发布日期：2026-1-25 20:43:48
引言
钛合金(Titanium alloys)凭借其优异的比强度、耐腐蚀性和良好的生物相容性，已成为航空航天、海洋工程及生物医学等先进工程领域的关键结构材料[1-3]。根据合金元素及室温微观组织特征，钛合金通常可分为α型[4-7]、α+β型[8-11]和β型[12-15]三类，其选型需紧密结合具体服役条件与性能要求。图1钛合金的主要分类及应用场景[4-15]
尽管传统制造技术(如铸造[16]、锻造[17]、粉末冶金[18]等)在大批量、结构简单零件生产中具备可靠性与一致性优势，但仍面临三大挑战:(1)能源消耗大、碳排放高，与绿色制造理念相悖;(2)热导率低且高温化学活性强,易引发组织缺陷并降低性能;(3)材料利用率低、成本高、加工周期长，难以实现复杂曲面结构的高效成型，加工效率与设计自由度受限，无法满足高性能构件需求。随着制造业升级与绿色、可持续发展需求，亟需突破传统技术瓶颈。近年来，增材制造(AdditiveManufacturing，AM)作为一种革命性成型技术，凭借其低能量损耗、高材料利用率与对复杂几何结构的高度制造柔性等优势，在高性能、高精度钛合金零部件的一体化制造方面展现巨大优势。
本文系统阐述了以激光、电弧及复合能量场为代表的金属AM技术在钛合金构件制备中的应用现状，深入分析了工艺参数优化对钛合金微观组织与性能的调控机制，阐明了热处理技术在改善钛合金微观组织及提升力学性能、腐蚀性能方面的作用机理，并基于当前研究进展对AM钛合金形性一体化调控技术的未来发展方向进行了展望。
1、钛合金的增材制造技术
金属AM技术基于“离散+堆积”原理，通过能量源将金属原材料逐层熔化、凝固成形，最终实现三维构件的直接制造[19]。根据能量源类型与原料形态的差异，适用于钛合金的主流AM技术可分为激光定向能量沉积(Laser Directed Energy Deposition，LDED)、激光选区熔化(Selective Laser Melting，SLM)[20]以及电弧熔丝增材制造(Wire Arc Additive Manufacturing，WAAM)[21]。相关研究表明[22-25]，在金属AM技术中引入外场可有效优化钛合金构件的成形质量和性能，为该领域的发展提供了重要技术支撑。
1.1激光定向能量沉积技术
LDED技术，亦称激光近净成型技术(Laser Engineered Net Shaping,LENS)，其工艺原理为通过喷嘴将金属粉末送至高能激光作用区域，粉末迅速熔化形成熔池，随喷嘴与工作台的同步移动实现逐层沉积，实现大型复杂构件的高效成型。图2激光、电弧及复合能量场技术原理图[26,34,38,39,55]
由于LDED光斑尺寸较大，成形件表面粗糙、尺寸偏差大[27,28]及微裂纹、孔洞等缺陷[29,30]。制约了该技术的进一步应用。为此，有必要系统研究不同工艺参数对熔覆层成形行为的影响，以实现钛合金构件形性一体化调控。当前，研究人员围绕熔覆层成形机理已开展多项工作[31,32]，黄辰阳等[33]建立了高精度多物理场数值模型，模拟了LDED过程中的激光-粉末-熔池的相互作用与流动凝固行为，并通过TC17合金单道熔覆层实验验证模型可靠性，基于该模型，系统预测了不同工艺参数下熔覆层形貌与尺寸变化趋势，揭示了粉末温度分布和基板能量分配比例对熔池流场及熔覆尺寸的关键影响，为成形精度控制提供了理论依据。然而，成形精度不足、组织各向异性等关键问题仍亟待解决。后续可通过多物理场耦合仿真与实验相结合的方式优化工艺参数，并借助热处理调控组织形貌以提升构件性能，最终推动大型高性能钛合金构件的精密化制造。
1.2激光选区熔化技术
SLM技术，亦称为激光粉末床熔融(Laser Powder Bed Fusion,LPBF)技术，是一种基于粉末床的AM技术。其工艺过程为:首先通过刮刀或铺粉辊将金属粉末均匀平铺在基板上，随后高能激光束依据三维模型的切片数据对粉末层进行选区扫描，使粉末熔化形成熔池，当前层成形后，基板下降一个层厚，重复进行铺粉与扫描过程，逐层堆积直至完成整个构建制造[34]。SLM成型过程中熔池的冷却速率极高(10~10~8K/s)，能有效抑制晶粒生长和合金元素偏析，在熔池内形成细小均匀的显微组织，从而提高成形件性能[35]。由于钛合金化学活性高、高温粘性大，SLM为其加工提供良好的成型环境和技术路径[36]。此外，SLM成型过程中因极高的冷却速率与逐层堆积带来的循环热历史，使构件内部产生显著的温度梯度，进而引发热收缩不均，最终导致残余应力累积，加剧构件变形与开裂风险并降低力学性能稳定性[37]。合适的热处理工艺可以极大地减小快速凝固成形过程中的残余应力，改变组织形貌与尺寸等，从而优化组织和力学性能。
1.3电弧熔丝增材制造
WAAM技术以电弧为热源将丝材熔化，依据规划路径逐层堆积成形构件。根据电弧热源特性，WAAM技术可分为熔化极气体保护焊(Gas Metal Arc Welding, GMAW)、非熔化极气体保护焊(Gas Tungsten Arc Welding,GTAW)和等离子弧焊(Plasma Arc Welding,PAW),其基本原理如图2(c-e)[38]所示。GMAW具备高沉积速率和热输入，适用于中大型构件制造，但高热输入易导致较大温度梯度，影响界面结合质量。作为其改进工艺，冷金属过渡焊(Cold Metal Transfer，CMT)技术(原理如图2(f)所示[39])通过精准控制焊丝回抽将熔滴送进熔池，降低热输入并抑制飞溅，稳定熔池以优化成形质量[40]。CMT-WAAM技术凭借加工成本低、沉积效率高等优势，已成功应用于TC4 [41, 42]、TC11 [42, 43]、TC17 [44]等中大型金属结构件的制造。在WAAM沉积过程中，钛合金经历快速冷却时，高温β相转变为亚稳相，这类组织易引发裂纹萌生与扩展，最终可能导致构件发生脆性断裂[45,46]。同时，多层堆积形成的热积累效应会使导致构件内部产生显著的残余应力[47]，进一步加剧结构失效风险。因此，WAAM沉积态钛合金构件需通过后处理工艺调控微观组织、优化力学性能并消除残余应力，以满足工程应用需求。
1.4复合能量场
为了解决AM技术成型钛合金过程中产生的微观缺陷(裂纹、孔洞等)、残余应力及力学性能各向异性的问题，研究人员提出了外场辅助的方法，通过外加能场与沉积材料的相互作用来调控其微观组织与力学性能[48]。辅助外场主要包括声场(Acoustic field,AF)(超声波振动(Ultrasonic vibration, UV))[49]、形变场(Deformation field, DF)[50](含滚压(Rolling)[51]、超声冲击(Ultrasonic impact treatment, UIT)[52]、激光冲击(Laser shock peening,LSP)[44]等)及磁场(Magnetic field,MF)[53,54],(图2(g-i)为各类外场辅助示意图[55])，其作用原理存在差异:AF利用空化和声流效应消除缺陷和破碎枝晶;DF通过使沉积层产生塑性变形来促使材料发生再结晶;MF则借助电磁力破碎枝晶来调控组织。外场的引入在不同程度上克服了AM的局限性[56]，具有易于调控微观组织、减小孔隙率、降低残余应力和改善力学性能等优势[57,58]，为从根本上提升钛合金的致密度及改善微观组织开辟了新路径，SLM工艺因需要在密闭腔体中进行，将DF和MF与SLM设备集成难度较大，相关研究相对较少，但可将超声装置安装在基板上，超声波通过基板间接作用在熔池中，但随着样品高度的增加，声波振动的作用衰减，不适用于尺寸较大的样品[59]。
上述系统论述了激光、电弧、复合能量场成型技术在钛合金制备中的应用现状，不同技术因工艺原理的固有差异，在成形精度、沉积效率及构件尺寸等方面各具优势，可满足不同场景下钛合金构件的制备需求。然而，成型工艺及后续热处理工艺的选择对调控钛合金微观组织特征和服役性能至关重要。
2、金属增材制造技术钛合金的显微组织及力学性能研究
2.1 LDED成型钛合金显微组织及力学性能研究
2.1.1工艺参数对LDED成型钛合金显微组织及力学性能的影响
在LDED成形钛合金过程中，激光功率(P)、扫描速度(v)、层间温度、扫描策略等工艺参数，通过调控熔池的热历史与流动行为，直接影响晶粒形态、相组成及缺陷分布，从而决定构件的力学性能[60-62]。夏超 [63]利用具有高P的LDED技术成型TA15合金，发现高P引入的高能量使得沉积态组织为粗 α板条状，性能呈现出低强度、高塑性特点。而工艺参数的协同作用是实现力学性能强塑性平衡的关键，艾佳华 [64]在LDED成型Ti-1300钛合金过程中，通过调控P、v与送粉速率( P r )等工艺参数，获得了稳定的熔宽和匹配性良好的强塑性。除了优化工艺参数外，层间强制冷却可降低层间温度，减少热积累并细化晶粒，协同提升钛合金的强度和塑性，Wang等[65]采用层间和轨间强制冷却(Inter Layer Cooling-In Track Cooling, ILC-ITC)6s,阻断β晶粒的连续生长并生成了柱状β晶粒(图3(a2)所示)，使TC4合金在垂直(0°)与平行(90°)于构建方向(Building Direction，BD)的极限抗拉强度(Ultimate Tensile Strength，UTS)和延伸率(Elongation，EL)均显著提升，实现强塑性的协同优化。扫描策略对残余应力、变形行为、及晶粒形态具有显著影响[66,67]。Zhang[68]采用数值模拟方法系统比较了12种扫描路径的影响规律，根据其热-力耦合仿真结果表明，层间扫描方向90°旋转有利于降低残余应力，而45°旋转策略则能获得最优的变形控制效果。Wang等[69]在TC4合金成型中采用层内反向扫描结合层间横纵向交替扫描策略(图3(b1-b2))，发现平行于基板的试样因篮状 α/α团簇结构及更细小晶粒，展现出最高的 UTS和屈服强度(YieldStrength，YS)、垂直于基板的试样(90°LDED试样)则因组织差异获得最大EL(图3(b3)所示)。
2.1.2热处理对LDED成型钛合金显微组织及力学性能的影响
LDED成型的钛合金中的典型的粗大柱状晶组织会引起力学性能的显著各向异性，而残余应力集中将导致边缘翘曲降低成形件的成形质量和成品率，热处理工艺可以调控LDED成型的钛合金组织形貌，合适的热处理工艺可以使组织性能均匀化 [71, 72]。荣鹏等 [73]研究了三种不同热处理对LDED成型TC4钛合金微观组织及力学性能的影响:经975℃/1 h/AC+600℃/4h/AC处理后获得了韧性更高的 α p 相宽度更宽，且原 β相晶界附近生成等轴 α p 相，使得试样具有较强的变形能力和高协调性，各向异性得到了改善。Ding[74]对LDED成型Ti55531钛合金采用超临界β退火+时效(SBA-A)、超临界β循环退火+时效(SBCA-A)等工艺，发现SBA-A与SBCA-A处理后，合金内部分别呈现出Widmanstatten晶界和锯齿状晶界(图4(a1-a2)为合金裂纹扩展示意图)，有效抑制裂纹扩展，其中SBA-A处理使合金的UTS达1045±12 MPa、EL达12.0%±1.2%，断裂韧性高达81.7±1.1 MPa m1/2，强塑性匹配性最优(图4(b1-b2))(详见表1)。曾宙[75]针对LDED成型TB6钛合金设计了多重热处理(固溶+一次时效+两次时效)。如图4(b)所示，840℃固溶形成单一β相;一次时效(840℃+760℃)析出初生 αp 、α GB 相并产生无相析出区(Precipitate-Free Zones，PFZ);二次时效(840℃+760℃+530℃)促使次生αs相弥散析出(形貌随温度升高从细针状转短棒状)，且PFZ被αs相填充;随二次时效温度升高，合金UTS降至973 MPa，EL提高至14.1%，530℃二次时效处理时强塑性平衡方面表现最好最佳。
综上所述，LDED成型钛合金的力学性能调控需以“热历史-微观组织-性能关联机制”为核心:通过优化P、v等参数控制能量输入，结合层间强制冷却与扫描策略实现晶粒细化及残余应力降低。LDED钛合金的热处理调控需结合合金类型与原始沉积组织:退火适用于残余应力释放与组织均匀化;固溶时效通过析出相各向同性分布抑制力学各向异性，适用于β型合金;多重热处理则通过精细调控相变与晶界结构，实现强塑性的协同突破。
表1不同热处理对LDED成型钛合金组织和力学性能的影响[73-75]
| Titanium | Heat treatment | Microstructure | UTS | YS | EL | Ref. |
| alloy | process | /MPa | /MPa | (%) | ||
| TC4 | 600℃/4 h/AC | coarsening of the α p , continuous aGB | 965±9 | 898±9 | 13.4±2.7 | [73] |
| 800℃/1 h/AC | coarsening of the ap, continuous aGB, fine as | 950±4 | 869±5 | 26.8±3.3 | ||
| 975℃/1h/AC+600℃/4h/AC | equiaxed a phase, lamellar a phase | 904±5 | 822±4 | 14.2±1.3 | ||
| Ti55531 | SBA-A | Widmanst atten aGB | 1045+12 | 943±10 | 12.0±1.2 | [74] |
| SBCA-A | zigzag aGB | 969±18 | 914±13 | 8.6±0.4 | ||
| TB6 | 840℃ | β phase | 846 | 783 | 23.2 | [75] |
| 840℃+760℃ | Primary a,p phase, PFZ | 896 | 820 | 20.6 | ||
| 840℃+760℃+500℃ | fine acicular as phase | 1257 | 1109 | 4.0 | ||
| 840℃+760℃+530℃ | fine acicular as phase | 1180 | 1034 | 5.5 |
2.2 SLM成型钛合金显微组织及力学性能研究
2.2.1工艺参数对SLM成型钛合金显微组织及力学性能影响
SLM成形质量的核心在于工艺参数匹配与能量输入控制，不当的参数组合易引发匙孔、未熔合孔洞等微观缺陷[76-78]。能量密度(Energy Density, E)作为关键调控指标可实现成形质量的精准控制[79, 80](E=P/(vht)，P为激光功率，v为扫描速度，h为扫描间距，t为层厚)。P和v的协同优化是控制E的核心，Zhang等[81]研究了P、v对SLM成型Ti-24Nb-4Zr-8Sn钛合金构件成形质量的影响，通过优化P、v值可实现致密度的提升。Cai等[82]研究了E对SLM成型TA15钛合金显微组织演变的影响:低E导致熔化不充分并产生气孔，高E引发过熔与球化效应，此结论与Liverani等[83]、Wei等[84]和Guan等[85]研究一致。PANWISAWAS等[86]和QIU等[87]研究t对合金表面质量的影响，较低的t利于合金表面的成形质量，当t超过0.04mm时使得表面粗糙度和孔隙率增大，继续增加t将恶化合金的成形质量。
此外，扫描策略可通过调整激光扫描路径与方向，改变热流传递路径与热量分布状态，调控晶粒取向与温度梯度，缓解热收缩不均带来的应力集中来降低残余应力[88,89]。陈德宁[90]对比岛式与蛇形扫描发现，岛式扫描因岛屿边缘二次升温使TC4合金的温度场分布更均匀，可减小应力集中，但温度梯度较低导致柱状晶更粗大;Ali等[67]证实，棋盘格扫描策略与连续层间旋转角度有助于降低残余应力;Shi等[91]将直线LINE、棋盘格CHESS、条纹STRIPE扫描与定向角度偏移(0°、45°、90°)组合，发现CHESS&45°策略下，TC4合金试样熔道连续，无明显孔洞，β相与α'相分布均匀;纵向截面可见沿成形方向排列的柱状β晶，试样表面粗糙度达14μm(如图5(b1-b2))，致密度达99.85%。
2.2.2热处理对SLM成型钛合金显微组织及力学性能影响
SLM成型钛合金过程中，激光高能束高频短时作用于钛合金，使其在凝固过程中发生晶粒外延生长导致柱状晶的生成 [92, 93]，最终使成型件呈现力学性能各向异性。受快速冷却过程的影响，β相来不及转化为α相从而在柱状晶内部形成了大量α'相使得钛合金强度提升，但塑韧性降低 [94]。为了获得优异力学性能的钛合金，Carrozza等[95]对 SLM成型的 Ti6246合金进行750℃/2h固溶处理后，α'相分解为片层状α+β，实现强塑性的良好平衡。Huang等[96]对SLM成型TC4钛合金进行不同退火处理发现试样的UTS和硬度均有所下降，而塑性有所提高。双重退火制度可显著消除晶界，柱状晶粒消失后的组织尺寸分布趋于均匀，这有利于提高合金的塑性同时使得力学性能的各向异性显著降低，其中在850℃/30 min/AC+600℃/2h/AC退火处理下力学性能各向异性改善效果最佳(详见表2)。
与传统的热处理工艺相比，多步热处理技术(Multi-Step Heat Treatment，MSHT)能有效促进a球化与等轴组织形成，强度塑性匹配效果更显著。Li等[97]对SLM成型TC4合金施加MSHT(工艺路线如图6(a1)，球化机制如图6(a2))，通过逐步升温保温与炉冷，先使 α'完全分解为 α+β，再经cylinderization、edge spheroidization等球化机制将片状 α转为近等轴α晶粒;该组织可降低力学各向异性与晶界滑动阻力，实现强塑性匹配。Wang等[98]对TA15合金进行低温-高温(Low-High Temperature,LHT)多步加热后(工艺路线如图6(b1))，形成片晶、等轴晶与短棒状a组成的三态组织(形成机制如图6(b2))，片状a晶粒保证了合金的强度，等轴和短棒状a晶粒降低晶界滑动阻力、激活多滑移系提升塑性。
表 2不同热处理对 SLM成型钛合金组织和力学性能的影响 [95−98]
| Titanium | Heat treatment | Microstructure | UTS | YS | EL | Ref. |
| alloy | process | /MPa | /MPa | (%) | ||
| Ti6246 | 750°C/2h | α ′ → α + β | 1146±41 | 1064±10 | 16.4±0.5 | [95] |
| TC4 | 850°C/30min/AC | columnar grain refinement, Widmanstatten | 900±20(X-Y) | 900±20(X-Y) | 11.5(X-Y) | [96] |
| 900℃/30min/AC | gradual melting of columnar grains, striated a/β phase | 850±10(X-Y) | 14.2(X-Y) | |||
| 950°C/30min/AC | disappearance of columnar grains, Basketweave, a phase coarsening | 700±8(X-Y) | 13.9(X-Y) | |||
| 850°C/30min/AC+600℃/2h/AC | short rod-like a phase, Striated a/β phase | 896(X-Y) | 13.2(X-Y) | |||
| TC4 | MSHT | α ′ → α + β, equiaxed | 953 | 900 | 21.8 | [97] |
| TA15 | LHT | αphase, short rod-like a phase | 1033±4 | 967±4 | 16.6±0.5 | [98] |
2.3 WAAM成型钛合金显微组织及力学性能研究
2.3.1工艺参数对WAAM成型钛合金显微组织及力学性能的影响
WAAM成型过程中焊道形貌可直观反映焊接质量[99]，孙清洁等[100]研究表明，调整电弧电流可有效调节Ti60合金焊道的宏观成形，增大熔宽和熔深，减少金属球化并提升焊道均匀性。Liu等[101]针对GTAM-WAAM成型TC4合金，采用Box-Behnken设计响应面实验构建熔覆层宽、高及熔深的回归模型，方差分析表明:焊接电流(I)、送丝速度(V)与焊枪移动速度(Vs)为关键影响因子。其可行性指标分布如图7(a1-a2)所示，最优参数对应图中红色区域;最优参数下，TC4薄壁件鞑课痪鹤橹琣相从顶部到底部逐渐粗化，显微硬度随之下降，拉伸性能因a相排列及晶粒取向呈现各向异性。
热输入过高会导致沉积层间温度升高、层高减小、宽度增大，引发尾部塌陷，影响成形质量与力学性能[102,103]。通过层间强制冷却和合理的路径规划能够使热输入均匀分布，减少局部过热或冷却过快引发的缺陷，细化晶粒促进等轴晶的生成，提升材料性能。如，Ogino等[104]发现，每道次成型后冷却并严格控制层间温度，可明显改善尾部塌陷;He等[105]通过梯度热输入结合层间冷却工艺，通过提高冷却速率抑制柱状晶粒外延生长，使Ti-6Al-2Zr-1Mo-1V(TC11)合金形成细柱状-等轴混合组织，其显微硬度、UTS和EL分别提高了5.3%、6.6%和37.6%。Wang等[106]对比分析了三种沉积策略(A:双向扫描+0s层间停留，B:单向扫描+24s层间停留，C:单向扫描+120s层间停留)对WAAM成型TC4合金的温度与应力应变场的影响:在策略B下，a片层边界形成无位错再结晶a晶粒，位错向先 β晶界富集，晶粒内部呈低储能状态(如图7(b1));单向扫描路径使热场分布均匀并形成水平层带(图7(b2));策略C更长的停留时间为已沉积层提供了更充足的散热时间，使得沉积过程中的热积累显著降低，且热场分布更均匀，α片层宽度变化平缓，最终获得等轴晶组织，显著提材料强度和硬度。
2.3.2热处理对WAAM成型钛合金显微组织及力学性能的影响
WAAM在逐层堆积的过程中使材料经历多次的热循环，同时材料在凝固过程中的冷却速度较大，使得原始柱状 β相会转变成不同形态的脆性 α相，造成合金强度和塑性等力学性能的各向异性 [107]。为了改善微观组织均匀性和材料力学性能的各向异性，研究人员对WAAM成型钛合金热处理工艺进行了深入研究。张帅锋等[108]在 CMT-WAAM成型Ti-6Al-3Nb-2Zr-1Mo(Ti6321)合金过程中发现，经700℃退火后，Ti6321合金UTS下降70 MPa，这是由于热处理导致位错密度降低，位错间的交互作用减弱，从而减少了对位错滑移的阻碍作用。当退火温度升高至800℃时，α片层进一步均匀化，其相邻片层间的亚稳 β相进一步转变分解，亚稳 β相转变为短棒状 α相， α/ β相界面数量增加，从而增强了对滑移的阻碍效果，促使强度升高。Lin等 [109]采用Gleeble热模拟构建了 WAAM成型 TC4合金不同热处理态(沉积态:AD;固溶态:AD-ST;固溶+时效态:AD-ST-Age)的微观结构梯度，AD-ST-Age态α相取向集中性高于AD-ST态(图8(a1-a2))，最优的热处理工艺为AD-ST-Age(830 ∘C/2h/WC+ 500 ∘C/4 h/FC，FC:炉冷)，ST使 α ′马氏体的细化，Age促进 α魏氏体的细化及 α'分解，最终使YS、UTS分别提高12.85%、3.33%。Wang等[110]对WAAM成型TC4合金采用了五种不同的热处理方案(HT1-HT5)研究其微观结构演变，与沉积态相比，经过HT1处理后，α/β界面相部分分解，导致了EL的降低;HT2处理后板条 α相粗化，并且在HT2试样中观察到了有利于提高塑性的 α/β界面相，导致了UTS的降低和EL的增加。而经HT5处理后，出现细小的不连续 α GB 相、 α p 相和αs相，αs相起到较强的弥散强化作用，β相中V元素的界面偏析获得了较多的α/β相界面(图8(b1-b2))，且细小不连续的 α GB 相避免了应力集中，使试样的UTS和EL分别达到886 MPa和 16.6%(详见表3)。
综上所述，WAAM热输入显著影响钛合金成形质量，均匀化热输入是改善组织形态、提升力学性能的重要技术路径。钛合金的强度源于a相细化、弥散强化及位错阻碍作用，塑性主要依赖 α/β相界面的变形协调能力。通过退火、固溶+时效等热处理工艺可进一步调控组织形态，包括a相、亚稳相及a/β相界面数量，实现强塑性的均衡提升。
表3不同热处理对WAAM成型钛合金组织和力学性能的影响[108-110]
| Titanium alloy | Heat treatment process | Microstructure | UTS /MPa | YS /MPa | EL (%) | Ref. |
| Ti6321 | 700℃退火2h | the dislocation density inside the a lamellae decreases | 1100 | 900 | 15 | [108] |
| 800℃退火2h | homogenization of a lamellae, decomposition of βphase | 1100 | 1000 | 12 | ||
| TC4 | 830°C/2h/WC | metastable a' martensite | 925.3 | 925.3 | 9 | [109] |
| 830°C/2h/WC+500°C/4h/AC | fine acicular secondary as phase, short rod-like aGB | 954.38 | 871.31 | 5.37 | ||
| 830°C/2h/WC+800°C/2h/AC | Short rod-like secondary a phase | 904.33 | 811.72 | 8 | ||
| 830°C/2h/WC+500°C/4h/FC | fine acicular secondary as phase, granular aGB | 946.46 | 902.62 | 5.38 | ||
| TC4 | 600℃/4h/AC | partial decomposition of the a/β interfacial phase | 854 | 772 | 11.8 | [110] |
| 850°C/2h/AC | a phase lath coarsening, secondary as phase | 845 | 734 | 13.6 | ||
| 930°C/1h/AC+550°C/4h/AC | a, a, residualβ phase | 865 | 783 | 9.9 |
2.4复合能量场成型钛合金显微组织及力学性能研究
随着航空航天、生物医学等高端领域对构件结构稳定性、性能可靠性及轻量化需求不断提升，传统单一调控手段已难以满足复杂工况要求，外场辅助调控技术(AF、DF、MF等)被引入以优化钛合金的成形质量并提升其力学性能[111]。
AF辅助通常是利用UV产生的声能与AM相结合，利用其独特的声流与空化效应来控制金属熔池的凝固过程[59,112,113]。Todaro等[59]将高强度超声共振场与LDED技术协同(图9(a1))，通过UV引发的熔池扰动与晶粒破碎，将TC4合金中粗大的柱状β晶细化为等轴晶，电子背散射衍射(Electron Backscatter Diffraction，EBSD)(图9(a2))表明，无超声时，α相、β相均呈现明显择优取向;施加超声使a相、β相的最大均匀分布倍数(Multiples of Uniform Distribution，MUD)减小，织构弱化， β相转为等轴晶粒且<001>织构消失，各向异性降低，UTS、YS较未处理态提高约12%。
在AM过程中引入DF使沉积层发生塑性变形，在下一层沉积时，塑性变形部分可能发生再结晶，从而改变材料微观组织与力学性能。Yang等[114]采用UIT辅助WAAM工艺，在Ti-6Al-4V沉积后实施两次UIT，使粗大柱状β晶转变为等轴晶与短柱状晶交替分布的组织，提升表层均匀性(图9(b1)UIT辅助WAAM工艺晶粒生长示意图)。Chen等[115]采用UIT辅助LDED制备TA15钛合金，晶粒细化使UTS和EL均提高。此外，DF还能将沉积表面一定深度范围内残余拉应力被转变为对材料力学性能有益的压应力[116]，孟宪凯团队[117]研究发现，LSP在TC6合金表层引入残余压应力，抑制疲劳裂纹的萌生与扩展，延长疲劳寿命;其开发的双脉冲LSP技术，通过延长冲击作用时间，诱导Ti6Al4V合金形成“细晶-粗晶-细晶”的复合结构，显著提升显微硬度与强度，且保持良好的塑性。
MF定向调控中，纵向与横向MF作用机制存在差异。纵向MF通过洛伦兹力驱动熔池环向流动，可增加焊道宽高比、降低表面粗糙度，并抑制边缘焊道流淌与塌陷[118,119];横向MF则通过偏转电弧诱导熔池单向对流，降低熔池底部等轴晶区域的占比与胞状枝晶间距，提升枝晶前沿成分过冷度[120]。Zhao等[121]将磁场与LDED相结合(如图9(c1)所示)，研究发现，在0.55T横向静磁场(Static Magnetic Field,SMF)下制备TC4钛合金的性能最优，SMF通过调控熔池流动与固态相变，增强a相晶界连续性(图9(c5))、分散取向;弱化β晶粒织构(图9(c3，c6))，增加α相形核数量并形成规则位错阵列与亚晶界(图9(c7))，有效降低力学性能各向异性;该团队[122]进一步提出高磁场(High Magnetic Field, HMF, 3T)与热处理相结合调控SLM成型TC4合金的组织，发现HMF可加速a相的粗化和球化，虽使UTS与YS相较原始态略有降低，但EL提高至14.1%-15.4%，实现更优的强塑性匹配。
综上所述，外场辅助技术通过调控AM钛合金微观组织特征，如改善织构强度、诱导柱状晶向等轴晶转变、引入残余压应力等方面，实现强度与塑性的同步提升，然而，当前关于外场辅助与热处理工艺耦合的系统性研究较为匮乏，其作用机制与工艺适配性的深入探索具有重要的理论与工程价值。
2.5有限元仿真模拟钛合金增材制造过程
有限元分析(Finite Element Analysis，FEA)通过构建多物理场耦合模型，可精准模拟从熔池演变到逐层堆积的全过程，量化工艺参数对应力、变形及微观组织的影响，已成为预测并优化金属AM质量的主流数值方法。该方法弥补了实验手段在瞬态场监测方面的局限，支持参数化仿真与快速工艺评估，为LDED、SLM、WAAM等工艺的成型控制提供了重要理论依据。
在LDED工艺中，循环热载荷导致工件剧烈的温度波动，冷却后形成残余拉应力。Deng等[123]建立了三维瞬态热分析有限元模型，模拟Ti60钛合金在LDED成型过程中的熔池演化(如图10(a1))，通过G和V的关联(图10(a2))揭示了晶粒生长模式对组织形态的影响，指出柱状晶向等轴晶转变(Columnar to Equiaxed Transition，CET))有助于缓解热收缩不均，降低残余应力，如图10(a3)所示，熔池内温度梯度方向的变化促使等轴晶多向生长，进而弱化织构。Wu等[124]针对LDED成型Ti6Al4V合金，构建热-力耦合有限元模型，提出可变激光功率沉积策略StrategyC(四种策略详见图10(b))，动态模拟温度与应力场演变。结果表明:该策略使试样平均基底温度降低12.68%-15.08%，最大主应力下降7.8%-32.14%;图10(c)为四种沉积策略下沿沉积方向的残余应力(σx)分布情况，其中StrategyC通过降低温度梯度，使残余应力分布更均匀，模拟与实验的温度及应力误差分别控制在10.12%和6.92%以内。
在SLM加工过程中，金属粉末受到高能能量束瞬时辐照，熔化形成微尺度熔池，随着能量热源移动，熔池在先前沉积的基底冷却作用下迅速凝固，使熔池内部表现出高温度梯度(G)(>10^2 K/mm)、高冷却速率(V)(约10^7 K/s)和高残余热应力累积的非平衡短时冶金特征[125]。这种极端加工条件和复杂流体动力学行为的耦合作用，极易产生气孔、匙孔孔隙、熔合不良、球化效应等缺陷[126]。为深入揭示工艺对缺陷形成的影响机制并实现精准调控，介观尺度数值模拟已成为重要研究手段，图11(a1)为SLM制造中多尺度、多物理场现象的示意图[127]。钟敏奎[128]通过多物理场模拟与实验相结合的方法，系统分析了P、v对SLM成型TC4钛合金熔池尺寸的影响(如图11(a2)所示):随着P增加，熔池宽度与深度均相应扩大;随着v的减小，热积累效应增强，熔池尺寸显著增大，证实了P、v的协同调控是优化熔池形貌、抑制缺陷的关键途径。Yin等[129]对SLM成型TC4合金的温度场进行有限元仿真，发现提高v和优化沉积高度可有效减少因晶粒取向差异导致的不均匀收缩，从而降低残余应力与变形。在扫描策略与辅助工艺优化方面，Cheng等[130]研究表明，SLM成型过程中X、Y方向的应力集中主要分布于沉积层边缘及基体界面区域，其中环形扫描模式下应力值最大，而45°斜线扫描可通过均匀化温度场分布，显著降低两个方向的残余应力。此外Zhou等[131]利用激光重熔(Laser Remelting,LR)多场耦合模型研究了LR对致密度、气孔等的调控，受成形过程预热的影响，LR形成的熔池尺寸更大，有助于促进熔体流动与孔隙填充，从而实现致密度提升与缺陷消除。
WAAM的沉积过程往往伴随着较大的热输入和局部热积累，导致残余应力分布不均匀和变形，还会导致粗晶组织 [132]。Li等 [133]结合多组分相场(Phase Field，PF)模型与FEA，预测WAAM成型Ti-Al-Fe-V合金的CET行为，PF模拟表明低G和高V利于等轴晶形成(图11(b1-b4);FEA进一步获取了瞬态G、V分布与温度场(图11(b5-b6))，揭示热输入密度对CET位置的关键影响:高能量输入促使CET提前发生。刘国昌等[134]采用Simufact Welding软件仿真激光电弧复合AM的热力场，并通过试验验证模型的可靠性，发现温度积累效应显著，等效应力逐步转化为残余应力，且应力集中于道间、层间结合区及基板连接处;基于仿真优化，通过不同堆积路径下应力分布图(图11(c1-c2))得出道间堆积采用同向式(左至右)、层间堆积采用交错式的最优路径方案，有效改善了应力分布与成形质量。
综上，FEA作为金属AM质量预测与工艺优化的核心数值方法，通过构建多物理场耦合模型，可精准模拟LDED、SLM、WAAM等典型工艺的熔池演变、逐层堆积及瞬态场演化全过程，有效弥补了实验手段在瞬态监测中的局限，为量化工艺参数对残余应力、变形及微观组织的影响提供了重要理论支撑。
3、增材制造钛合金的耐腐蚀性能研究
3.1激光增材制造钛合金的耐腐蚀性
激光成型钛合金的耐腐蚀性能与其显微组织特征密切相关。较低的v有利于形成细小的 α ′马氏体，从而提高表面钝化膜的致密性与均匀性，显著增强合金的耐腐蚀性能 [135]。Lu等[136]研究表明，在高P(250W)与中等v(1200mm/s)下成型的TC4合金具有优良的综合性能:其内部为规则生长的柱状β晶与分散分布的针状 α ′马氏体，不仅力学性能优异，且表面可快速形成以TiO2为主的致密钝化膜，这是其耐腐蚀性能突出的关键因素。由于显微组织的差异，SLM成型钛合金的耐蚀性能是各向异性的。Dai等[137]通过电化学测试与组织分析比较了TC4合金XY与XZ平面的耐蚀行为。经Tafel拟合结果(如图12(a-b)所示)，在3.5 wt% NaCl溶液中，两平面的钝化电流密度相近;而在1MHCl溶液中，XZ平面的钝化电流密度高于XY平面，说明XY平面的耐蚀性更优。其原因在于XZ平面α相含量较高、 β相较少( β相是一种良好的腐蚀抑制剂)，导致其耐蚀性较差(如图12(c-d)所示)。退火与热等静压(HotIsostatic Pressing，HIP)等热处理也对耐腐蚀性能具有重要影响[92,138]。退火处理可使 α/β相分布更均匀，降低材料各向异性;HIP处理则能有效闭合SLM成型过程中形成的缺陷，显著提高TC4合金在腐蚀介质中的耐腐蚀性能。Li等[139]针对 SLM成型Ti-6Al-4V-3Cu合金，研究了不同温度(760°C、820°C、875C)保温2h后水冷的组织演变及其对耐腐蚀性能的影响。结果表明:760℃热处理为最优工艺，可实现 α ′马氏体部分分解( α ′ → α + β)与残余应力释放，同时避免晶粒粗化与Ti 2Cu相非均匀析出，所得致密稳定的钝化膜(以TiO2为主)，耐腐蚀性能最佳。Anantharam等[140]发现，经800℃/2h退火处理的LDED成型Ti-6Al-4V合金腐蚀电流密度显著降低，耐腐蚀性最优。其原因为退火促使α'相转变为a+β相双向组织，减少a/β界面面积，提升电化学稳定性;未处理的沉积样品由于缺乏β相，表现出更高的腐蚀倾向。
3.2电弧增材制造钛合金的耐腐蚀性
WAAM成型的钛合金，其微观结构常呈现晶粒取向与 α/ α ′相形态的各向异性，导致耐腐蚀性能普遍低于传统锻件。研究表明，钛合金的腐蚀行为强烈依赖于其微观结构和服役环境 [141]。热处理是调控组织并影响耐蚀性能的关键手段，但其效果因合金成分与工艺条件而异。例如，在3.5wt%NaCl溶液和5MHCl溶液中，Ti-6Al-3Nb-2Zr-1Mo合金的耐腐蚀性会随退火温度从850℃升至1000℃而提升，主要归因于β相体积分数增加与α相片层厚度减小[142];而Ti-4Al-5Mo-3V-5Cr-Fe合金经750℃、870℃固溶处理并在500℃时效6h后，呈现层状与双峰结构，其在2MHCl溶液中的耐腐蚀性能却有所下降[143]，说明热处理对耐蚀性的影响具有合金特异性。钛合金的腐蚀行为还取决于钝化膜的形成，该钝化膜主要由TiO2构成，可自发覆盖于合金表面，且钝化膜稳定性越高，合金的耐腐蚀性越优异 [144]。Cheng等 [145]对比了锻造与WAAM成型TC4合金在模拟质子交换膜水电解(Proton Exchange Membrane Water Electrolysis, PEMWE)阳极环境中的电化学行为，发现经1050 ∘C热处理后，WAAM TC4合金中V2p3/2谱仅呈现钒氧化物信号(图13(i,l))，而锻造与沉积态样品中则检测到金属V(图13(c,f))。该合金腐蚀电流密度最低(54μA/cm2)，钝化电流密度为19.5 μA/cm²，氧化钛(Ti 2O3与TiO2)占比达80.9%，表明高比例钛氧化物有助于形成更稳定的钝化膜，显著提升耐腐蚀性能。除了热处理外，WAAM过程中的保护气体成分也对组织均匀性与钝化膜稳定性有重要影响。Chen等[146]指出，在CMT-WAAM成型Ti-6Al-4V的过程中，随着保护气体中He的比例增加，电弧电压升高，电弧稳定性增强;当He含量为50%时，部分a'马氏体分解为a+β篮状组织，促进两相平衡分布，这种组织均匀化有助于形成更致密的钝化膜，从而改善耐腐蚀性能。
3.3复合能量场成型钛合金的耐腐蚀性
复合能量场成型技术通过多场协同作用优化钛合金的微观结构与表面状态，为提升耐腐蚀性提供了新途径。LSP具有更高能量、高应变率的特点，不仅能改善材料的拉伸与疲劳性能[147,148]，还可通过组织调控增强耐腐蚀性[149,150]。Jiang等[151]提出电脉冲联合激光冲击强化(Electro-pulsing Combined with Laser Shock Peening,EP-LSP)复合工艺,促使Ti-6Al-4V合金表面晶粒细化、 α相向 β相转化，为钝化膜提供更多形核位点，加速形成均匀致密的钝化膜(图14(a1-a2)为原始态和1次EP-LSP样品的腐蚀示意图)。经1次EP-LSP处理后，试样的腐蚀电流密度降低，腐蚀电位提高，耐腐蚀性能提升(图14(a3)为对应的Tafel极化曲线)。除LSP技术外，磁弧振荡也被用于优化WAAM成型钛合金的耐腐蚀性能。Wu等[152]在TC4沉积过程中引入弧旋转(ArcRotation，AR)与弧纵向(Arc Longitudinal，AL)两种磁弧振荡模式(图14(b1-b2)所示)，相较于电弧稳定(Arc Stability,AS)状态，磁弧振荡可细化a片层，提高位错密度并强化晶粒取向集中。AL试样表面形成约22nm钝化膜与3nm过钝化膜，结构紧密无缺陷，能有效阻断腐蚀介质。电化学阻抗谱(Electrochemical Impedance Spectroscopy，EIS)(图14b3)显示， AR与AL试样的电荷转移电阻(Rct)远高于AS试样，Nyquist图中阻抗弧半径更大，表明磁弧振荡显著提升了表面膜层的防护性能。此外，Ji等 [153]提出的耦合电脉冲和超声处理(Coupled Electric Pulse and Ultrasonic Treatment,CEPUT)可以同步去除TC4钛合金表面的疏松氧化层并生成致密α相层(图14(c1)为CEPUT作用合金微观组织变化)。经400A峰值电流处理后，合金在0.9%NaCl溶液中的自腐蚀电流密度降低(如图14(c2)所示)，较未处理样品降低两个数量级，耐腐蚀性大幅提升。
综上所述，致密的微观组织与稳定的表面钝化膜是提升AM钛合金耐蚀性能的两大核心要素。通过精准的工艺参数调控与适配的热处理，可进一步增强钝化膜的完整性与稳定性;而采用多场协同调控技术细化晶粒并优化表面致密度，能够有效降低腐蚀电流密度，最终实现耐蚀性能的显著提升。
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（注，原文标题：钛合金增材制造技术及组织性能研究进展）
tag标签:钛合金,增材制造,多元化发展,精准调控,单一能量场,复合能量场