉积物会更厚,并且截面轮廓形貌将更加陡峭,如图18 所示,当然也可以通过提高送粉率来实现。沉积物的厚度轨迹会随着喷嘴移动速度的变化而改变,这是由单位时间内或单位面积内沉积的粉末数量的不同导致的,而减小喷嘴移动速度和提高送粉率均会增大单位时间内或单位面积内沉积的粉末数量。推进气体通过超音速喷嘴的流动特性导致了轨迹的变化。根据流体力学理论,中心区域的粒子速度和沉积效率比外部区域高[40,49,83]。由于速度的径向变化,沉积物的截面轮廓呈现出高斯分布的形状,如图18 所示。当后续粒子继续沉积时,这些粒子将呈一定的角度撞击在沉积物的倾斜侧,这进一步降低了粒子的沉积效率并使倾斜侧更加陡峭。因此,随着喷嘴移动速度的降低和送粉率的升高,沉积物的轮廓越来越陡峭。综上,在冷喷涂实际应用中,通过调控喷嘴移动速度和送粉率,可以实现对单道次沉积物厚度和轮廓的控制[106-107]

  • 图18 喷嘴移动速度对单道次沉积物厚度和截面轮廓的影响[110]

  • Fig.18 Effect of nozzle traverse speed on the single-track deposit thickness and cross-sectional profile [110]

  • 喷嘴移动速度对涂层的微观结构和性能也有显著的影响。涂层的致密度随着喷嘴移动速度的减小而升高,但同时涂层的力学性能也会下降,如弹性模量、涂层强度和粘结强度[111,113-114]。图19 为Ti-6Al-4V涂层/Ti-6Al-4V基体在不同喷嘴移动速度下的截面形貌[111](箭头表示涂层/基体的界面)。由图19 可知,随着喷嘴移动速度的增加,涂层的孔隙率增大。此外,当喷嘴移动速度最低时,如图19( a) 所示,涂层在基体表面发生层离,这是由于界面处残余应力过高, 导致粘结强度下降[71,111]。其他的一些研究结果同样表明,当喷嘴移动速度较低或送粉率较高时,会导致涂层在基体表面的分层现象,这在一些冷喷涂实验中也常常发生[71]。喷嘴移动速度另一个潜在的影响是高温冲击射流对涂层或基体的热效应。当喷嘴移动速度较低时,会导致基体和涂层的温度升高, 这将有利于粒子沉积[111,115],但同时会导致界面处产生热应力[116]

  • 图19 Ti-6Al-4 V涂层/Ti-6Al-4 V基体在不同喷嘴移动速度下的截面形貌[111]

  • Fig.19 Cross-sectional morphologies of Ti6Al4V deposits onto Ti6Al4V substrates fabricated with different nozzle traverse speeds [111]

  • 目前,关于喷嘴移动速度的选择还没有统一的规定。然而,根据现有的研究结果和作者经验,采用较低的喷嘴移动速度往往会导致涂层和基体之间的局部残余应力较高、粘结强度较低, 这对于使用冷喷涂技术修复破损零件是不利的[71]。因此,作者建议在冷喷涂应用中尽量避免选择较低的喷嘴移动速度。

  • 3.2.2 喷嘴扫描间距

  • 冷喷涂涂层的沉积是通过喷嘴按照预定的轨迹在基板表面逐行逐层扫描来实现的。换句话说,涂层是由多个单道次沉积形成的沉积物叠加而成的。叠加策略是最常用的扫描方法,如图20 所示,两个相邻的单道次沉积物互相叠加。扫描间距是指任意两个相邻的单道次沉积物中心线之间的距离。扫描间距主要对冷喷涂涂层厚度的均匀性和表面形貌产生影响,选择合适的扫描间距可以得到厚度均一、表面光滑的涂层。

  • 图20 扫描间距示意图[13]

  • Fig.20 Schematic of scanning step [13]

  • 扫描间距的选择取决于单道次沉积物的宽度。在作者过去的实验中,为了保证涂层表面的平整度,通常将扫描间距设置为单道次沉积物宽度的1/2。然而,有研究结果表明,通过对扫描间距进一步优化可以减少涂层表面的宏观起伏(两道次之间)。在这项研究中,研究人员使用自行开发的软件工具包预测了最佳的扫描间距[117]。图21 给出了使用软件工具包模拟的冷喷涂Al涂层的厚度值和通过实验测量的实际厚度值。显然,扫描间距为4 mm时涂层的厚度比扫描间距为7 mm时的涂层厚度更高,表面起伏更小,由此可以看出扫描间距在冷喷涂过程中的重要性。但是,目前关于不同扫描间距对涂层影响方面的研究相对较少,扫描间距对涂层性能的影响机制尚不清楚,亟待更多的深入研究。

  • 图21 扫描间距为4 和7 mm时冷喷涂Al涂层表面平整度的预测结果和实验结果[117]

  • Fig.21 Simulation and measured results of surface flatness of cold sprayed Al deposit at scanning step of 4 and 7 mm [117]

  • 3.2.3 喷涂距离

  • 喷涂距离是指喷嘴出口与基体表面之间的距离。在超音速射流中,由于射流和大气之间的动量交换,射流核心区的强度沿着射流中心轴线逐渐减小[49-50]。射流核心区的粒子在拖曳力的作用下被快速加速。然而,在气体离开喷嘴扩张段后的很短一段距离内,气体的速度降至粒子速度之下,由此产生的负阻力导致粒子速度开始下降。粒子的碰撞速度和沉积效率随着喷涂距离从0 开始增加而增加,在到达最佳喷涂距离之后开始下降[45]。这在PATTISON J等[45] 冷喷涂铝、铜和钛涂层和LI W Y等[118]冷喷涂铜涂层的实验中得到了验证,如图22 所示。然而,在LI W Y等[118] 的实验结果中发现了一个非常近的最佳喷涂距离,当喷涂距离从10 mm增加到110 mm时,冷喷涂铝涂层和钛涂层的沉积效率单调下降。此外, 还有一些研究集中在喷涂距离对沉积涂层的影响[119-122]。由于研究的数量有限,目前尚不能就喷涂距离在冷喷涂过程中的影响达成共识。尽管在目前大多数的研究中将喷涂距离设置在10~40 mm,但喷涂距离对沉积涂层性能的影响尚不明确。因此,未来需要更加深入的研究。

  • 3.2.4 喷涂角度

  • 喷涂角度是指喷嘴轴线与基体表面的夹角, 它主要通过影响粒子碰撞速度的有效沉积分量(法向分量),从而对沉积涂层的质量产生影响。当以非垂直于基体表面的角度喷涂时,粒子速度的法向分量使颗粒沉积,而速度的切向分量则发挥相反的作用使颗粒离开基体表面[123]。随着喷涂角度的减小,粒子速度的法向分量减小,切向分量增大,粒子撞击基体的有效速度降低,沉积涂层的质量明显下降。沉积效率、涂层强度和粘结强度均会随着喷涂角度的减小而降低[67,97,119,124-127]。如图23 所示,随着喷涂角度的减小,冷喷涂钛涂层的孔隙率增加[97]。此外,模拟实验结果表明残余应力会随着喷涂角度的减小而减小,然而这一结果还有待实验验证[100]。喷涂角度同样会对单道次喷涂沉积物的截面轮廓形貌产生影响。当以一定的角度喷涂时,沉积物截面的二维轮廓形貌将会发向一侧发生倾斜, 如图24 所示。由于喷嘴呈一定角度的倾斜,粒子的喷涂距离不同,从而导致颗粒碰撞区域的沉积效率不均匀[112],这可能会影响到沉积涂层的均匀性。总之,以一定角度喷涂会对沉积涂层的整体性能产生不利影响。因此,在冷喷涂过程中,应尽可能使喷嘴与基体表面垂直。

  • 图22 沉积效率与喷涂距离的关系[45,118]

  • Fig.22 Deposition efficiency as a function of standoff distance [45,118]

  • 3.3 粉末特性及送粉参数

  • 3.3.1 粉末特性

  • 粉末特性主要包括粉末颗粒尺寸、形貌以及种类(密度差异)。目前冷喷涂已经实现了多种材料的沉积,主要包括金属及其合金、金属基复合材料、金属陶瓷、陶瓷、聚合物以及纳米结构材料等,其中以金属及其合金为主。由于冷喷涂过程中的温度较低,对基体和粉末材料的热影响小,在喷涂过程中基本没有氧化现象,因此,特别适用于制备温度敏感材料(如纳米材料[128]、非晶材料[129])、易氧化材料(如铜[130]、钛[131]、铝[132] 等)、易相变材料(如WC-Co [133])等涂层。

  • 粉末形貌由它的制造工艺决定,采用气雾化法制备的粉末通常为球形,而采用氢化-脱氢法和机械合金化法制备的粉末通常为非球形的不规则形状。粒子的速度和粉末形貌有关,不同的粉末形貌会对涂层的微观结构和性能产生影响。非球形颗粒的表面积较大,在流动中受到更大的气体拖曳力,在同样的条件下与球形颗粒相比会达到更高的碰撞速度,更有利于颗粒的沉积[134]

  • 粉末粒径对粒子的加速行为和粒子速度有着显著影响。冷喷涂粉末的粒径通常具有一个分布范围,粒径的尺寸一般为5~50 μm。如图25 所示,在相同的条件下,粒子的速度随着颗粒尺寸的增加而减小,因此粒径相对较小的颗粒更容易获得较高的速度从而沉积在基体表面[64,86]。而粒径太小的颗粒由于受到高速气流作用在基体表面冲击波的影响较大,在到达基体之前会发生偏离,无法形成涂层。此外,粉末粒径对粒子的临界速度也会产生影响。

  • 图23 不同喷涂角度的冷喷涂钛涂层截面形貌[97]

  • Fig.23 Cross-sectional morphologies of cold sprayed titanium deposits produced with different spray angles [97]

  • 图24 喷涂角度对单道次沉积涂层截面轮廓形貌的影响[112]

  • Fig.24 Effect of spray angle on cross-sectional profile of single-track deposit [112]

  • 图25 粒子临界速度和撞击速度随粒径的变化[86]

  • Fig.25 Change of vcrit and vimpact with particle size [86]

  • 3.3.2 送粉率

  • 送粉率是指单位时间内进入喷嘴的粉末量, 它是唯一一个由送粉器控制的参数。送粉率对冷喷涂涂层性能的影响主要体现在以下3 个方面:首先,送粉率对通过喷嘴的气流产生影响,进而对粒子的速度产生影响[69,71,135]。图26 显示了喷嘴出口处粒子速度和送粉率的关系[136]。当装载粉末量较大时,由于气-固两相的强相互作用, 粒子速度随着送粉率的增加而减小,导致了涂层的孔隙率略有增加,沉积效率、硬度和拉伸性能下降。在冷喷涂过程中, 送粉率通常远小于100 g/s,一般为10~30 g/s,在此范围内,送粉率对粒子速度的影响不明显[71]。其次,送粉率会对单道次沉积物的厚度和截面二维轮廓产生影响,当送粉率较高时,涂层厚度会更厚,轮廓也更加陡峭[106-107]。在这点上,送粉率和喷嘴移动速度的影响相似,在确定单道次沉积物的截面轮廓时,必须要同时考虑这两个因素。最后,当送粉率较高时,会导致涂层与基体之间产生较大的局部残余应力。残余应力过高会使涂层在冷喷涂过程中从基体表面分层剥离[69,71]。综上所述,冷喷涂过程中的送粉率不宜过高。

  • 图26 喷嘴出口处粒子速度和送粉率的关系[136]

  • Fig.26 Relationship between particle velocity and powder feed rate at nozzle exit [136]

  • 4 结论与展望

  • (1) 影响冷喷涂粒子加速的主要因素包括: 工作气体参数(压力、温度、种类)、送粉气体参数(温度、种类)、喷嘴尺寸参数(扩张比、扩张段长度)、粉末特性(尺寸、形貌、材料种类)、送粉率和喷涂距离。有些参数越高越好,比如气体压力与温度,但受设备能力限制,只能采用较高值。有些参数需要采用适中值,比如喷嘴扩张比、扩张段长度、粒子尺寸、送粉率和喷涂距离。由于喷涂应用的需要,材料种类基本不可选择,粉末形貌可做一定选择:球形或非球形。而气体种类的选择也要根据质量与成本因素协调考虑。

  • (2) 影响粒子碰撞温度的主要因素包括:工作气体温度、送粉气体温度、喷嘴收缩段长度、送粉喷管位置、粉末尺寸与种类。受设备能力与喷涂材料熔点的限制,气体温度只能选择较高条件。根据需要调整送粉位置与喷嘴收缩段长度, 但过高的粒子温度造成喷嘴堵塞的倾向增加。

  • (3) 考虑到冷喷涂层沉积质量,工艺参数的优化除了获得尽量高的粒子速度、适当的粒子温度外,还应考虑实际被涂敷构件条件,适当选择喷嘴移动速度、喷涂角度和喷嘴扫描间距等。

  • 尽管现有研究已经获得了工艺条件设计方法与喷嘴设计准则,但从基础理论角度出发,仍有一些关键问题需要解决:①喷嘴堵塞的关键因素及其影响规律;②喷嘴移动速度与轨迹的协同控制方法,以期获得更好的涂层形状;③喷涂距离与喷涂角度对涂层质量的协同影响机制;④送粉率对涂层质量的影响机制;⑤极端条件下(比如真空、水下、强磁等)的粒子加速加热行为。

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