非晶合金具有高強度、高硬度和高彈性極限等優(yōu)異性能，受到了極大的關注[1~3] 但是，非晶合金沒有位錯等缺陷[1, 4, 5]，其室溫塑性變形主要集中在極窄的剪切帶[6]，使其表現出脆性斷裂 為了克服非晶合金的脆性斷裂，可在其中生成合適的第二相 第二相能阻礙剪切帶的擴展并誘發(fā)剪切帶多重化、分支、相互交叉，可改善其室溫塑性[1, 7, 8] 依據此原理，可制備出各種非晶復合材料 例如：Johnson等用半固態(tài)處理方法制備出Ti基[9, 10]，Zr基[11, 12]，CuZr基[13]等非晶復合材料；張海峰等[14~17]用熔體?滲法制備出一系列難熔金屬增強非晶復合材料；李毅等[18, 19]、喬珺威等[20, 21]和陳光等[22, 23]用Bridgman方法調控溫度梯度和凝固速率開發(fā)出一系列具有不同體積分數和尺寸的晶態(tài)相增強非晶復合材料 這些非晶復合材料，都具有良好的室溫壓縮塑性 根據在非晶基體里引入晶態(tài)相的方式，非晶復合材料可分為外加型非晶復合材料和內生型非晶復合材料[24] 內生型非晶復合材料，是在熔體凝固過程中原位析出晶態(tài)相或者非晶合金進行適當的熱處理使非晶合金晶化析出晶態(tài)相[20] 這種類型的非晶復合材料最大的優(yōu)點是其內生晶態(tài)相是原位生成的，與非晶基體界面結合良好 在載荷作用下，內生晶態(tài)相能有效地抑制剪切帶的擴展，加劇剪切帶的相互作用，從而使非晶合金的室溫塑性顯著提高 但是，內生型非晶復合材料對成分、冷卻速率和熱處理溫度等因素極其敏感，較難精準地調控非晶復合材料中晶態(tài)相的體積分數、尺寸和形貌 特別是，內生型非晶復合材料的應用非常有限 外加型非晶復合材料，是外加纖維、顆?；蜴u絲等晶態(tài)相增強非晶復合材料[25] 在工程應用領域，根據實際需要可設計出不同體積分數、外加晶態(tài)相和形態(tài)的非晶復合材料 這表明，外加型非晶復合材料的結構可靈活調控 外加型非晶復合材料的這些優(yōu)點，使其在工程應用領域倍受關注 但是，在外加型非晶復合材料中非晶相與晶態(tài)相不相容，在非晶基體與外加相的界面處容易生成金屬間化合物 這導致其塑性變形不如內生型非晶復合材料，甚至惡化其性能

TiZr基非晶合金和鈦合金都是輕質合金，因此鈦合金增韌的Ti基非晶復合材料具有潛在的應用價值 ZT3非晶合金[26] (名義成分：Ti32.8Zr30.2Ni5.3Cu9Be22.7，原子分數，%)的非晶形成能力極高，其壓縮斷裂強度高達1800 MPa TC21鈦合金(名義成分：Ti-6Al-2Sn-2Zr-3Mo-1Cr-2Nb-0.1Si，質量分數，%)的室溫塑性良好[27, 28] 鑒于此，本文選取ZT3非晶合金和TC21鈦合金設計ZT3/TC21雙層復合材料，研究制備工藝參數對這種雙層復合材料界面結構和力學性能的影響

1 實驗方法

用純度高于99.8%(質量分數)的純金屬按Ti32.8Zr30.2Ni5.3Cu9Be22.7(ZT3，原子分數，%)配制100 g金屬混合物 將這些金屬混合物在高純氬氣保護下進行電弧熔煉 重復熔煉4次，得到ZT3母合金錠 從TC21鈦合金上線切割出尺寸為80 mm×10 mm×5 mm的條樣并將其磨拋，然后用無水乙醇超聲清洗 將處理干凈的TC21鈦合金條樣固定在尺寸為100 mm×10 mm×10 mm模具的一側，在模具的另一側放入適量的ZT3母合金錠 然后，將模具置于管式電阻爐中并抽真空，待真空度達到3.5 kPa時加熱母合金錠到選定的溫度(1073、1123和1173 K)，充入氬氣并保溫3 min以使母合金熔體滲入并填滿模具的空隙 最后將模具水淬，制備出ZT3/TC21雙層復合材料

用銅模吸鑄法將ZT3母合金制成直徑為2 mm的棒材，并從中截取直徑和高都為2 mm的圓柱作為熔滴棒材 再截取直徑為8 mm、厚度為2 mm的TC21鈦合金片并將其磨拋，用無水乙醇超聲清洗后作為潤濕實驗的基片 將ZT3熔滴棒材置于鈦合金基片的表面并放在潤濕性測試裝置內，調整水平后以10 K/min的升溫速率加熱到不同溫度并保溫一定的時間 在這期間實時觀察液滴的形態(tài)

用Leo Supra 55掃描電子顯微鏡(帶有X射線能量分散譜(EDS))觀察雙層復合材料失效前后的微觀形貌 在Instron 5582萬能力學試驗機上進行三點彎曲實驗，應變速率為0.1 mm/min，跨度為20 mm，試樣的尺寸為25 mm×4 mm×2 mm，ZT3非晶合金與TC21鈦合金在厚度方向上的比為1∶1 用分離式霍普金森壓桿測試圓棒樣品的動態(tài)壓縮力學性能 樣品的直徑和長度都為4 mm

2 結果和討論2.1 ZT3非晶合金在TC21鈦合金上的潤濕行為

用外加法制備雙相復合材料，最關鍵的是兩相的界面結合[29~31] 用液相工藝制備復合材料，外加相與液相的結合涉及到溶解、擴散和界面反應 圖1a給出了ZT3合金熔體/TC21鈦合金的潤濕角隨溫度的變化 可以看出，開始時接觸角很大，隨著溫度的升高潤濕角逐漸減小 溫度進一步升高使液滴在TC21鈦合金基片的鋪展明顯加快隨后又逐漸減緩，最終潤濕角降低到10° 這表明，提高溫度可改善ZT3與TC21鈦合金基片的濕潤性[30]

圖1



圖1潤濕角與溫度和時間的關系

Fig.1Relationship between contact angle and temperature during continuous heating process (a) and increasing time (b)

圖1b給出了保溫溫度為963 K時ZT3合金熔體/TC21鈦合金潤濕角隨時間的變化 可以看出，在溫度為963 K時初始潤濕角約為41°，與連續(xù)升溫過程中溫度達963 K時的接觸角相同(圖1a)，但是此時接觸角并沒有達到穩(wěn)態(tài) 保溫30 s后潤濕角減小到22°，繼續(xù)保溫到60 s潤濕角降至約12° 然后，隨著保溫時間的增加，潤濕角低于10°并保持穩(wěn)定 隨著溫度的升高和時間的延長，ZT3合金熔體的粘度降低，潤濕阻滯力隨之降低；同時，在溫度升高和時間增加的過程中，ZT3合金熔體與鈦合金基片之間的溶解擴散加劇，潤濕驅動力增大使熔體在基片上迅速鋪展開，潤濕速率提高使?jié)櫇窠茄杆贉p小 隨著潤濕過程的進行，潤濕驅動力減小直至等于粘滯阻力，潤濕進入平衡過程后潤濕角趨于恒定 這表明，ZT3非晶合金與TC21鈦合金基片具有良好的潤濕性，制備ZT3/TC21雙層復合材料是可行的

2.2 雙層復合材料的微觀結構

圖2a給出了在不同溫度制備雙層非晶復合材料的示意圖，圖2b~d給出了在1073、1123和1173 K制備的雙層復合材料的界面形貌掃描圖 可以看出，這種雙層復合材料與ZT3/Ti55的界面特征相似[30]，界面處都沒有生成金屬間化合物，但是鈦合金向非晶一側溶解擴散 這種界面屬于第二類界面，其濕潤性非常好，與潤濕實驗的結果一致 從圖2可見，在ZT3非晶合金與TC21鈦合金的界面生成了界面層，是非晶合金熔體與TC21鈦合金發(fā)生劇烈固/液交互作用的結果 鈦合金向非晶一側溶解擴散，在界面生成了界面層 這種界面層的厚度，受復合材料制備溫度的影響 制備溫度越高，則界面層越厚 從圖2還能觀察到，界面層明顯向非晶合金的熔體里生長，呈現出典型的樹枝狀 提高制備溫度，則樹枝狀界面層向非晶合金熔體內生長得更深、更粗 這些樹枝晶在保溫過程中部分從界面層剝落而溶解進非晶合金熔體里，在快冷過程中從非晶合金熔體里以枝晶相的形式析出 制備溫度越高，非晶合金里的枝晶相就越粗、分布范圍越廣、體積分數越高 其原因是，制備溫度的升高能促進界面層的生成和以樹枝晶的形式向非晶合金熔體里生長，并加劇界面層的溶解

圖2



圖2在不同溫度制備的雙層復合材料的示意圖和界面處的微觀結構掃描圖

Fig.2Schematic diagram of the whole dual-layer composites (a) and SEM images of the microstructures at the interfaces between metallic glasses and TC21 titanium alloys for the dual-layer composites prepared under different temperatures (b~d)

ZT3/TC21的復合主要是通過溶解擴散連接的 影響溶解擴散的因素很多 根據菲克第一定律[32]

J=-D?C?X

濃度梯度D固定時原子的擴散主要與擴散系數相關，ZT3/TC21的結合屬于典型的原子擴散 式中J為擴散通量(單位時間內沿擴散方向通過單位面積的擴散物質量)；D為擴散系數；X為沿擴散方向的距離 ZT3/TC21的結合，其組元性質、組元濃度等在初始時都相同 因此，溫度是影響界面層溶解擴散的主要因素 根據Arrhenius公式D=D0exp(QKT)，溫度越高則原子動能越大，擴散系數D越大，擴散速率隨之提高 在ZT3/TC21復合過程中，隨著溫度的升高，界面處變得更活躍的原子使固態(tài)鈦合金向非晶熔體里溶解擴散的速率提高 因此，隨著溫度的升高，鈦合金擴散的量更多，擴散遷移的距離更遠，最后在非晶基體中生成枝晶相 圖2給出了界面的形貌

在ZT3/TC21的固/液交互作用過程中，固態(tài)TC21鈦合金成分擴散使TC21鈦合金溶解 同時，因為ZT3非晶合金熔體中的Zr、Cu、Ni原子濃度比固態(tài)TC21鈦合金高、擴散驅動力較大，使其向固態(tài)的TC21鈦合金中擴散 ZT3體系的非晶形成能力非常高[26],微量成分的擴散不會明顯降低非晶合金的形成能力 ZT3非晶合金熔體里的Cu、Ni、Be元素在平衡的β枝晶相里的固溶度較低，在凝固過程中優(yōu)先固溶于非晶合金基體中，這有利于非晶合金的形成，又不會產生明顯的擴散[7, 8] 而Zr元素的部分擴散不會使非晶合金形成能力的急劇降低 根據菲克第一定律，Zr元素向TC21鈦合金內擴散的驅動力呈梯度變化 這種梯度變化，反映在與TC21鈦合金連接的界面層的成分分布，如圖3所示 從圖3可見，樹枝狀、與非晶合金相連接的晶態(tài)相為枝晶相，其成分均勻，而與TC21鈦合金連接的界面層的成分呈現梯度變化 界面層的主要成分是Ti、Zr、Al Ti元素是界面層的主要成分，Zr元素是非晶合金熔體內的成分向TC21鈦合金擴散而累積的 Al元素主要源于TC21鈦合金，在固/液交互作用過程中也向非晶熔體內擴散，因其含量很低而沒有明顯的特征 制備溫度的升高使成分(主要Zr元素)擴散的驅動力變大，從而使界面層增厚 界面層變厚又促進界面層以樹枝晶的形式向非晶熔體內生長，從而加劇了界面層的溶解

圖3



圖3在1173 K制備的雙層復合材料界面處的微觀結構線性掃描圖和對應的成分分布

Fig.3Line scanning analysis result and the corresponding element profiles for the dual-layer composites prepared at 1173 K

為了進一步明確成分的擴散，對在1123 K制備的雙層復合材料界面處非晶一側的析出相進行EDS檢測，得到的成分列于表1 根據菲克第一定律，濃度差產生成分的相互擴散 開始時，Ti、Al、Cr、Nb、Mo和Sn元素的含量明顯高于非晶合金，界面兩側的濃度差導致成分擴散 析出相含有Al、Cr、Nb、Mo和Sn元素，表明在制備復合材料的過程中這些元素跨越界面擴散到非晶熔體一側，凝固時富集在析出相內 析出相的Ti含量明顯比非晶基體的高，其原因是鈦合金里的Ti元素擴散到非晶合金熔體一側并在凝固過程中以枝晶相的形式析出

Table 1

表1

表1在1123 K制備的雙層復合材料界面處的枝晶相與非晶基體的含量

Table 1Compositions of dendrites and metallic glass matrix in dual-layer composite prepared at the temperature of 1123 K (atomic fraction, %)

Compositions	Al	Ti	Cr	Ni	Cu	Zr	Nb	Mo	Sn
Dendrites	4.72	69.61	1.27	1.99	3.60	16.98	0.25	1.03	0.54
Metallic glass matrix	3.69	58.07	1.13	5.37	7.95	23.56	0.44	0.42	0.31

2.3 雙層復合材料的彎曲力學性能

圖4a給出了ZT3非晶合金和在不同溫度制備的雙層復合材料的彎曲應力-位移曲線 彎曲力學實驗如圖4a中的插圖所示，ZT3非晶合金承受壓應力，TC21鈦合金承受拉應力 韌性的TC21鈦合金處于拉應力一側，能限制ZT3非晶合金的開裂，防止材料過早失效 雖然ZT3非晶合金的彎曲強度很高，但是發(fā)生了脆性斷裂 雙層復合材料的變形，屬于彈性變形和塑性變形 在1073和1123 K制備的雙層復合材料其彎曲應力-位移曲線達到最大應力值(分別為2045和2177 MPa)后，隨著位移的增加，彎曲應力逐漸降低 其原因是，試樣在彎曲過程中出現部分裂紋而使橫截面積減小 但是，在1173 K制備的復合材料表現出明顯的加工硬化，抗彎強度達到2137 MPa時并沒有出現應力達到最大值后逐漸下降的現象 三種溫度制備的雙層復合材料其三點彎曲應力-位移曲線出現鋸齒現象(圖4b)是二次剪切帶形核和剪切帶擴展所致 這表明，非晶合金里的單一主剪切帶多重化促進了材料的彎曲塑性 三種溫度制備的雙層復合材料的塑性相近，但是1073 K制備的材料其抗彎強度略低，為2045 MPa

圖4



圖4ZT3非晶合金和在不同溫度制備的雙層復合材料的彎曲應力-撓度曲線和在1173 K制備的復合材料的彎曲應力-撓度曲線的局部放大圖

Fig.4Flexural stress-deflection curves of ZT3 BMG and the dual-layer composites under different temperature (a) and local enlarge flexural stress-deflection curve of the composites prepared at 1173 K (b)

圖5給出了彎曲試驗后樣品的表面形貌 可以看出，在每個試樣的拉應力一側產生滑移帶，在壓應力一側產生剪切帶 進行彎曲實驗時處于拉應力一側的應力最大且最先達到材料的屈服點，主導著材料的最終斷裂 但是TC21鈦合金具有良好的塑性變形能力，在受載過程中處于拉應力一側的應力得到了釋放，使材料不易發(fā)生斷裂 這是雙層復合材料具有良好彎曲塑性的主要原因 但是，處于壓應力一側的非晶合金很脆，在受載過程中容易發(fā)生災難性斷裂 這表明，控制雙層復合材料彎曲性能的區(qū)域是處于壓應力一側的非晶合金

圖5



圖5在不同溫度制備的雙層復合材料樣品彎曲失效后的側面掃描圖

Fig.5SEM image of the dual-layer composites prepared at 1073 K (a~c), 1123 K (d~f) and 1173 K (g~i) after failure

在非晶合金的一側，觀察到大量剪切帶和明顯的剪切臺階 主剪切帶沿著與自由平面呈約50°的方向擴展，與文獻[33]報道的非晶合金在彎曲載荷作用下剪切帶的擴展一致 二次剪切帶和三次剪切帶大量分叉，且其間距不均勻 靠近樣品自由平面的主剪切帶處，材料處于壓應力高度束縛狀態(tài)，二次剪切帶形成團簇分支 剪切帶的分叉使彼此間相互交叉和纏結，有利于改善雙層復合材料的韌性，避免非晶合金中的剪切帶很快演化成裂紋而使材料失效 樣品持續(xù)彎曲時，間距較大的主剪切帶很快擴展到靠近材料的中軸 從自由界面到中軸處應力逐漸降低，剪切帶擴展的尖端應力也隨之降低[34] 這些剪切帶的擴展減緩了其他剪切帶的應力集中，具有良好的應力屏蔽作用

雙層復合材料的界面是裂紋產生的形核點 界面處應力的高度集中，使裂紋在界面處萌生[35, 36] 從圖5可見，所有雙層復合材料的最后彎曲斷裂都是裂紋從界面處產生并擴展所致 圖1表明，ZT3非晶合金與TC21鈦合金具有良好的潤濕性，其界面結合良好 大部分層狀復合材料在載荷作用過程中均出現界面分層，最終使材料失效[37, 38] 從圖5可見，裂紋雖然從界面處萌生，但是當前制備的雙層復合材料在載荷持續(xù)增加過程中并沒有出現ZT3非晶合金與TC21鈦合金分層 這進一步說明，ZT3非晶合金與TC21鈦合金界面結合牢固 這也是當前制備的雙層復合材料具有較好彎曲性能的主要原因

TC21鈦合金具有良好的韌性，在載荷作用下不會先開裂生成裂紋 界面處的高應力集中，只能使裂紋在非晶合金一側啟動 裂紋先從界面處萌生，在非晶合金的一側擴展 從圖5還可見，在裂紋擴展過程中主裂紋周圍出現一些明顯的剪切帶 這些剪切帶，能有效緩解非晶合金的局部應力集中 裂紋尖端的塑性變形，是材料增韌的主要機制之一[39]，能使裂紋鈍化而避免非晶合金過早失效，有利于提高材料的抗損傷能力 但是從圖5可見，在三種溫度制備的復合材料其斷裂特征明顯不同 1073和1123 K制備的復合材料最后都斷裂，而1173 K制備的復合材料最后雖然失效但是并沒有斷裂 1123 K制備的復合材料斷裂裂紋明顯比1073 K制備的復合材料偏轉幅度大，有利于提高材料的抗斷裂能力 對比圖5a、d和g可見，制備溫度提高使裂紋的數量增加 在受載過程中多重裂紋的產生能釋放裂紋尖端的應力集中，避免材料過早失效 對比圖5b、e和h可見，1073 K制備的復合材料萌生裂紋后，裂紋的尖端雖然明顯鈍化，但是其擴展路徑對垂直于界面方向的偏離較小 制備溫度高于1123 K的材料，裂紋萌生后其擴展方向嚴重偏離與界面垂直的方向，而且裂紋在擴展過程中還與其他裂紋相匯 這種模式的裂紋擴展，明顯提高了材料的抗損傷能力 同時，制備溫度的提高使非晶合金中枝晶相的體積分數和尺寸增大，能阻礙裂紋擴展而使裂紋擴展路徑變得曲折，如圖5所示 從圖4也可見，制備溫度的提高，使材料的加工硬化能力更明顯 這種能力的提高源于多重裂紋的產生以及裂紋的大幅度偏轉擴展 多重裂紋的產生，其實與界面處的界面層厚度(包含界面處生長的枝晶相)有關 從圖5i可見，較厚的界面層使裂紋直接在界面層內產生，并沿著平行于界面層的方向擴展 這意味著，這種復合材料中的界面層是裂紋的形核點，而且其抗損傷能力較弱 因此，制備溫度的提高使界面處生成的界面層厚度增加，有利于裂紋的產生 從圖5c、f和i可見，1073和1123 K制備的非晶復合材料其界面層較薄，在一個應力集中點處只產生單一的裂紋 但是，1173 K制備的非晶復合材料其界面層較厚，在一個應力集中點處萌生兩個裂紋

從圖4可見，1073 K制備的雙層復合材料其強度低于在其他兩個溫度制備的復合材料 實際上，TC21鈦合金的韌性非常好，其性能對材料最終的性能有很大的影響 制備溫度不同，對TC21鈦合金的性能也有很大的影響 圖6給出了在1073、1123和1173 K處理過后的TC21鈦合金拉伸應力-應變曲線 可以看出，TC21鈦合金在三種制備溫度下均表現出良好的加工硬化能力，是雙層復合材料具有優(yōu)異加工硬化能力的主要原因 隨著制備溫度的提高，TC21鈦合金的加工硬化隨之增強，也使雙層復合材料的加工硬化能力的提高，如圖4a所示 從圖中還可見，1073 K制備的TC21鈦合金的斷裂強度最低，為831 MPa 而1123和1173 K制備的TC21鈦合金的斷裂強度比較接近，與1073 K處理的鈦合金相比明顯提高，分別達到995和1017 MPa 1123和1173 K制備的TC21鈦合金其韌性并沒有降低而是改善了，不會降低制備出的雙層復合材料的韌性 TC21鈦合金處于拉應力一側，其斷裂強度對材料的最終失效起關鍵性作用 在1073 K制備的復合材料中TC21鈦合金的斷裂強度最低，從而使雙層復合材料的彎曲強度最低

圖6



圖6在不同溫度處理的TC21鈦合金的拉伸應力-應變曲線

Fig.6Tensile stress-strain curves of the TC21 titanium alloy after heating treatment under different temperature

2.4 雙層復合材料的動態(tài)壓縮力學性能

在實際的工程應用中，材料有時承受動態(tài)載荷或高應變速率載荷 Johnson等[40]和Jiang等[41]研究了Zr基非晶合金遭受準靜態(tài)載荷和動態(tài)載荷時截然不同的特征 Zr基非晶合金承受準靜態(tài)壓縮載荷時表現出顯著的塑性變形，而承受動態(tài)載荷作用時卻表現出典型的脆性斷裂 因此，有必要研究雙層復合材料的動態(tài)壓縮力學性能 圖7給出了在1073、1123和1173 K制備的雙層復合材料的動態(tài)壓縮應力-應變曲線和對應的應變速率隨時間的變化 動態(tài)壓縮實驗的應變速率很高，如圖7b所示 應變速率為1000 s-1時，ZT3非晶合金的動態(tài)壓縮強度約為700 MPa，且其動態(tài)壓縮強度隨著應變速率的增加而降低[42] 本文制備的雙層復合材料，其動態(tài)壓縮強度為901~1326 MPa 對比結果表明，雙層復合材料的動態(tài)壓縮強度明顯比ZT3非晶合金更優(yōu)異 其主要原因是：首先，TC21鈦合金對ZT3非晶合金的束縛作用避免ZT3非晶合金過早失效；其次，應變速率為1500 s-1時TC21鈦合金的動態(tài)壓縮強度和塑性應變分別為1086~1287 MPa和4.4%~6.5%[43] TC21鈦合金良好的動態(tài)壓縮性能既能提高ZT3非晶合金的動態(tài)壓縮強度又能通過塑性變形釋放材料的部分應變能，最終使材料的動態(tài)壓縮力學性能提高

圖7



圖7在不同溫度制備的雙層復合材料的動態(tài)壓縮應力-應變曲線和在動態(tài)壓縮過程中試樣的應變速率與時間的關系

Fig.7True dynamic compressive stress-strain curves for the dual-layer composites under different temperature (a) and the variation of strain rate with time under compressive loading for every sample (b)

動態(tài)壓縮應力-應變曲線表明，應力達到屈服強度后所有的雙層復合材料都進入軟化階段，直至最后斷裂 文獻[34]揭示，非晶合金或者非晶復合材料的動態(tài)壓縮力學性能并沒有表現出準靜態(tài)載荷條件作用下的穩(wěn)定塑性流變行為，因為在動態(tài)變形過程中沒有足夠的時間觸動剪切帶多重化 另外，該雙層復合材料中的TC21鈦合金只限制非晶合金一側的變形而對非晶合金的變形束縛較少 在1073 K制備的非晶復合材料其動態(tài)壓縮強度最大，為1264~1326 MPa 隨著制備溫度的提高，材料的動態(tài)壓縮強度降低 在1173 K制備的雙層復合材料，其強度降低到901~916 MPa 產生這種動態(tài)壓縮性能不同的主要原因是：在高應變速率載荷作用下不會發(fā)生在靜態(tài)載荷條件下出現的裂紋穩(wěn)定擴展 而隨著制備溫度的提高界面層的厚度增大，容易誘發(fā)裂紋的產生 極高的應變速率產生的裂紋，使材料迅速失效

3 結論

(1) ZT3非晶合金與TC21鈦合金之間具有良好的潤濕性 隨著制備溫度的提高，潤濕角很快減小，制備溫度提高到1070 K，潤濕角降低至10°；在963 K保溫過程中，潤濕角隨著時間的延長極快地減小，最后穩(wěn)定在10°以下

(2) 在不同溫度制備ZT3非晶合金/TC21鈦合金雙層復合材料，TC21鈦合金發(fā)生不同程度的溶解，在界面生成一層明顯的界面層，在非晶合金一側析出部分枝晶相 隨著制備溫度的提高，界面層變厚、枝晶相的析出增加、枝晶相分布的范圍更廣

(3) 不同溫度制備的ZT3非晶合金/TC21鈦合金雙層復合材料具有良好的室溫彎曲塑性，并保持其彎曲強度達到2177 MPa，其動態(tài)壓縮強度為901~1326 MPa 隨著制備溫度的提高，材料的動態(tài)壓縮強度降低

參考文獻

View Option 原文順序文獻年度倒序文中引用次數倒序被引期刊影響因子

[1]

Lu Y, Su S, Zhang S, et al.

Controllable additive manufacturing of gradient bulk metallic glass composite with high strength and tensile ductility

[J]. Acta Mater., 2021, 206: 116632

DOIURL [本文引用: 3]

[2]

Zhang C, Wang W, Xing W, et al.

Understanding on toughening mechanism of bioinspired bulk metallic glassy composites by thermal spray additive manufacturing

[J]. Scr. Mater., 2020, 177: 112

DOIURL

[3]

Lin S F, Liu D M, Zhu Z W, et al.

New Ti-based bulk metallic glasses with exceptional glass forming ability

[J]. J. Non-Cryst. Solids., 2018, 502: 71

DOIURL [本文引用: 1]

[4]

Xing D, Chen S S, Chen P D, et al.

Effect of Fe microalloying on plastic deformation behavior of Cu-Zr-Al metallic glasses

[J]. Chin. J. Mater. Res., 2021, 35(11): 850

DOI [本文引用: 1] " />

The mechanical properties of bulk metallic glasses (BMGs) and their composites have been under intense investigation for many years, owing to their unique combination of high strength and elastic limit. However, because of their highly localized deformation mechanism, BMGs are typically considered to be brittle materials and are not suitable for structural applications. Recently, highly-toughened BMG composites have been created in a Zr-Ti-based system with mechanical properties comparable with high-performance crystalline alloys. In this work, we present a series of low-density, Ti-based BMG composites with combinations of high strength, tensile ductility, and excellent fracture toughness.

[10]

Kolodziejska J A, Kozachkov H, Kranjc K, et al.

Towards an understanding of tensile deformation in Ti-based bulk metallic glass matrix composites with BCC dendrites

[J]. Sci. Rep., 2016, 6(1): 22563

DOI [本文引用: 1] " />

Deformation and fracture behavior of Zr41.25Ti13.75Ni10Cu12.5Be22.5 bulk metallic glass and its composite containing transverse tungsten fibers in compression were investigated. The monolithic metallic glass and the tungsten fiber composite specimens with aspect ratios of 2 and 1 are shown to have essentially the same ultimate strength under compression. The damage processes in the bulk metallic glass composite consisted of fiber cracking, followed by initiation of shear band in the glassy matrix mainly from the impingement of the fiber crack on the fiber/matrix interface. The site of the shear band initiation in the matrix is consistent with the prediction of finite element modeling. Evidence is present that the tungsten fiber can resist the propagation of the shear band in the glassy matrix. However, the compressive strain to failure substantially decreased in the present composite compared with the composites containing longitudinal tungsten fibers. Finally, the two composite specimens fractured in a shear mode and almost all the tungsten fibers contained cracks.

[17]

Li Z K, Fu H M, Sha P F, et al.

Atomic interaction mechanism for designing the interface of W/Zr-based bulk metallic glass composites

[J]. Sci. Rep., 2015, 5(1): 8967

DOI [本文引用: 1] " />

We present a systematic study of homogeneous deformation in a La-based bulk metallic glass and two in situ composites based on the same glass. In contrast to prior investigations, which focused on relatively dilute composites, in this work the reinforcement volume percentages were more concentrated at 37% and 52%—near or above the percolation threshold (35–40%). Hot uniaxial compressive testing was conducted over a wide strain rate range from 10?2to 10?5s?1at a temperature near the glass transition. For such concentrated composites, the homogeneous deformation behavior appeared to be dominated by the properties of the reinforcement phase; in the present case the La reinforcements deformed by glide-controlled creep. Post-deformation analysis suggested that bulk metallic glass matrix composites were susceptible to microstructural evolution, which appeared to be enhanced by deformation, in contrast with a stress-free anneal. Consequently, unreinforced bulk metallic glass appeared to be more structurally stable than its composites during deformation near the glass transition.

[20]

Qiao J W.

In-situ dendrite/metallic glass matrix composites: a review

[J]. J. Mater. Sci. Technol., 2013, 29(8): 685

DOI [本文引用: 2] " />

Zr52.5Cu17.9Ni14.6Al10Ti5 bulk metallic glass (BMG) alloy samples in both rod and plate geometry were prepared. Different free volume states were obtained through thermal treatment. The plastic deformation ability of the BMGs was investigated through both a three-point bending test and compression test. The three-point bending results reveal the important role of free volume content on the formation of multiple shear bands, as the shear band propagation can be efficiently stopped due to the existence of the stress gradient from the surface to the neutral plane. In compression, the sample size rather than free volume controls the shear banding behavior.

[35]

Guo W, Kato H, Yamada R, et al.

Fabrication and mechanical properties of bulk metallic glass matrix composites by in-situ dealloying method

[J]. J. Alloys Compd., 2017, 707: 332

DOIURL [本文引用: 1]

[36]

Wu F F, Chan K C, Li S T, et al.

Stabilized shear banding of ZrCu-based metallic glass composites under tensile loading

[J]. J. Mater. Sci., 2013, 49(5): 2164

DOIURL [本文引用: 1]

[37]

Liu B X, Huang L J, Kaveendran B, et al.

Tensile and bending behaviors and characteristics of laminated Ti-(TiBw/Ti) composites with different interface status

[J]. Composites B, 2017, 108: 377

DOIURL [本文引用: 1]

[38]

Liu B X, Huang L J, Rong X D, et al.

Bending behaviors and fracture characteristics of laminated ductile-tough composites under different modes

[J]. Compos. Sci. Technol., 2016, 126: 94

DOIURL [本文引用: 1]

[39]

Ritchie R O.

The conflicts between strength and toughness

[J]. Nat. Mater., 2011, 10(11): 817

DOIPMID [本文引用: 1] class="outline_tb" " />

Cu(47.8－x)Zr46.2Al6Fex (x=0, 0.8, 1.2, 1.6) alloy were prepared by copper-mold injection casting method and the effect of Fe microalloying on the glass-forming ability and mechanical properties of Cu(47.8－x)Zr46.2Al6Fex (x=0, 0.8, 1.2, 1.6) metallic glasses were investigated. The results show that the glass-forming ability of the alloy decreases with increasing of Fe content, while the plastic deformation ability at room temperature increases obviously. It is found that with the increase of minor Fe content more free volume will be introduced into the glassy matrix, and the inhomogeneity of composition and free volume distribution in the matrix will increase as a result of the positive mixing enthalpy of Fe and Cu. These factors jointly result in enhanced plasticity of metallic glass with high Fe content.

邢 棟, 陳雙雙, 宋佩頔 等.

Fe微合金化對Cu-Zr-Al非晶合金塑性變形行為的影響及其機理

[J]. 材料研究學報, 2021, 35(11): 850

[5]

Li T T, Hu Y, Cui X M, et al.

Micro-hardness and Shear Bands of Zr-Al-Cu-Ni-Ag Bulk Metallic Glass Composites

[J]. Chin. J. Mater. Res., 2014, 28(10): 730

李亭亭, 胡 勇, 崔曉明 等.

Zr-Al-Cu-Ni-Ag非晶復合材料的顯微硬度和剪切帶形貌

[J]. 材料研究學報, 2014, 28(10): 730

[6]

Lewandowski J J, Greer A L.

Temperature rise at shear bands in metallic glasses

[J]. Nat. Mater., 2005, 5(1): 15

[7]

Lin S F, Ge S F, Zhu Z W, et al.

Double toughening Ti-based bulk metallic glass composite with high toughness, strength and tensile ductility via phase engineering

[J]. Appl. Mater. Today., 2021, 22: 100944

[本文引用: 2]

[8]

Lin S F, Zhu Z W, Ge S F, et al.

Designing new work-hardenable ductile Ti-based multilayered bulk metallic glass composites with ex-situ and in-situ hybrid strategy

[J]. J. Mater. Sci. Technol., 2020, 50: 128

[本文引用: 2]

[9]

Hofmann D C, Suh J Y, Wiest A, et al.

Development of tough, low-density titanium-based bulk metallic glass matrix composites with tensile ductility

[J]. PNAS., 2008, 105(51): 20136

PMID " />

The microstructure and tension ductility of a series of Ti-based bulk metallic glass matrix composite (BMGMC) is investigated by changing content of the β stabilizing element vanadium while holding the volume fraction of dendritic phase constant. The ability to change only one variable in these novel composites has previously been difficult, leading to uninvestigated areas regarding how composition affects properties. It is shown that the tension ductility can range from near zero percent to over ten percent simply by changing the amount of vanadium in the dendritic phase. This approach may prove useful for the future development of these alloys, which have largely been developed experimentally using trial and error.

[11]

Hofmann D C, Suh J Y, Wiest A, et al.

Designing metallic glass matrix composites with high toughness and tensile ductility

[J]. Nature, 2008, 451(7182): 1085

[12]

Szuecs F, Kim C P, Johnson W L.

Mechanical properties of Zr56.2Ti13.8Nb5.0Cu6.9Ni5.6Be12.5 ductile phase reinforced bulk metallic glass composite

[J]. Acta Mater., 2001, 49(9): 1507

[13]

Kozachkov H, Kolodziejska J, Johnson W L, et al.

Effect of cooling rate on the volume fraction of B2 phases in a CuZrAlCo metallic glass matrix composite

[J]. Intermetallic., 2013, 39: 89

[14]

Zhang H F, Li H, Wang A M, et al.

Synthesis and characteristics of 80 vol.% tungsten (W) fibre/Zr based metallic glass composite

[J]. Intermetallic., 2009, 17(12): 1070

[15]

Zhang B, Fu H M, Zhang H F, et al.

Synthesis and property of short tungsten fibre/Zr-based metallic glass composite

[J]. J. Mater. Sci. Technol., 2019, 35: 1347

[16]

Zhang H, Liu L Z, Zhang Z F, et al.

Deformation and fracture behavior of tungsten fiber-reinforced bulk metallic glass composite subjected to transverse loading

[J]. J. Mater. Res., 2006, 21(6): 1375

" />

The interaction between active element Zr and W damages the W fibers and the interface and decreases the mechanical properties, especially the tensile strength of the W fibers reinforced Zr-based bulk metallic glass composites (BMGCs). From the viewpoint of atomic interaction, the W-Zr interaction can be restrained by adding minor elements that have stronger interaction with W into the alloy. The calculation about atomic interaction energy indicates that Ta and Nb preferred to segregate on the W substrate surface. Sessile drop experiment proves the prediction and corresponding in-situ coating appears at the interface. Besides, the atomic interaction mechanism was proven to be effective in many other systems by the sessile drop technique. Considering the interfacial morphology, Nb was added into the alloy to fabricate W/Zr-based BMGCs. As expected, the Nb addition effectively suppressed the W-Zr reaction and damage to W fibers. Both the compressive and tensile properties are improved obviously.

[18]

Tang H, Zhang Y, Li Y.

Synthesis of La-based in-situ bulk metallic glass matrix composite

[J]. Intermetallic, 2002, 10(11-12): 1203

[19]

Fu X L, Li Y, Schuh C A.

Homogeneous flow of bulk metallic glass composites with a high volume fraction of reinforcement

[J]. J. Mater. Res., 2011, 22(6): 1564

" />

<p>The advanced fabrication of in-situ dendrite/metallic glass matrix (MGM) composites is reviewed. Herein, the semi-solid processing and Bridgman solidification are two methods, which can make the dendrites homogeneously dispersed within the metallic glass matrix. Upon quasi-static compressive loading at room temperature, almost all the in-situ composites exhibit improved plasticity, due to the effective block to the fast propagation of shear bands. Upon quasi-static tensile loading at room temperature, although the composites possess tensile ductility, the inhomogeneous deformation and associated softening dominates. High volume-fractioned dendrites and network structures make in-situ composites distinguishingly plastic upon dynamic compression. In-situ composite exhibits high tensile strength and softening (necking) in the supercooled liquid region, since the presence of high volume-fractioned dendrites lowers the rheology of the viscous glass matrix at high temperatures. At cryogenic temperatures, a distinguishingly-increased maximum strength is available; however, a ductile-to-brittle transition seems to be present by lowering the temperature. Besides, improved tension&ndash;tension fatigue limit of 473&nbsp;MPa and four-point-bending fatigue limit of 567&nbsp;MPa are gained for Zr_58.5Ti_14.3Nb_5.2Cu_6.1Ni_4.9Be_11.0 MGM composites. High volume-fraction dendrites within the glass matrix induce increased effectiveness on the blunting and propagating resistance of the fatigue-crack tip. The fracture toughness of in-situ composites is comparable to those of the toughest steels and crystalline Ti alloys. During steady-state crack-growth, the confinement of damage by in-situ dendrites results in enhancement of the toughness.</p>

[21]

Qiao J W, Wang S, Zhang Y, et al.

Large plasticity and tensile necking of Zr-based bulk-metallic-glass-matrix composites synthesized by the Bridgman solidification

[J]. Appl. Phys. Lett., 2009, 94(15): 151905

[22]

Cheng J L, Chen G, Xu F, et al.

Correlation of the microstructure and mechanical properties of Zr-based in-situ bulk metallic glass matrix composites

[J]. Intermetallic, 2010, 18(12): 2425

[23]

Zhang X L, Chen G, Du Y L.

Synthesis of plastic Mg-based bulk-metallic-glass matrix composites by bridgman solidification

[J]. Metall. Mater. Trans. A, 2012, 43(8): 2604

[24]

Qiao J W, Jia H L, Liaw P K,

Metallic glass matrix composites

[J]. Mater. Sci. Eng. R., 2016, 100: 1

[25]

Chen S, Li W Q, Zhang L, et al.

Dynamic compressive mechanical properties of the spiral tungsten wire reinforced Zr-based bulk metallic glass composites

[J]. Composites B, 2020, 199: 108219

[26]

Tang M Q, Zhang H F, Zhu Z W, et al.

TiZr-base bulk metallic glass with over 50 mm in diameter

[J]. J. Mater. Sci. Technol., 2010, 26(6): 481

[本文引用: 2]

[27]

Wen X, Wan M P, Huang C W, et al.

Effect of microstructure on tensile properties, impact toughness and fracture toughness of TC21 alloy

[J]. Mater. Des., 2019, 180: 107898

[28]

Long W, Zhang S, Liang Y L, et al.

Influence of multi-stage heat treatment on the microstructure and mechanical properties of TC21 titanium alloy

[J]. Int. J. Miner. Metall. Mater., 2020, 28(2): 296

[29]

Ding S, Kong J, Schroers J.

Wetting of bulk metallic glass forming liquids on metals and ceramics

[J]. J. Appl. Phys., 2011, 110(4): 043508

[30]

Ma G, Lv S, Lu Z, et al.

Wetting behavior and interfacial characteristic of Ti32.8Zr30.2Cu9Ni5.3Be22.7/Ti55 alloy system

[J]. Mater. Chem. Phys., 2021, 270: 124759

[本文引用: 2]

[31]

Ma G F, Li Z K, He C L, et al.

Wetting behaviors and interfacial characteristics of TiZr-based bulk metallic glass/W substrate

[J]. J. Alloys Compd., 2013, 549: 254

[32]

Ghoneim A, Ojo O A.

Numerical modeling and simulation of a diffusion-controlled liquid-solid phase change in polycrystalline solids

[J]. Comput. Mater. Sci., 2011, 50(3): 1102

[33]

Conner R D, Li Y, Nix W D, et al.

Shear band spacing under bending of Zr-based metallic glass plates

[J]. Acta Mater., 2004, 52(8): 2429

[34]

Zhang L, Jiang F, Zhao Y, et al.

Shear band multiplication aided by free volume under three-point bending

[J]. J. Mater. Res., 2011, 25(2): 283

[本文引用: 2] " />

The attainment of both strength and toughness is a vital requirement for most structural materials; unfortunately these properties are generally mutually exclusive. Although the quest continues for stronger and harder materials, these have little to no use as bulk structural materials without appropriate fracture resistance. It is the lower-strength, and hence higher-toughness, materials that find use for most safety-critical applications where premature or, worse still, catastrophic fracture is unacceptable. For these reasons, the development of strong and tough (damage-tolerant) materials has traditionally been an exercise in compromise between hardness versus ductility. Drawing examples from metallic glasses, natural and biological materials, and structural and biomimetic ceramics, we examine some of the newer strategies in dealing with this conflict. Specifically, we focus on the interplay between the mechanisms that individually contribute to strength and toughness, noting that these phenomena can originate from very different lengthscales in a material's structural architecture. We show how these new and natural materials can defeat the conflict of strength versus toughness and achieve unprecedented levels of damage tolerance within their respective material classes.

[40]

Lu J, Ravichandran G, Johnson W L.

Deformation behavior of the Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass over a wide range of strain-rates and temperatures

[J]. Acta Mater., 2003, 51(12): 3429

[41]

Li M C, Jiang M Q, Yang S, et al.

Effect of strain rate on yielding strength of a Zr-based bulk metallic glass

[J]. Mater. Sci. Eng. A, 2017, 680: 21

[42]

Li W Q, Zhu Z W, Li G J, et al.

Correlation between dynamic compressive strength and fracture behaviors of bulk metallic glasses

[J]. Acta Metall. Sin. (Engl. Lett.), 2020, 33(10): 1407

[43]

Zhang J X, Yi X B, Shen J C, et al.

Influence of solution and ambient temperature on dynamic compression mechanical properties and adiabatic shear sensitivity of TC21 titanium alloy

[J]. Materials Reports, 2020, 34(12): 24092

張俊喜, 易湘斌, 沈建成 等.

固溶和工作溫度對TC21鈦合金動態(tài)壓縮性能和絕熱剪切敏感性的影響

[J]. 材料導報, 2020, 34(12): 24092

Controllable additive manufacturing of gradient bulk metallic glass composite with high strength and tensile ductility

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2021