國 立 交 通 大 學
材 料 科 學 與 工 程 學 系
博 士 論 文
錳含量對銅錳鋁合金相變化之影響
研 究 生：楊 勝 裕
指導教授：劉 增 豐 博士
中 華 民 國 九 十 五 月 一 月
Effects of Manganese Content on the Phase
Transformations of the Cu-Mn-Al Alloys
研 究 生：楊勝裕 Student: Chih-Hao Chen
指導教授：劉增豐 博士 Advisor: Dr. Tzeng-Feng Liu
國 立 交 通 大 學
材 料 科 學 與 工 程 學 系
博 士 論 文
A Dissertation
Submitted to Department of Materials Science and Engineering College of Engineering
National Chiao Tung University in Partial Fulfillment of the Requirements
for the Degree of Doctor of Philosophy
in
Materials Science and Engineering January 2005
Hsinchu, Taiwan, Republic of China
誌 謝
由衷感謝指導教授劉增豐博士七年多來的悉心指導與諄諄教誨，使
得學生的研究工作得以順利進行，並如期完成本論文。在這七年多的過
程中，吾師除了在繁忙的公務中抽空指導實驗工作外，並不時引導學生
如何由參考文獻中發覺問題，進而尋找論文之研究方向與解決方法，以
及如何撰寫科技論文等，實是受益良多；特別是在吾師擔任工學院院長
期間，校內公務日漸繁重，無法時常陪伴師母與子女左右，卻仍犧牲假
日家庭時間，陪伴學生討論實驗結果、指導論文後續的研究方向，令學
生感到十二萬分的敬佩。在生活上，特別感謝吾師劉增豐教授與師母林
美慧老師無微不至的關懷和鼓勵，謹致以最高的敬意與誠摯的感謝。在
課業上，感謝系上教授們提供良好的學習環境。口試時，承蒙賀俊教授、
吳泰伯教授、莊振益教授、朝春光教授等口試委員悉心指正，更是受益
匪淺。
感謝交大羽球隊教練廖威彰老師的栽培，提供良好的羽球學習環境
以及球隊寒、暑假嚴苛的密集訓練，讓我不但擁有在球技上的成長更獲
得充沛的體能熬夜做實驗。另外，從日常與教練的談話中體會出如何待
人處世之道，是我在交大學生生涯中最難忘的一段回憶，我會永遠以曾
經身為交大羽球隊的一員為榮。另外感謝球隊學長新松、仁宗、智揚、
偉賓、志壕、振泓(白猴)、文億、祐生、旭正、力衡、小勇、廷彰、花
輪、克彬以及其他學弟妹們多年來的照顧，感謝大家一起陪我走過這一
段既艱辛又甘甜的旅途。
研究所期間，承蒙學長李堅瑋博士、陳志壕博士及鄭祥誠博士在電
子顯微鏡之分析與金屬相變化上的指導，在此特別值得一提的是志壕學
長，若無他的帶領進入球隊，我無法認識那麼多的好朋友。此外，就讀
交大研究所期間，受到堅瑋及志壕學長許多的提攜，使我得以如此順利
取得學位。感謝承舜學長、俊瑋及瑞陞學弟在論文完稿過程中實驗上的
協助，尤其是俊瑋及瑞陞學弟，在我準備論文最忙之際，慨然地幫助我
打字與校稿，幫我節省了許多寶貴的時間，由衷感激。一路走來得到實
驗室學長學弟一貫的相互扶持與鼓勵，讓我在研究過程中，有最溫馨的
感覺。此外，國科會在研究經費上之贊助，使得本論文得以順利完成，
在此一併致上衷心的謝意。
最後，僅將論文獻給我最敬愛的奶奶、
父母親及心愛的老婆薇伶，感謝 他們多年來的辛勞、支持與鼓勵，使我能在安定舒適的環境中順利地完成學 業。
特別值得一提的是老婆薇伶，她是我在交大研究所求學生涯中最大的收 穫。
同時也感謝關心我的岳父母、茂勝、慶潭以及其他所有親友們。錳含量對銅錳鋁合金相變化之影響
研究生：楊勝裕 指 導 教 授 ： 劉 增 豐 博 士國立交通大學材料科學與工程研究所
中文摘要
本論文利用光學顯微鏡，掃描穿透式電子顯微鏡和X光能量散佈分析儀等， 研究觀察不同之錳含量對銅-錳-鋁三元合金顯微結構組織的影響。 本論文所得到的具體研究結果如下: (一)、在淬火狀態下，Cu2.9Mn0.1Al(Cu-2.7at.%Mn-25.1at.%Al)合金顯微結構為D03 相與淬火過程中經由麻田散相變化轉變成γ1΄麻田散相之混合相。然而我們 發 現 在 淬 火 狀 態 下 ， Cu2.8Mn0.2Al(Cu-5.1at.%Mn-25.3at.%Al) 與 Cu2.7Mn0.3Al(Cu-7.6at.%Mn-25.1at.%Al)合金，其顯微結構為D03相和極細微 之L-J混合相。但是在Cu2.6Mn0.4Al(Cu-10.3at.%Mn-25.2at.%Al)合金在淬火 狀態下之顯微結構則變成為D03、L21與L-J之混合相，此結果與先前Bouchard 等其他學者在銅-錳-鋁三元合金系統中所發現到的結果不同。在本研究中ii Cu2.7Mn0.3Al合金中，這是一個強而有力的直接證據證明D03 相是經由β → B2 → D03連續規律化變態所形成的。此處特別值得一提的是，至今a/4<111> 反向晶界從未被其他學者在銅-錳-鋁合金系統中發現過。 (二)、當Cu2.7Mn0.3Al (銅-7.6at.%錳-25.1at.%鋁)合金在固溶處理後急速淬火後， 其顯微結構為D03和極細微之L-J混合相，其中D03相是在淬火過程中經由β → B2 → D03連續規律化變態所形成的。當此合金在500℃做適當時間之時 效處理後，γ-brass相會開始在D03 基地中沿著a/2<100 >反向晶界析出。 然而，隨著時效時間的增加，L-J析出物開始在γ-brass顆粒周圍的鄰近區 域析出，此γ-brass與L-J的共存現象至今從未被其他學者在銅-錳-鋁合金 系統中發現過。此合金在500℃至700℃溫度範圍內做時效處理後其顯微結 構之變化依序為：(γ-brass + L-J + D03) → (γ-brass + L-J + B2) → β。此結果與其他學者在Cu3-xMnxAl三元合金中當X ≤ 0.32時所發現到的結 果截然不同。 (三)、在淬火狀態下，Cu1.6Mn1.4Al (銅-35.1at.%錳-25.1at.%鋁)合金的淬火顯微 結構為L21、B2與L-J之混合相，這個發現和其他學者在Cu3-xMnxAl合金（X ≤ 1.0）合金中所發現到的結果不同。當此合金在460℃做短時間時效處理後， γ-brass顆粒會開始在L21基地中沿著反向晶界析出。隨著時效時間的增
加，γ-brass析出物逐漸成長並且β-Mn析出物開始在γ-brass析出物之周
圍析出，γ-brass與β-Mn之間的方向關係為(001 )γ-brass//(012 )β-Mn and
(011)γ-brass// (031)β-Mn ，此γ-brass與β-Mn的共存現象至今從未被其他
學者在銅-錳-鋁合金系統中發現過。此合金在460℃至700℃溫度範圍內做 時效處理後其顯微結構之變化依序為： (γ-brass + β-Mn) → (β-Mn + B2) → β。
iv
Effects of Manganese Content on the Phase
Transformations of the Cu-Mn-Al alloys
Student: Sheng-Yu Yang Advisor: Dr. Tzeng-Feng Liu
Department of Materials Science and Engineering
National Chao Tung University
Abstract
Effects of the manganese (Mn) content on the phase transformations of the Cu-Mn-Al ternary alloys have been investigated by means of optical microscopy, scanning transmission electron microscopy and energy- dispersive X-ray spectrometry. On the basis of the experimental examinations, several results can be summarized as follows:
[1].We have studied the Cu3-xMnxAl alloy systems at room temperature. In the
as-quenched condition, the microstructure of the Cu2.9Mn0.1Al (Cu-2.7
at.%Mn-25.1at.%Al) alloy was a mixture of (D03 + γ1΄ martensite) phases.
However, the as-quenched microstructures of the Cu2.8Mn0.2Al (Cu-
5.1at.%Mn-25.3at.%Al) and Cu2.7Mn0.3Al (Cu-7.6at.%Mn-25.1at.%Al) alloys
were found to be D03 phase containing extremely fine L-J precipitates.
(Cu-10.3at.%Mn-25.2at.%Al) alloy, it was a mixture of (D03 + L21 + L-J)
phases in the as-quenched condition. These results are different from those proposed by Bouchard et al. The D03 phase in the Cu2.9Mn0.1Al, Cu2.8Mn0.2Al
and Cu2.7Mn0.3Al alloys was formed by a β → B2 → D03 continuous ordering
transition during quenching, because of the presence of a/4<111 >
anti-phase boundaries (APBs). It is a strong evidence to demonstrate that
the existing D03 phase was formed by a β → B2 → D03 continuous ordering
transition during quenching. It is worthwhile to note here also that the a/4<111 > APBs have never been found in the Cu-Mn-Al alloy systems before.
[2].The as-quenched microstructure of the Cu2.7Mn0.3Al (Cu-7.6at.%Mn-
25.1at.%Al) alloy was D03 phase containing extremely fine L-J precipitates,
where the D03 phase existing was formed by a β → B2 → D03 continuous
ordering transition during quenching. When the as-quenched alloy was aged at 500℃ for moderate times, the γ-brass particles were found to nuclear preferentially at a/2<100 > APBs. However, with increasing the aged times at 500℃, the L-J precipitates started to appear at the regions contiguous to the γ-brass particles. The coexistence of (γ-brass + L-J) phases has never been observed by other workers in the Cu-Mn-Al alloy systems before. As the aging temperature was increased from 500℃ to
700℃, the phase transition sequence was found to be (γ-brass + L-J + D03)
vi
previous workers in Cu3-xMnxAl alloys with X ≤ 0.32.
[3].In the as-quenched condition, the microstructure of the Cu1.6Mn1.4Al (Cu-
35.1at.%Mn-25.1at.%Al) alloy was a mixture of (L21 + B2 + L-J) phases.
This is different from that observed by previous workers in the Cu3-xMnxAl
alloys with X ≤ 1.0. When the as-quenched alloy was aged at 460℃ for short times, γ-brass precipitates started to occur at APBs. After prolonged aging time at 460℃, the γ-brass precipitates grew and β-Mn precipitates generated at the regions contiguous to the γ-brass precipitates. The
orientation relationship between the γ-brass and β-Mn was (001 )γ-brass //
(012 )β-Mn and (011 )γ-brass // (031 )β-Mn. The coexistence of (γ-brass + β-Mn)
has never been observed by previous workers in Cu-Mn-Al alloy systems before. When the as-quenched alloy was aged at temperatures ranging from 460℃ to 700℃, the phase transition sequence was found to be (γ-brass + β-Mn) → (β-Mn + B2) → β.
Contents
page 中文摘要 ... i Abstract ... iv Contents ... vii List of Tables ... ix List of Figures ...xChapter 1. General Introduction... 錯誤! 尚未定義書籤。 Chapter 2. As-quenched Microstructures of Cu3-xMnxAl Alloys ... 15
2-1 Introduction... 17
2-2 Experimental procedure... 19
2-3 Results and discussion ... 21
2-4 Conclusions... 43
References... 45
Chapter 3. Phase Transformations in a Cu2.7Mn0.3Al Alloy... 47
3-1 Introduction... 49
3-2 Experimental procedure... 51
3-3 Results and discussion ... 52
3-4 Conclusions... 74
References... 75
Chapter 4. Phase Transformations in a Cu1.6Mn1.4Al Alloy ... 77
4-1 Introduction... 79
4-2 Experimental procedure... 81
4-3 Results... 82
viii
4-5 Conclusion ... 107
References... 109
Chapter 5. Summary ... 111
List of Tables
Table 2.1 Atomic and Chemical compositions of the present alloys by inductively coupled plasma-mass spectrometer (ICP) ... 20 Table 3.1 Chemical Compositions of the Phases Revealed by an Energy-
Dispersive X-ray Spectrometer (EDS) ... 73 Table 4.1 Chemical Compositions of the Phases Revealed by an Energy-
x
List of Figures
Figure 1.1 A schematic drawing of the phase diagram of the Cu-Al alloy system with A2 → B2 and B2 → D03 order-disorder transition
temperatures and martensitic transformation temperatures (Ms) [6-7]... 12 Figure 1.2 A schematic drawing of the ordering temperatures Tc (B2) and Tc
(D03 + L21) and the miscibility gap of the (Cu-Mn)3Al alloy [25].13
Figure 1.3 Schematic representation of the ordering sequence of the quenched Cu2.5Mn0.5Al alloy (vertically) and its isothermal
decomposition (horizontally) [19, 25, 39]... 14 Figure 2.1 Influence of Manganese concentration on the microstructures of
Cu-Mn-Al alloys. (a) Cu2.9Mn0.1Al (b) Cu2.8Mn0.2Al (c) Cu2.7Mn0.3Al
(d) Cu2.6Mn0.4Al. ... 23
Figure 2.2 Electron micrographs of the as-quenched Cu2.9Mn0.1Al alloy. (a)
BF, (b) through (c) three SADPs. The zone axes of the D03 phase,
γ1΄ martensite and internal twin are (b) [ 001 ], [10 ] and [ 011 1 ], (c) [ 011 ], [111] and [100] (d) [111 ], [01 ] and [ 102 2 ], respectively (hkl= D03 phase, hkl=γ1΄ martensite, hklT=internal twin). (e) and (f)
(111) and (200) D03 DF, respectively, (g) (121) γ1΄ DF... 28
Figure 2.3 Electron micrographs of the as-quenched Cu2.8Mn0.2Al alloy. (a)
are [100], [110] and [111], respectively (hkl= D03 phase, hkl1or2=
L-J phase, 1: variant 1; 2: variant 2). (e) and (f) (111) and (002) D03 DF, respectively, (g) (1001)L-J DF... 32
Figure 2.4 Electron micrographs of the as-quenched Cu2.7Mn0.3Al alloy. (a)
BF, (b) and (c) two SADPs. The zone axes of the D03 phase are
[100] and [110], respectively. (hkl= D03 phase, hkl1or2= L-J phase,
1: variant 1; 2: variant 2). (d) and (e) (
1
11
) and (002) D03 DF,respectively. (f) (1001) L-J DF... 36
Figure 2.5 Electron micrographs of the as-quenched Cu2.6Mn0.4Al alloy. (a)
BF, (b) and (c) two SADPs. The zone axes of the D03 phase are
[100] and [110], respectively. (hkl= (D03 + L21) phase, hkl1or2= L-J
phase, 1: variant 1; 2: variant 2). (d) and (e) (111) and (002) D03
DF, respectively, (f) (1001) L-J DF... 40
Figure 3.1 Electron micrographs of the as-quenched alloy. (a) BF, (b) and (c) two SADPs. The zone axes of the D03 phase are (b) [100] and (c)
[110], respectively (hkl= D03, hkl1,2= L-J phase, 1: variant 1;
2:variant 2), (d) and (e) (
1
11
) and (002) D03 DF, respectively. (f)(0201) L-J DF... 55
Figure 3.2 Electron micrographs of the alloy aged at 500 ℃ for 20 minutes. (a) BF, (b) and (c) two SADPs. The zone axes of the D03 phase is
[100] and [110], respectively. (hkl=D03, hkl1=L-J phase and
xii
(f) (100) γ-brass DF... 59 Figure 3.3 Electron micrographs of the alloy aged at 500℃ for 2 hours. (a)
BF, (b) and (c) two SADPs. The zone axes of the D03 phase are
[100] and [110]. (hkl=D03, hkl1=L-J phase and hkl=γ-brass),
respectively. (d) and (e) (1001) L-J and (111) D03 DF, respectively.
... 62 Figure 3.4 Electron micrographs of the alloy aged at 600 ℃ for 1 hour. (a)
BF, (b) an SADP taken from the irregular-shaped γ-brass particle. The zone axis of the γ-brass phase is [001]. (c) an SADP taken from the D03 matrix. The zone axis of the D03 phase is [110].
(hkl=D03, hkl1=L-J phase). (d) (
0
2
0
1) L-J DF. (e) and (f) (111) and(002) D03 DF, respectively... 66
Figure 3.5 Electron micrographs of the alloy aged at 700 ℃ for 1 hour. (a) and (b) (
1
11
) and (002) D03 DF, respectively. ... 68Figure 3.6 Three typical EDS spectra obtained from (a) as-quenched alloy, (b) a γ-brass particle, and (c) an L-J precipitate in the alloy aged at 500℃ for 2 hours, respectively. ... 72 Figure 4.1 Electron micrographs of the as-quenched alloy. (a) BF, (b) through
(c) two SADPs. The zone axes of the L21 phase are [100] and
[ 110 ], respectively (hkl= L21, hkl1,2= L-J phase, 1:variant 1;
2:variant 2). (d) and (e) (111) and (002) L21 DF, respectively. (f)
Figure 4.2 Electron micrographs of the alloy aged at 460℃ for 10 minutes. (a) and (b) (111) and (002) L21 DF, respectively. (c) (1001) L-J DF.
... 88 Figure 4.3 Electron micrographs of the alloy aged at 460℃ for 30 minutes.
(a) (002) L21 DF, (b) and (c) two SADPs. The zone axes of the L21
phase is [100 ] and [110 ]. (hkl= L21, hkl=γ-brass)... 90
Figure 4.4 Electron micrographs of the alloy aged at 460℃ for 6 hours. (a) BF, (b) and (c) two SADPs. The zone axes of the β-Mn are [ 001] and [ 011]. (d) and (e) two SADPs. The zone axes of the γ-brass are [ 001] and [ 011]. (f) an SADP. The zone axis of the β-Mn and the γ-brass is [ 100 ] and [ 100 ], respectively. (hkl=β-Mn, hkl=γ-brass). ... 93 Figure 4.5 BF electron micrograph of the alloy aged at 460℃ for 12 hours.
... 96 Figure 4.6 Electron micrographs of the alloy aged at 600℃ for 30 minutes.
(a) BF, (b) and (c) two SADPs. The zone axes are [20 ]1 β–Mn,
[100 ]β-Mn for the β-Mn and [100 ]L21 , [ 201]L21 for the L21 matrix,
respectively. (hkl=β-Mn, hkl1=L-J phase, hkl=γ-brass). (d) and (e)
(111) and (002 ) L21 DF, respectively. (f) (1001) L-J DF... 99
Figure 4.7 Electron micrographs of the alloy aged at 700℃ for 1 hour. (a) and (b) (111) and (
002
) L21 DF, respectively. ... 100xiv
(b) a γ-brass precipitate as well as (c) a β-Mn precipitate in the alloy aged at 460℃ for 6 hours. ... 103
