引言

鈦合金(Titanium alloys)憑借其優(yōu)異的比強(qiáng)度、耐腐蝕性和良好的生物相容性，已成為航空航天、海洋工程及生物醫(yī)學(xué)等先進(jìn)工程領(lǐng)域的關(guān)鍵結(jié)構(gòu)材料[1-3]。根據(jù)合金元素及室溫微觀組織特征，鈦合金通常可分為α型[4-7]、α+β型[8-11]和β型[12-15]三類，其選型需緊密結(jié)合具體服役條件與性能要求。圖1鈦合金的主要分類及應(yīng)用場(chǎng)景[4-15]

盡管傳統(tǒng)制造技術(shù)(如鑄造[16]、鍛造[17]、粉末冶金[18]等)在大批量、結(jié)構(gòu)簡(jiǎn)單零件生產(chǎn)中具備可靠性與一致性優(yōu)勢(shì)，但仍面臨三大挑戰(zhàn):(1)能源消耗大、碳排放高，與綠色制造理念相悖;(2)熱導(dǎo)率低且高溫化學(xué)活性強(qiáng),易引發(fā)組織缺陷并降低性能;(3)材料利用率低、成本高、加工周期長(zhǎng)，難以實(shí)現(xiàn)復(fù)雜曲面結(jié)構(gòu)的高效成型，加工效率與設(shè)計(jì)自由度受限，無(wú)法滿足高性能構(gòu)件需求。隨著制造業(yè)升級(jí)與綠色、可持續(xù)發(fā)展需求，亟需突破傳統(tǒng)技術(shù)瓶頸。近年來(lái)，增材制造(AdditiveManufacturing，AM)作為一種革命性成型技術(shù)，憑借其低能量損耗、高材料利用率與對(duì)復(fù)雜幾何結(jié)構(gòu)的高度制造柔性等優(yōu)勢(shì)，在高性能、高精度鈦合金零部件的一體化制造方面展現(xiàn)巨大優(yōu)勢(shì)。

本文系統(tǒng)闡述了以激光、電弧及復(fù)合能量場(chǎng)為代表的金屬AM技術(shù)在鈦合金構(gòu)件制備中的應(yīng)用現(xiàn)狀，深入分析了工藝參數(shù)優(yōu)化對(duì)鈦合金微觀組織與性能的調(diào)控機(jī)制，闡明了熱處理技術(shù)在改善鈦合金微觀組織及提升力學(xué)性能、腐蝕性能方面的作用機(jī)理，并基于當(dāng)前研究進(jìn)展對(duì)AM鈦合金形性一體化調(diào)控技術(shù)的未來(lái)發(fā)展方向進(jìn)行了展望。

1、鈦合金的增材制造技術(shù)

金屬AM技術(shù)基于“離散+堆積”原理，通過(guò)能量源將金屬原材料逐層熔化、凝固成形，最終實(shí)現(xiàn)三維構(gòu)件的直接制造[19]。根據(jù)能量源類型與原料形態(tài)的差異，適用于鈦合金的主流AM技術(shù)可分為激光定向能量沉積(Laser Directed Energy Deposition，LDED)、激光選區(qū)熔化(Selective Laser Melting，SLM)[20]以及電弧熔絲增材制造(Wire Arc Additive Manufacturing，WAAM)[21]。相關(guān)研究表明[22-25]，在金屬AM技術(shù)中引入外場(chǎng)可有效優(yōu)化鈦合金構(gòu)件的成形質(zhì)量和性能，為該領(lǐng)域的發(fā)展提供了重要技術(shù)支撐。

1.1激光定向能量沉積技術(shù)

LDED技術(shù)，亦稱激光近凈成型技術(shù)(Laser Engineered Net Shaping,LENS)，其工藝原理為通過(guò)噴嘴將金屬粉末送至高能激光作用區(qū)域，粉末迅速熔化形成熔池，隨噴嘴與工作臺(tái)的同步移動(dòng)實(shí)現(xiàn)逐層沉積，實(shí)現(xiàn)大型復(fù)雜構(gòu)件的高效成型。圖2激光、電弧及復(fù)合能量場(chǎng)技術(shù)原理圖[26,34,38,39,55]

由于LDED光斑尺寸較大，成形件表面粗糙、尺寸偏差大[27,28]及微裂紋、孔洞等缺陷[29,30]。制約了該技術(shù)的進(jìn)一步應(yīng)用。為此，有必要系統(tǒng)研究不同工藝參數(shù)對(duì)熔覆層成形行為的影響，以實(shí)現(xiàn)鈦合金構(gòu)件形性一體化調(diào)控。當(dāng)前，研究人員圍繞熔覆層成形機(jī)理已開展多項(xiàng)工作[31,32]，黃辰陽(yáng)等[33]建立了高精度多物理場(chǎng)數(shù)值模型，模擬了LDED過(guò)程中的激光-粉末-熔池的相互作用與流動(dòng)凝固行為，并通過(guò)TC17合金單道熔覆層實(shí)驗(yàn)驗(yàn)證模型可靠性，基于該模型，系統(tǒng)預(yù)測(cè)了不同工藝參數(shù)下熔覆層形貌與尺寸變化趨勢(shì)，揭示了粉末溫度分布和基板能量分配比例對(duì)熔池流場(chǎng)及熔覆尺寸的關(guān)鍵影響，為成形精度控制提供了理論依據(jù)。然而，成形精度不足、組織各向異性等關(guān)鍵問(wèn)題仍亟待解決。后續(xù)可通過(guò)多物理場(chǎng)耦合仿真與實(shí)驗(yàn)相結(jié)合的方式優(yōu)化工藝參數(shù)，并借助熱處理調(diào)控組織形貌以提升構(gòu)件性能，最終推動(dòng)大型高性能鈦合金構(gòu)件的精密化制造。

1.2激光選區(qū)熔化技術(shù)

SLM技術(shù)，亦稱為激光粉末床熔融(Laser Powder Bed Fusion,LPBF)技術(shù)，是一種基于粉末床的AM技術(shù)。其工藝過(guò)程為:首先通過(guò)刮刀或鋪粉輥將金屬粉末均勻平鋪在基板上，隨后高能激光束依據(jù)三維模型的切片數(shù)據(jù)對(duì)粉末層進(jìn)行選區(qū)掃描，使粉末熔化形成熔池，當(dāng)前層成形后，基板下降一個(gè)層厚，重復(fù)進(jìn)行鋪粉與掃描過(guò)程，逐層堆積直至完成整個(gè)構(gòu)建制造[34]。SLM成型過(guò)程中熔池的冷卻速率極高(10~10~8K/s)，能有效抑制晶粒生長(zhǎng)和合金元素偏析，在熔池內(nèi)形成細(xì)小均勻的顯微組織，從而提高成形件性能[35]。由于鈦合金化學(xué)活性高、高溫粘性大，SLM為其加工提供良好的成型環(huán)境和技術(shù)路徑[36]。此外，SLM成型過(guò)程中因極高的冷卻速率與逐層堆積帶來(lái)的循環(huán)熱歷史，使構(gòu)件內(nèi)部產(chǎn)生顯著的溫度梯度，進(jìn)而引發(fā)熱收縮不均，最終導(dǎo)致殘余應(yīng)力累積，加劇構(gòu)件變形與開裂風(fēng)險(xiǎn)并降低力學(xué)性能穩(wěn)定性[37]。合適的熱處理工藝可以極大地減小快速凝固成形過(guò)程中的殘余應(yīng)力，改變組織形貌與尺寸等，從而優(yōu)化組織和力學(xué)性能。

1.3電弧熔絲增材制造

WAAM技術(shù)以電弧為熱源將絲材熔化，依據(jù)規(guī)劃路徑逐層堆積成形構(gòu)件。根據(jù)電弧熱源特性，WAAM技術(shù)可分為熔化極氣體保護(hù)焊(Gas Metal Arc Welding, GMAW)、非熔化極氣體保護(hù)焊(Gas Tungsten Arc Welding,GTAW)和等離子弧焊(Plasma Arc Welding,PAW),其基本原理如圖2(c-e)[38]所示。GMAW具備高沉積速率和熱輸入，適用于中大型構(gòu)件制造，但高熱輸入易導(dǎo)致較大溫度梯度，影響界面結(jié)合質(zhì)量。作為其改進(jìn)工藝，冷金屬過(guò)渡焊(Cold Metal Transfer，CMT)技術(shù)(原理如圖2(f)所示[39])通過(guò)精準(zhǔn)控制焊絲回抽將熔滴送進(jìn)熔池，降低熱輸入并抑制飛濺，穩(wěn)定熔池以優(yōu)化成形質(zhì)量[40]。CMT-WAAM技術(shù)憑借加工成本低、沉積效率高等優(yōu)勢(shì)，已成功應(yīng)用于TC4 [41, 42]、TC11 [42, 43]、TC17 [44]等中大型金屬結(jié)構(gòu)件的制造。在WAAM沉積過(guò)程中，鈦合金經(jīng)歷快速冷卻時(shí)，高溫β相轉(zhuǎn)變?yōu)閬喎�(wěn)相，這類組織易引發(fā)裂紋萌生與擴(kuò)展，最終可能導(dǎo)致構(gòu)件發(fā)生脆性斷裂[45,46]。同時(shí)，多層堆積形成的熱積累效應(yīng)會(huì)使導(dǎo)致構(gòu)件內(nèi)部產(chǎn)生顯著的殘余應(yīng)力[47]，進(jìn)一步加劇結(jié)構(gòu)失效風(fēng)險(xiǎn)。因此，WAAM沉積態(tài)鈦合金構(gòu)件需通過(guò)后處理工藝調(diào)控微觀組織、優(yōu)化力學(xué)性能并消除殘余應(yīng)力，以滿足工程應(yīng)用需求。

1.4復(fù)合能量場(chǎng)

為了解決AM技術(shù)成型鈦合金過(guò)程中產(chǎn)生的微觀缺陷(裂紋、孔洞等)、殘余應(yīng)力及力學(xué)性能各向異性的問(wèn)題，研究人員提出了外場(chǎng)輔助的方法，通過(guò)外加能場(chǎng)與沉積材料的相互作用來(lái)調(diào)控其微觀組織與力學(xué)性能[48]。輔助外場(chǎng)主要包括聲場(chǎng)(Acoustic field,AF)(超聲波振動(dòng)(Ultrasonic vibration, UV))[49]、形變場(chǎng)(Deformation field, DF)[50](含滾壓(Rolling)[51]、超聲沖擊(Ultrasonic impact treatment, UIT)[52]、激光沖擊(Laser shock peening,LSP)[44]等)及磁場(chǎng)(Magnetic field,MF)[53,54],(圖2(g-i)為各類外場(chǎng)輔助示意圖[55])，其作用原理存在差異:AF利用空化和聲流效應(yīng)消除缺陷和破碎枝晶;DF通過(guò)使沉積層產(chǎn)生塑性變形來(lái)促使材料發(fā)生再結(jié)晶;MF則借助電磁力破碎枝晶來(lái)調(diào)控組織。外場(chǎng)的引入在不同程度上克服了AM的局限性[56]，具有易于調(diào)控微觀組織、減小孔隙率、降低殘余應(yīng)力和改善力學(xué)性能等優(yōu)勢(shì)[57,58]，為從根本上提升鈦合金的致密度及改善微觀組織開辟了新路徑，SLM工藝因需要在密閉腔體中進(jìn)行，將DF和MF與SLM設(shè)備集成難度較大，相關(guān)研究相對(duì)較少，但可將超聲裝置安裝在基板上，超聲波通過(guò)基板間接作用在熔池中，但隨著樣品高度的增加，聲波振動(dòng)的作用衰減，不適用于尺寸較大的樣品[59]。

上述系統(tǒng)論述了激光、電弧、復(fù)合能量場(chǎng)成型技術(shù)在鈦合金制備中的應(yīng)用現(xiàn)狀，不同技術(shù)因工藝原理的固有差異，在成形精度、沉積效率及構(gòu)件尺寸等方面各具優(yōu)勢(shì)，可滿足不同場(chǎng)景下鈦合金構(gòu)件的制備需求。然而，成型工藝及后續(xù)熱處理工藝的選擇對(duì)調(diào)控鈦合金微觀組織特征和服役性能至關(guān)重要。

2、金屬增材制造技術(shù)鈦合金的顯微組織及力學(xué)性能研究

2.1 LDED成型鈦合金顯微組織及力學(xué)性能研究

2.1.1工藝參數(shù)對(duì)LDED成型鈦合金顯微組織及力學(xué)性能的影響

在LDED成形鈦合金過(guò)程中，激光功率(P)、掃描速度(v)、層間溫度、掃描策略等工藝參數(shù)，通過(guò)調(diào)控熔池的熱歷史與流動(dòng)行為，直接影響晶粒形態(tài)、相組成及缺陷分布，從而決定構(gòu)件的力學(xué)性能[60-62]。夏超 [63]利用具有高P的LDED技術(shù)成型TA15合金，發(fā)現(xiàn)高P引入的高能量使得沉積態(tài)組織為粗 α板條狀，性能呈現(xiàn)出低強(qiáng)度、高塑性特點(diǎn)。而工藝參數(shù)的協(xié)同作用是實(shí)現(xiàn)力學(xué)性能強(qiáng)塑性平衡的關(guān)鍵，艾佳華 [64]在LDED成型Ti-1300鈦合金過(guò)程中，通過(guò)調(diào)控P、v與送粉速率( P r )等工藝參數(shù)，獲得了穩(wěn)定的熔寬和匹配性良好的強(qiáng)塑性。除了優(yōu)化工藝參數(shù)外，層間強(qiáng)制冷卻可降低層間溫度，減少熱積累并細(xì)化晶粒，協(xié)同提升鈦合金的強(qiáng)度和塑性，Wang等[65]采用層間和軌間強(qiáng)制冷卻(Inter Layer Cooling-In Track Cooling, ILC-ITC)6s,阻斷β晶粒的連續(xù)生長(zhǎng)并生成了柱狀β晶粒(圖3(a2)所示)，使TC4合金在垂直(0°)與平行(90°)于構(gòu)建方向(Building Direction，BD)的極限抗拉強(qiáng)度(Ultimate Tensile Strength，UTS)和延伸率(Elongation，EL)均顯著提升，實(shí)現(xiàn)強(qiáng)塑性的協(xié)同優(yōu)化。掃描策略對(duì)殘余應(yīng)力、變形行為、及晶粒形態(tài)具有顯著影響[66,67]。Zhang[68]采用數(shù)值模擬方法系統(tǒng)比較了12種掃描路徑的影響規(guī)律，根據(jù)其熱-力耦合仿真結(jié)果表明，層間掃描方向90°旋轉(zhuǎn)有利于降低殘余應(yīng)力，而45°旋轉(zhuǎn)策略則能獲得最優(yōu)的變形控制效果。Wang等[69]在TC4合金成型中采用層內(nèi)反向掃描結(jié)合層間橫縱向交替掃描策略(圖3(b1-b2))，發(fā)現(xiàn)平行于基板的試樣因籃狀 α/α團(tuán)簇結(jié)構(gòu)及更細(xì)小晶粒，展現(xiàn)出最高的 UTS和屈服強(qiáng)度(YieldStrength，YS)、垂直于基板的試樣(90°LDED試樣)則因組織差異獲得最大EL(圖3(b3)所示)。

2.1.2熱處理對(duì)LDED成型鈦合金顯微組織及力學(xué)性能的影響

LDED成型的鈦合金中的典型的粗大柱狀晶組織會(huì)引起力學(xué)性能的顯著各向異性，而殘余應(yīng)力集中將導(dǎo)致邊緣翹曲降低成形件的成形質(zhì)量和成品率，熱處理工藝可以調(diào)控LDED成型的鈦合金組織形貌，合適的熱處理工藝可以使組織性能均勻化 [71, 72]。榮鵬等 [73]研究了三種不同熱處理對(duì)LDED成型TC4鈦合金微觀組織及力學(xué)性能的影響:經(jīng)975℃/1 h/AC+600℃/4h/AC處理后獲得了韌性更高的 α p 相寬度更寬，且原 β相晶界附近生成等軸 α p 相，使得試樣具有較強(qiáng)的變形能力和高協(xié)調(diào)性，各向異性得到了改善。Ding[74]對(duì)LDED成型Ti55531鈦合金采用超臨界β退火+時(shí)效(SBA-A)、超臨界β循環(huán)退火+時(shí)效(SBCA-A)等工藝，發(fā)現(xiàn)SBA-A與SBCA-A處理后，合金內(nèi)部分別呈現(xiàn)出Widmanstatten晶界和鋸齒狀晶界(圖4(a1-a2)為合金裂紋擴(kuò)展示意圖)，有效抑制裂紋擴(kuò)展，其中SBA-A處理使合金的UTS達(dá)1045±12 MPa、EL達(dá)12.0%±1.2%，斷裂韌性高達(dá)81.7±1.1 MPa m1/2，強(qiáng)塑性匹配性最優(yōu)(圖4(b1-b2))(詳見(jiàn)表1)。曾宙[75]針對(duì)LDED成型TB6鈦合金設(shè)計(jì)了多重?zé)崽幚?固溶+一次時(shí)效+兩次時(shí)效)。如圖4(b)所示，840℃固溶形成單一β相;一次時(shí)效(840℃+760℃)析出初生 α_p 、α GB 相并產(chǎn)生無(wú)相析出區(qū)(Precipitate-Free Zones，PFZ);二次時(shí)效(840℃+760℃+530℃)促使次生α_s相彌散析出(形貌隨溫度升高從細(xì)針狀轉(zhuǎn)短棒狀)，且PFZ被α_s相填充;隨二次時(shí)效溫度升高，合金UTS降至973 MPa，EL提高至14.1%，530℃二次時(shí)效處理時(shí)強(qiáng)塑性平衡方面表現(xiàn)最好最佳。

綜上所述，LDED成型鈦合金的力學(xué)性能調(diào)控需以“熱歷史-微觀組織-性能關(guān)聯(lián)機(jī)制”為核心:通過(guò)優(yōu)化P、v等參數(shù)控制能量輸入，結(jié)合層間強(qiáng)制冷卻與掃描策略實(shí)現(xiàn)晶粒細(xì)化及殘余應(yīng)力降低。LDED鈦合金的熱處理調(diào)控需結(jié)合合金類型與原始沉積組織:退火適用于殘余應(yīng)力釋放與組織均勻化;固溶時(shí)效通過(guò)析出相各向同性分布抑制力學(xué)各向異性，適用于β型合金;多重?zé)崽幚韯t通過(guò)精細(xì)調(diào)控相變與晶界結(jié)構(gòu)，實(shí)現(xiàn)強(qiáng)塑性的協(xié)同突破。

表1不同熱處理對(duì)LDED成型鈦合金組織和力學(xué)性能的影響[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成型鈦合金顯微組織及力學(xué)性能研究

2.2.1工藝參數(shù)對(duì)SLM成型鈦合金顯微組織及力學(xué)性能影響

SLM成形質(zhì)量的核心在于工藝參數(shù)匹配與能量輸入控制，不當(dāng)?shù)膮��?shù)組合易引發(fā)匙孔、未熔合孔洞等微觀缺陷[76-78]。能量密度(Energy Density, E)作為關(guān)鍵調(diào)控指標(biāo)可實(shí)現(xiàn)成形質(zhì)量的精準(zhǔn)控制[79, 80](E=P/(vht)，P為激光功率，v為掃描速度，h為掃描間距，t為層厚)。P和v的協(xié)同優(yōu)化是控制E的核心，Zhang等[81]研究了P、v對(duì)SLM成型Ti-24Nb-4Zr-8Sn鈦合金構(gòu)件成形質(zhì)量的影響，通過(guò)優(yōu)化P、v值可實(shí)現(xiàn)致密度的提升。Cai等[82]研究了E對(duì)SLM成型TA15鈦合金顯微組織演變的影響:低E導(dǎo)致熔化不充分并產(chǎn)生氣孔，高E引發(fā)過(guò)熔與球化效應(yīng)，此結(jié)論與Liverani等[83]、Wei等[84]和Guan等[85]研究一致。PANWISAWAS等[86]和QIU等[87]研究t對(duì)合金表面質(zhì)量的影響，較低的t利于合金表面的成形質(zhì)量，當(dāng)t超過(guò)0.04mm時(shí)使得表面粗糙度和孔隙率增大，繼續(xù)增加t將惡化合金的成形質(zhì)量。

此外，掃描策略可通過(guò)調(diào)整激光掃描路徑與方向，改變熱流傳遞路徑與熱量分布狀態(tài)，調(diào)控晶粒取向與溫度梯度，緩解熱收縮不均帶來(lái)的應(yīng)力集中來(lái)降低殘余應(yīng)力[88,89]。陳德寧[90]對(duì)比島式與蛇形掃描發(fā)現(xiàn)，島式掃描因島嶼邊緣二次升溫使TC4合金的溫度場(chǎng)分布更均勻，可減小應(yīng)力集中，但溫度梯度較低導(dǎo)致柱狀晶更粗大;Ali等[67]證實(shí)，棋盤格掃描策略與連續(xù)層間旋轉(zhuǎn)角度有助于降低殘余應(yīng)力;Shi等[91]將直線LINE、棋盤格CHESS、條紋STRIPE掃描與定向角度偏移(0°、45°、90°)組合，發(fā)現(xiàn)CHESS&45°策略下，TC4合金試樣熔道連續(xù)，無(wú)明顯孔洞，β相與α'相分布均勻;縱向截面可見(jiàn)沿成形方向排列的柱狀β晶，試樣表面粗糙度達(dá)14μm(如圖5(b1-b2))，致密度達(dá)99.85%。

2.2.2熱處理對(duì)SLM成型鈦合金顯微組織及力學(xué)性能影響

SLM成型鈦合金過(guò)程中，激光高能束高頻短時(shí)作用于鈦合金，使其在凝固過(guò)程中發(fā)生晶粒外延生長(zhǎng)導(dǎo)致柱狀晶的生成 [92, 93]，最終使成型件呈現(xiàn)力學(xué)性能各向異性。受快速冷卻過(guò)程的影響，β相來(lái)不及轉(zhuǎn)化為α相從而在柱狀晶內(nèi)部形成了大量α'相使得鈦合金強(qiáng)度提升，但塑韌性降低 [94]。為了獲得優(yōu)異力學(xué)性能的鈦合金，Carrozza等[95]對(duì) SLM成型的 Ti6246合金進(jìn)行750℃/2h固溶處理后，α'相分解為片層狀α+β，實(shí)現(xiàn)強(qiáng)塑性的良好平衡。Huang等[96]對(duì)SLM成型TC4鈦合金進(jìn)行不同退火處理發(fā)現(xiàn)試樣的UTS和硬度均有所下降，而塑性有所提高。雙重退火制度可顯著消除晶界，柱狀晶粒消失后的組織尺寸分布趨于均勻，這有利于提高合金的塑性同時(shí)使得力學(xué)性能的各向異性顯著降低，其中在850℃/30 min/AC+600℃/2h/AC退火處理下力學(xué)性能各向異性改善效果最佳(詳見(jiàn)表2)。

與傳統(tǒng)的熱處理工藝相比，多步熱處理技術(shù)(Multi-Step Heat Treatment，MSHT)能有效促進(jìn)a球化與等軸組織形成，強(qiáng)度塑性匹配效果更顯著。Li等[97]對(duì)SLM成型TC4合金施加MSHT(工藝路線如圖6(a1)，球化機(jī)制如圖6(a2))，通過(guò)逐步升溫保溫與爐冷，先使 α'完全分解為 α+β，再經(jīng)cylinderization、edge spheroidization等球化機(jī)制將片狀 α轉(zhuǎn)為近等軸α晶粒;該組織可降低力學(xué)各向異性與晶界滑動(dòng)阻力，實(shí)現(xiàn)強(qiáng)塑性匹配。Wang等[98]對(duì)TA15合金進(jìn)行低溫-高溫(Low-High Temperature,LHT)多步加熱后(工藝路線如圖6(b1))，形成片晶、等軸晶與短棒狀a組成的三態(tài)組織(形成機(jī)制如圖6(b2))，片狀a晶粒保證了合金的強(qiáng)度，等軸和短棒狀a晶粒降低晶界滑動(dòng)阻力、激活多滑移系提升塑性。

表 2不同熱處理對(duì) SLM成型鈦合金組織和力學(xué)性能的影響 [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成型鈦合金顯微組織及力學(xué)性能研究

2.3.1工藝參數(shù)對(duì)WAAM成型鈦合金顯微組織及力學(xué)性能的影響

WAAM成型過(guò)程中焊道形貌可直觀反映焊接質(zhì)量[99]，孫清潔等[100]研究表明，調(diào)整電弧電流可有效調(diào)節(jié)Ti60合金焊道的宏觀成形，增大熔寬和熔深，減少金屬球化并提升焊道均勻性。Liu等[101]針對(duì)GTAM-WAAM成型TC4合金，采用Box-Behnken設(shè)計(jì)響應(yīng)面實(shí)驗(yàn)構(gòu)建熔覆層寬、高及熔深的回歸模型，方差分析表明:焊接電流(I)、送絲速度(V)與焊槍移動(dòng)速度(Vs)為關(guān)鍵影響因子。其可行性指標(biāo)分布如圖7(a1-a2)所示，最優(yōu)參數(shù)對(duì)應(yīng)圖中紅色區(qū)域;最優(yōu)參數(shù)下，TC4薄壁件韃課瘓�为网历Q櫓�，a相從頂部到底部逐漸粗化，顯微硬度隨之下降，拉伸性能因a相排列及晶粒取向呈現(xiàn)各向異性。

熱輸入過(guò)高會(huì)導(dǎo)致沉積層間溫度升高、層高減小、寬度增大，引發(fā)尾部塌陷，影響成形質(zhì)量與力學(xué)性能[102,103]。通過(guò)層間強(qiáng)制冷卻和合理的路徑規(guī)劃能夠使熱輸入均勻分布，減少局部過(guò)熱或冷卻過(guò)快引發(fā)的缺陷，細(xì)化晶粒促進(jìn)等軸晶的生成，提升材料性能。如，Ogino等[104]發(fā)現(xiàn)，每道次成型后冷卻并嚴(yán)格控制層間溫度，可明顯改善尾部塌陷;He等[105]通過(guò)梯度熱輸入結(jié)合層間冷卻工藝，通過(guò)提高冷卻速率抑制柱狀晶粒外延生長(zhǎng)，使Ti-6Al-2Zr-1Mo-1V(TC11)合金形成細(xì)柱狀-等軸混合組織，其顯微硬度、UTS和EL分別提高了5.3%、6.6%和37.6%。Wang等[106]對(duì)比分析了三種沉積策略(A:雙向掃描+0s層間停留，B:單向掃描+24s層間停留，C:單向掃描+120s層間停留)對(duì)WAAM成型TC4合金的溫度與應(yīng)力應(yīng)變場(chǎng)的影響:在策略B下，a片層邊界形成無(wú)位錯(cuò)再結(jié)晶a晶粒，位錯(cuò)向先 β晶界富集，晶粒內(nèi)部呈低儲(chǔ)能狀態(tài)(如圖7(b1));單向掃描路徑使熱場(chǎng)分布均勻并形成水平層帶(圖7(b2));策略C更長(zhǎng)的停留時(shí)間為已沉積層提供了更充足的散熱時(shí)間，使得沉積過(guò)程中的熱積累顯著降低，且熱場(chǎng)分布更均勻，α片層寬度變化平緩，最終獲得等軸晶組織，顯著提材料強(qiáng)度和硬度。

2.3.2熱處理對(duì)WAAM成型鈦合金顯微組織及力學(xué)性能的影響

WAAM在逐層堆積的過(guò)程中使材料經(jīng)歷多次的熱循環(huán)，同時(shí)材料在凝固過(guò)程中的冷卻速度較大，使得原始柱狀 β相會(huì)轉(zhuǎn)變成不同形態(tài)的脆性 α相，造成合金強(qiáng)度和塑性等力學(xué)性能的各向異性 [107]。為了改善微觀組織均勻性和材料力學(xué)性能的各向異性，研究人員對(duì)WAAM成型鈦合金熱處理工藝進(jìn)行了深入研究。張帥鋒等[108]在 CMT-WAAM成型Ti-6Al-3Nb-2Zr-1Mo(Ti6321)合金過(guò)程中發(fā)現(xiàn)，經(jīng)700℃退火后，Ti6321合金UTS下降70 MPa，這是由于熱處理導(dǎo)致位錯(cuò)密度降低，位錯(cuò)間的交互作用減弱，從而減少了對(duì)位錯(cuò)滑移的阻礙作用。當(dāng)退火溫度升高至800℃時(shí)，α片層進(jìn)一步均勻化，其相鄰片層間的亞穩(wěn) β相進(jìn)一步轉(zhuǎn)變分解，亞穩(wěn) β相轉(zhuǎn)變?yōu)槎贪魻?α相， α/ β相界面數(shù)量增加，從而增強(qiáng)了對(duì)滑移的阻礙效果，促使強(qiáng)度升高。Lin等 [109]采用Gleeble熱模擬構(gòu)建了 WAAM成型 TC4合金不同熱處理態(tài)(沉積態(tài):AD;固溶態(tài):AD-ST;固溶+時(shí)效態(tài):AD-ST-Age)的微觀結(jié)構(gòu)梯度，AD-ST-Age態(tài)α相取向集中性高于AD-ST態(tài)(圖8(a1-a2))，最優(yōu)的熱處理工藝為AD-ST-Age(830 ∘C/2h/WC+ 500 ∘C/4 h/FC，F(xiàn)C:爐冷)，ST使 α ′馬氏體的細(xì)化，Age促進(jìn) α魏氏體的細(xì)化及 α'分解，最終使YS、UTS分別提高12.85%、3.33%。Wang等[110]對(duì)WAAM成型TC4合金采用了五種不同的熱處理方案(HT1-HT5)研究其微觀結(jié)構(gòu)演變，與沉積態(tài)相比，經(jīng)過(guò)HT1處理后，α/β界面相部分分解，導(dǎo)致了EL的降低;HT2處理后板條 α相粗化，并且在HT2試樣中觀察到了有利于提高塑性的 α/β界面相，導(dǎo)致了UTS的降低和EL的增加。而經(jīng)HT5處理后，出現(xiàn)細(xì)小的不連續(xù) α GB 相、 α p 相和α_s相，α_s相起到較強(qiáng)的彌散強(qiáng)化作用，β相中V元素的界面偏析獲得了較多的α/β相界面(圖8(b1-b2))，且細(xì)小不連續(xù)的 α GB 相避免了應(yīng)力集中，使試樣的UTS和EL分別達(dá)到886 MPa和 16.6%(詳見(jiàn)表3)。

綜上所述，WAAM熱輸入顯著影響鈦合金成形質(zhì)量，均勻化熱輸入是改善組織形態(tài)、提升力學(xué)性能的重要技術(shù)路徑。鈦合金的強(qiáng)度源于a相細(xì)化、彌散強(qiáng)化及位錯(cuò)阻礙作用，塑性主要依賴 α/β相界面的變形協(xié)調(diào)能力。通過(guò)退火、固溶+時(shí)效等熱處理工藝可進(jìn)一步調(diào)控組織形態(tài)，包括a相、亞穩(wěn)相及a/β相界面數(shù)量，實(shí)現(xiàn)強(qiáng)塑性的均衡提升。

表3不同熱處理對(duì)WAAM成型鈦合金組織和力學(xué)性能的影響[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復(fù)合能量場(chǎng)成型鈦合金顯微組織及力學(xué)性能研究

隨著航空航天、生物醫(yī)學(xué)等高端領(lǐng)域?qū)��?gòu)件結(jié)構(gòu)穩(wěn)定性、性能可靠性及輕量化需求不斷提升，傳統(tǒng)單一調(diào)控手段已難以滿足復(fù)雜工況要求，外場(chǎng)輔助調(diào)控技術(shù)(AF、DF、MF等)被引入以優(yōu)化鈦合金的成形質(zhì)量并提升其力學(xué)性能[111]。

AF輔助通常是利用UV產(chǎn)生的聲能與AM相結(jié)合，利用其獨(dú)特的聲流與空化效應(yīng)來(lái)控制金屬熔池的凝固過(guò)程[59,112,113]。Todaro等[59]將高強(qiáng)度超聲共振場(chǎng)與LDED技術(shù)協(xié)同(圖9(a1))，通過(guò)UV引發(fā)的熔池?cái)_動(dòng)與晶粒破碎，將TC4合金中粗大的柱狀β晶細(xì)化為等軸晶，電子背散射衍射(Electron Backscatter Diffraction，EBSD)(圖9(a2))表明，無(wú)超聲時(shí)，α相、β相均呈現(xiàn)明顯擇優(yōu)取向;施加超聲使a相、β相的最大均勻分布倍數(shù)(Multiples of Uniform Distribution，MUD)減小，織構(gòu)弱化， β相轉(zhuǎn)為等軸晶粒且<001>織構(gòu)消失，各向異性降低，UTS、YS較未處理態(tài)提高約12%。

在AM過(guò)程中引入DF使沉積層發(fā)生塑性變形，在下一層沉積時(shí)，塑性變形部分可能發(fā)生再結(jié)晶，從而改變材料微觀組織與力學(xué)性能。Yang等[114]采用UIT輔助WAAM工藝，在Ti-6Al-4V沉積后實(shí)施兩次UIT，使粗大柱狀β晶轉(zhuǎn)變?yōu)榈容S晶與短柱狀晶交替分布的組織，提升表層均勻性(圖9(b1)UIT輔助WAAM工藝晶粒生長(zhǎng)示意圖)。Chen等[115]采用UIT輔助LDED制備TA15鈦合金，晶粒細(xì)化使UTS和EL均提高。此外，DF還能將沉積表面一定深度范圍內(nèi)殘余拉應(yīng)力被轉(zhuǎn)變?yōu)閷?duì)材料力學(xué)性能有益的壓應(yīng)力[116]，孟憲凱團(tuán)隊(duì)[117]研究發(fā)現(xiàn)，LSP在TC6合金表層引入殘余壓應(yīng)力，抑制疲勞裂紋的萌生與擴(kuò)展，延長(zhǎng)疲勞壽命;其開發(fā)的雙脈沖LSP技術(shù)，通過(guò)延長(zhǎng)沖擊作用時(shí)間，誘導(dǎo)Ti6Al4V合金形成“細(xì)晶-粗晶-細(xì)晶”的復(fù)合結(jié)構(gòu)，顯著提升顯微硬度與強(qiáng)度，且保持良好的塑性。

MF定向調(diào)控中，縱向與橫向MF作用機(jī)制存在差異。縱向MF通過(guò)洛倫茲力驅(qū)動(dòng)熔池環(huán)向流動(dòng)，可增加焊道寬高比、降低表面粗糙度，并抑制邊緣焊道流淌與塌陷[118,119];橫向MF則通過(guò)偏轉(zhuǎn)電弧誘導(dǎo)熔池單向?qū)α鳎�降低熔池底部等軸晶區(qū)域的占比與胞狀枝晶間距，提升枝晶前沿成分過(guò)冷度[120]。Zhao等[121]將磁場(chǎng)與LDED相結(jié)合(如圖9(c1)所示)，研究發(fā)現(xiàn)，在0.55T橫向靜磁場(chǎng)(Static Magnetic Field,SMF)下制備TC4鈦合金的性能最優(yōu)，SMF通過(guò)調(diào)控熔池流動(dòng)與固態(tài)相變，增強(qiáng)a相晶界連續(xù)性(圖9(c5))、分散取向;弱化β晶粒織構(gòu)(圖9(c3，c6))，增加α相形核數(shù)量并形成規(guī)則位錯(cuò)陣列與亞晶界(圖9(c7))，有效降低力學(xué)性能各向異性;該團(tuán)隊(duì)[122]進(jìn)一步提出高磁場(chǎng)(High Magnetic Field, HMF, 3T)與熱處理相結(jié)合調(diào)控SLM成型TC4合金的組織，發(fā)現(xiàn)HMF可加速a相的粗化和球化，雖使UTS與YS相較原始態(tài)略有降低，但EL提高至14.1%-15.4%，實(shí)現(xiàn)更優(yōu)的強(qiáng)塑性匹配。

綜上所述，外場(chǎng)輔助技術(shù)通過(guò)調(diào)控AM鈦合金微觀組織特征，如改善織構(gòu)強(qiáng)度、誘導(dǎo)柱狀晶向等軸晶轉(zhuǎn)變、引入殘余壓應(yīng)力等方面，實(shí)現(xiàn)強(qiáng)度與塑性的同步提升，然而，當(dāng)前關(guān)于外場(chǎng)輔助與熱處理工藝耦合的系統(tǒng)性研究較為匱乏，其作用機(jī)制與工藝適配性的深入探索具有重要的理論與工程價(jià)值。

2.5有限元仿真模擬鈦合金增材制造過(guò)程

有限元分析(Finite Element Analysis，F(xiàn)EA)通過(guò)構(gòu)建多物理場(chǎng)耦合模型，可精準(zhǔn)模擬從熔池演變到逐層堆積的全過(guò)程，量化工藝參數(shù)對(duì)應(yīng)力、變形及微觀組織的影響，已成為預(yù)測(cè)并優(yōu)化金屬AM質(zhì)量的主流數(shù)值方法。該方法彌補(bǔ)了實(shí)驗(yàn)手段在瞬態(tài)場(chǎng)監(jiān)測(cè)方面的局限，支持參數(shù)化仿真與快速工藝評(píng)估，為L(zhǎng)DED、SLM、WAAM等工藝的成型控制提供了重要理論依據(jù)。

在LDED工藝中，循環(huán)熱載荷導(dǎo)致工件劇烈的溫度波動(dòng)，冷卻后形成殘余拉應(yīng)力。Deng等[123]建立了三維瞬態(tài)熱分析有限元模型，模擬Ti60鈦合金在LDED成型過(guò)程中的熔池演化(如圖10(a1))，通過(guò)G和V的關(guān)聯(lián)(圖10(a2))揭示了晶粒生長(zhǎng)模式對(duì)組織形態(tài)的影響，指出柱狀晶向等軸晶轉(zhuǎn)變(Columnar to Equiaxed Transition，CET))有助于緩解熱收縮不均，降低殘余應(yīng)力，如圖10(a3)所示，熔池內(nèi)溫度梯度方向的變化促使等軸晶多向生長(zhǎng)，進(jìn)而弱化織構(gòu)。Wu等[124]針對(duì)LDED成型Ti6Al4V合金，構(gòu)建熱-力耦合有限元模型，提出可變激光功率沉積策略StrategyC(四種策略詳見(jiàn)圖10(b))，動(dòng)態(tài)模擬溫度與應(yīng)力場(chǎng)演變。結(jié)果表明:該策略使試樣平均基底溫度降低12.68%-15.08%，最大主應(yīng)力下降7.8%-32.14%;圖10(c)為四種沉積策略下沿沉積方向的殘余應(yīng)力(σx)分布情況，其中StrategyC通過(guò)降低溫度梯度，使殘余應(yīng)力分布更均勻，模擬與實(shí)驗(yàn)的溫度及應(yīng)力誤差分別控制在10.12%和6.92%以內(nèi)。

在SLM加工過(guò)程中，金屬粉末受到高能能量束瞬時(shí)輻照，熔化形成微尺度熔池，隨著能量熱源移動(dòng)，熔池在先前沉積的基底冷卻作用下迅速凝固，使熔池內(nèi)部表現(xiàn)出高溫度梯度(G)(>10^2 K/mm)、高冷卻速率(V)(約10^7 K/s)和高殘余熱應(yīng)力累積的非平衡短時(shí)冶金特征[125]。這種極端加工條件和復(fù)雜流體動(dòng)力學(xué)行為的耦合作用，極易產(chǎn)生氣孔、匙孔孔隙、熔合不良、球化效應(yīng)等缺陷[126]。為深入揭示工藝對(duì)缺陷形成的影響機(jī)制并實(shí)現(xiàn)精準(zhǔn)調(diào)控，介觀尺度數(shù)值模擬已成為重要研究手段，圖11(a1)為SLM制造中多尺度、多物理場(chǎng)現(xiàn)象的示意圖[127]。鐘敏奎[128]通過(guò)多物理場(chǎng)模擬與實(shí)驗(yàn)相結(jié)合的方法，系統(tǒng)分析了P、v對(duì)SLM成型TC4鈦合金熔池尺寸的影響(如圖11(a2)所示):隨著P增加，熔池寬度與深度均相應(yīng)擴(kuò)大;隨著v的減小，熱積累效應(yīng)增強(qiáng)，熔池尺寸顯著增大，證實(shí)了P、v的協(xié)同調(diào)控是優(yōu)化熔池形貌、抑制缺陷的關(guān)鍵途徑。Yin等[129]對(duì)SLM成型TC4合金的溫度場(chǎng)進(jìn)行有限元仿真，發(fā)現(xiàn)提高v和優(yōu)化沉積高度可有效減少因晶粒取向差異導(dǎo)致的不均勻收縮，從而降低殘余應(yīng)力與變形。在掃描策略與輔助工藝優(yōu)化方面，Cheng等[130]研究表明，SLM成型過(guò)程中X、Y方向的應(yīng)力集中主要分布于沉積層邊緣及基體界面區(qū)域，其中環(huán)形掃描模式下應(yīng)力值最大，而45°斜線掃描可通過(guò)均勻化溫度場(chǎng)分布，顯著降低兩個(gè)方向的殘余應(yīng)力。此外Zhou等[131]利用激光重熔(Laser Remelting,LR)多場(chǎng)耦合模型研究了LR對(duì)致密度、氣孔等的調(diào)控，受成形過(guò)程預(yù)熱的影響，LR形成的熔池尺寸更大，有助于促進(jìn)熔體流動(dòng)與孔隙填充，從而實(shí)現(xiàn)致密度提升與缺陷消除。

WAAM的沉積過(guò)程往往伴隨著較大的熱輸入和局部熱積累，導(dǎo)致殘余應(yīng)力分布不均勻和變形，還會(huì)導(dǎo)致粗晶組織 [132]。Li等 [133]結(jié)合多組分相場(chǎng)(Phase Field，PF)模型與FEA，預(yù)測(cè)WAAM成型Ti-Al-Fe-V合金的CET行為，PF模擬表明低G和高V利于等軸晶形成(圖11(b1-b4);FEA進(jìn)一步獲取了瞬態(tài)G、V分布與溫度場(chǎng)(圖11(b5-b6))，揭示熱輸入密度對(duì)CET位置的關(guān)鍵影響:高能量輸入促使CET提前發(fā)生。劉國(guó)昌等[134]采用Simufact Welding軟件仿真激光電弧復(fù)合AM的熱力場(chǎng)，并通過(guò)試驗(yàn)驗(yàn)證模型的可靠性，發(fā)現(xiàn)溫度積累效應(yīng)顯著，等效應(yīng)力逐步轉(zhuǎn)化為殘余應(yīng)力，且應(yīng)力集中于道間、層間結(jié)合區(qū)及基板連接處;基于仿真優(yōu)化，通過(guò)不同堆積路徑下應(yīng)力分布圖(圖11(c1-c2))得出道間堆積采用同向式(左至右)、層間堆積采用交錯(cuò)式的最優(yōu)路徑方案，有效改善了應(yīng)力分布與成形質(zhì)量。

綜上，F(xiàn)EA作為金屬AM質(zhì)量預(yù)測(cè)與工藝優(yōu)化的核心數(shù)值方法，通過(guò)構(gòu)建多物理場(chǎng)耦合模型，可精準(zhǔn)模擬LDED、SLM、WAAM等典型工藝的熔池演變、逐層堆積及瞬態(tài)場(chǎng)演化全過(guò)程，有效彌補(bǔ)了實(shí)驗(yàn)手段在瞬態(tài)監(jiān)測(cè)中的局限，為量化工藝參數(shù)對(duì)殘余應(yīng)力、變形及微觀組織的影響提供了重要理論支撐。

3、增材制造鈦合金的耐腐蝕性能研究

3.1激光增材制造鈦合金的耐腐蝕性

激光成型鈦合金的耐腐蝕性能與其顯微組織特征密切相關(guān)。較低的v有利于形成細(xì)小的 α ′馬氏體，從而提高表面鈍化膜的致密性與均勻性，顯著增強(qiáng)合金的耐腐蝕性能 [135]。Lu等[136]研究表明，在高P(250W)與中等v(1200mm/s)下成型的TC4合金具有優(yōu)良的綜合性能:其內(nèi)部為規(guī)則生長(zhǎng)的柱狀β晶與分散分布的針狀 α ′馬氏體，不僅力學(xué)性能優(yōu)異，且表面可快速形成以TiO2為主的致密鈍化膜，這是其耐腐蝕性能突出的關(guān)鍵因素。由于顯微組織的差異，SLM成型鈦合金的耐蝕性能是各向異性的。Dai等[137]通過(guò)電化學(xué)測(cè)試與組織分析比較了TC4合金XY與XZ平面的耐蝕行為。經(jīng)Tafel擬合結(jié)果(如圖12(a-b)所示)，在3.5 wt% NaCl溶液中，兩平面的鈍化電流密度相近;而在1MHCl溶液中，XZ平面的鈍化電流密度高于XY平面，說(shuō)明XY平面的耐蝕性更優(yōu)。其原因在于XZ平面α相含量較高、 β相較少( β相是一種良好的腐蝕抑制劑)，導(dǎo)致其耐蝕性較差(如圖12(c-d)所示)。退火與熱等靜壓(HotIsostatic Pressing，HIP)等熱處理也對(duì)耐腐蝕性能具有重要影響[92,138]。退火處理可使 α/β相分布更均勻，降低材料各向異性;HIP處理則能有效閉合SLM成型過(guò)程中形成的缺陷，顯著提高TC4合金在腐蝕介質(zhì)中的耐腐蝕性能。Li等[139]針對(duì) SLM成型Ti-6Al-4V-3Cu合金，研究了不同溫度(760°C、820°C、875C)保溫2h后水冷的組織演變及其對(duì)耐腐蝕性能的影響。結(jié)果表明:760℃熱處理為最優(yōu)工藝，可實(shí)現(xiàn) α ′馬氏體部分分解( α ′ → α + β)與殘余應(yīng)力釋放，同時(shí)避免晶粒粗化與Ti 2Cu相非均勻析出，所得致密穩(wěn)定的鈍化膜(以TiO2為主)，耐腐蝕性能最佳。Anantharam等[140]發(fā)現(xiàn)，經(jīng)800℃/2h退火處理的LDED成型Ti-6Al-4V合金腐蝕電流密度顯著降低，耐腐蝕性最優(yōu)。其原因?yàn)橥嘶鸫偈?alpha;'相轉(zhuǎn)變?yōu)閍+β相雙向組織，減少a/β界面面積，提升電化學(xué)穩(wěn)定性;未處理的沉積樣品由于缺乏β相，表現(xiàn)出更高的腐蝕傾向。

3.2電弧增材制造鈦合金的耐腐蝕性

WAAM成型的鈦合金，其微觀結(jié)構(gòu)常呈現(xiàn)晶粒取向與 α/ α ′相形態(tài)的各向異性，導(dǎo)致耐腐蝕性能普遍低于傳統(tǒng)鍛件。研究表明，鈦合金的腐蝕行為強(qiáng)烈依賴于其微觀結(jié)構(gòu)和服役環(huán)境 [141]。熱處理是調(diào)控組織并影響耐蝕性能的關(guān)鍵手段，但其效果因合金成分與工藝條件而異。例如，在3.5wt%NaCl溶液和5MHCl溶液中，Ti-6Al-3Nb-2Zr-1Mo合金的耐腐蝕性會(huì)隨退火溫度從850℃升至1000℃而提升，主要?dú)w因于β相體積分?jǐn)?shù)增加與α相片層厚度減小[142];而Ti-4Al-5Mo-3V-5Cr-Fe合金經(jīng)750℃、870℃固溶處理并在500℃時(shí)效6h后，呈現(xiàn)層狀與雙峰結(jié)構(gòu)，其在2MHCl溶液中的耐腐蝕性能卻有所下降[143]，說(shuō)明熱處理對(duì)耐蝕性的影響具有合金特異性。鈦合金的腐蝕行為還取決于鈍化膜的形成，該鈍化膜主要由TiO2構(gòu)成，可自發(fā)覆蓋于合金表面，且鈍化膜穩(wěn)定性越高，合金的耐腐蝕性越優(yōu)異 [144]。Cheng等 [145]對(duì)比了鍛造與WAAM成型TC4合金在模擬質(zhì)子交換膜水電解(Proton Exchange Membrane Water Electrolysis, PEMWE)陽(yáng)極環(huán)境中的電化學(xué)行為，發(fā)現(xiàn)經(jīng)1050 ∘C熱處理后，WAAM TC4合金中V2p3/2譜僅呈現(xiàn)釩氧化物信號(hào)(圖13(i,l))，而鍛造與沉積態(tài)樣品中則檢測(cè)到金屬V(圖13(c,f))。該合金腐蝕電流密度最低(54μA/cm2)，鈍化電流密度為19.5 μA/cm²，氧化鈦(Ti 2O3與TiO2)占比達(dá)80.9%，表明高比例鈦氧化物有助于形成更穩(wěn)定的鈍化膜，顯著提升耐腐蝕性能。除了熱處理外，WAAM過(guò)程中的保護(hù)氣體成分也對(duì)組織均勻性與鈍化膜穩(wěn)定性有重要影響。Chen等[146]指出，在CMT-WAAM成型Ti-6Al-4V的過(guò)程中，隨著保護(hù)氣體中He的比例增加，電弧電壓升高，電弧穩(wěn)定性增強(qiáng);當(dāng)He含量為50%時(shí)，部分a'馬氏體分解為a+β籃狀組織，促進(jìn)兩相平衡分布，這種組織均勻化有助于形成更致密的鈍化膜，從而改善耐腐蝕性能。

3.3復(fù)合能量場(chǎng)成型鈦合金的耐腐蝕性

復(fù)合能量場(chǎng)成型技術(shù)通過(guò)多場(chǎng)協(xié)同作用優(yōu)化鈦合金的微觀結(jié)構(gòu)與表面狀態(tài)，為提升耐腐蝕性提供了新途徑。LSP具有更高能量、高應(yīng)變率的特點(diǎn)，不僅能改善材料的拉伸與疲勞性能[147,148]，還可通過(guò)組織調(diào)控增強(qiáng)耐腐蝕性[149,150]。Jiang等[151]提出電脈沖聯(lián)合激光沖擊強(qiáng)化(Electro-pulsing Combined with Laser Shock Peening,EP-LSP)復(fù)合工藝,促使Ti-6Al-4V合金表面晶粒細(xì)化、 α相向 β相轉(zhuǎn)化，為鈍化膜提供更多形核位點(diǎn)，加速形成均勻致密的鈍化膜(圖14(a1-a2)為原始態(tài)和1次EP-LSP樣品的腐蝕示意圖)。經(jīng)1次EP-LSP處理后，試樣的腐蝕電流密度降低，腐蝕電位提高，耐腐蝕性能提升(圖14(a3)為對(duì)應(yīng)的Tafel極化曲線)。除LSP技術(shù)外，磁弧振蕩也被用于優(yōu)化WAAM成型鈦合金的耐腐蝕性能。Wu等[152]在TC4沉積過(guò)程中引入弧旋轉(zhuǎn)(ArcRotation，AR)與弧縱向(Arc Longitudinal，AL)兩種磁弧振蕩模式(圖14(b1-b2)所示)，相較于電弧穩(wěn)定(Arc Stability,AS)狀態(tài)，磁弧振蕩可細(xì)化a片層，提高位錯(cuò)密度并強(qiáng)化晶粒取向集中。AL試樣表面形成約22nm鈍化膜與3nm過(guò)鈍化膜，結(jié)構(gòu)緊密無(wú)缺陷，能有效阻斷腐蝕介質(zhì)。電化學(xué)阻抗譜(Electrochemical Impedance Spectroscopy，EIS)(圖14b3)顯示， AR與AL試樣的電荷轉(zhuǎn)移電阻(Rct)遠(yuǎn)高于AS試樣，Nyquist圖中阻抗弧半徑更大，表明磁弧振蕩顯著提升了表面膜層的防護(hù)性能。此外，Ji等 [153]提出的耦合電脈沖和超聲處理(Coupled Electric Pulse and Ultrasonic Treatment,CEPUT)可以同步去除TC4鈦合金表面的疏松氧化層并生成致密α相層(圖14(c1)為CEPUT作用合金微觀組織變化)。經(jīng)400A峰值電流處理后，合金在0.9%NaCl溶液中的自腐蝕電流密度降低(如圖14(c2)所示)，較未處理樣品降低兩個(gè)數(shù)量級(jí)，耐腐蝕性大幅提升。

綜上所述，致密的微觀組織與穩(wěn)定的表面鈍化膜是提升AM鈦合金耐蝕性能的兩大核心要素。通過(guò)精準(zhǔn)的工藝參數(shù)調(diào)控與適配的熱處理，可進(jìn)一步增強(qiáng)鈍化膜的完整性與穩(wěn)定性;而采用多場(chǎng)協(xié)同調(diào)控技術(shù)細(xì)化晶粒并優(yōu)化表面致密度，能夠有效降低腐蝕電流密度，最終實(shí)現(xiàn)耐蝕性能的顯著提升。

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（注，原文標(biāo)題：鈦合金增材制造技術(shù)及組織性能研究進(jìn)展）

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tag標(biāo)簽:鈦合金,增材制造,多元化發(fā)展,精準(zhǔn)調(diào)控,單一能量場(chǎng),復(fù)合能量場(chǎng)

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