【摘要】：高強(qiáng)高導(dǎo)Cu-Cr-Zr合金廣泛應(yīng)用于集成電路引線框架、高速鐵路電氣接觸線以及航空航天等眾多領(lǐng)域�，F(xiàn)代工業(yè)技術(shù)的不斷發(fā)展,對(duì)高強(qiáng)高導(dǎo)銅合金性能的要求也越來越高。這就需要我們及時(shí)開發(fā)出新的Cu-Cr-Zr合金以及與之配套的加工技術(shù),并深入探討合金組織的成因與性能變化規(guī)律。本文在Cu-0.81Cr-0.12Zr合金(質(zhì)量百分比,下同)基礎(chǔ)上添加微量稀土La和Y元素,采用真空感應(yīng)熔煉法制備合金鑄錠,經(jīng)均勻化退火后進(jìn)行熱軋,接著進(jìn)行固溶、冷軋和時(shí)效處理,用光學(xué)顯微鏡和掃描電子顯微鏡分析了各工藝階段合金的顯微組織,用X射線衍射儀分析了試樣的相組成,用高分辨透射電子顯微鏡分析了時(shí)效析出相的結(jié)構(gòu),用數(shù)顯硬度計(jì)測試了顯微硬度,用萬能力學(xué)試驗(yàn)機(jī)測試了強(qiáng)度,用微歐計(jì)測定了導(dǎo)電率。同時(shí)采用快速凝固單輥旋鑄法制備了合金薄帶試樣,獲得了完全過飽和固溶體合金,測試了時(shí)效處理前后試樣的顯微硬度和導(dǎo)電率。此外還采用液態(tài)金屬冷卻定向凝固法制備了Cu-0.81Cr合金棒狀試樣,考察了合金的組織以及力學(xué)與電學(xué)性能。主要研究結(jié)論如下:Cu-0.81Cr-0.12Zr-0.05La-0.05Y鑄錠的相組成不因稀土的加入而改變,均包含Cu、Cr和Cu5Zr三相,其中大部分Cr相以Cr+Cu共晶形態(tài)或顆粒狀分布于Cu的晶界處,少量Cr顆粒分布于Cu基體內(nèi)部,Cu5Zr則僅存在于Cu晶界處,但稀土元素的加入可以明顯細(xì)化鑄錠組織。Cu-0.81Cr-0.12Zr-0.05La-0.05Y鑄錠在1193 K溫度下均勻化退火60分鐘后熱軋,再于1223 K溫度下固溶處理60分鐘后冷卻至室溫進(jìn)行冷軋,詳細(xì)考察了不同軋比冷變形合金在系列溫度時(shí)效不同時(shí)間后的性能,發(fā)現(xiàn)在冷變形60%、773 K時(shí)效處理60分鐘優(yōu)化工藝處理后的試樣,其顯微硬度達(dá)186 HV,導(dǎo)電率達(dá)81%IACS。對(duì)上述合金進(jìn)一步施以40%的冷變形,再于723 K時(shí)效30分鐘,顯微硬度提高至203 HV,導(dǎo)電率提升至81.9%IACS,此時(shí)的抗拉強(qiáng)度和延伸率分別達(dá)604 MPa和8.5%。經(jīng)過60%冷軋加工的Cu-0.81Cr-0.12Zr-0.05La-0.05Y合金以20 K/min的速率連續(xù)加熱時(shí),分別于653 K-698 K和743 K-823 K發(fā)生沉淀相的集中析出和基體Cu的再結(jié)晶。冷軋態(tài)Cu-0.81Cr-0.12Zr-0.05La-0.05Y合金微應(yīng)變值高于純銅,其XRD圖譜中(111)Cu衍射峰強(qiáng)度隨著時(shí)效溫度的升高而不斷降低,(220)Cu衍射峰強(qiáng)度則不斷增大。Cu-0.81Cr-0.12Zr-0.05La-0.05Y合金在時(shí)效過程中析出體心立方的Cr相和面心立方的Cu5Zr相。在最佳綜合性能處,部分析出相仍與基體保持共格關(guān)系,其中Cr析出相與Cu基體之間呈現(xiàn)Nishiyama-Wassermann位向關(guān)系:(111)Cu//(110)Cr;[01_1]Cu//[001]Cr;[2_11] Cu // [1_10] Cr�？焖倌藽u-0.81Cr-0.12Zr-0.05La-0.05Y合金為完全過飽和固溶體,合金在以20 K/min的速率連續(xù)加熱時(shí),反映過飽和固溶體脫溶和析出相形成的放熱峰開始于655 K,結(jié)束于688 K�？齑銞l帶在773 K時(shí)效15分鐘后具有最好的綜合性能:顯微硬度達(dá)215 HV,導(dǎo)電率為77.6%IACS。該顯微硬度比60%冷變形后再行時(shí)效的合金還高出29 HV,表明快淬時(shí)效比常規(guī)固溶時(shí)效具有更好的強(qiáng)化效果。定向凝固Cu-0.81Cr自生復(fù)合材料組織由定向排列的α-Cu枝(胞)晶和分布在其晶界上的Cu+Cr共晶增強(qiáng)體組成。共晶組織中的兩相雖然仍為非定向性排列,但定向凝固組織中共晶體沿初生ɑ-Cu晶界縱向分布仍顯著提高了定向凝固合金的強(qiáng)度、塑性和導(dǎo)電性。提高定向凝固時(shí)的溫度梯度,使組織細(xì)化,在試樣縱向的連續(xù)性得到改善,試樣的力學(xué)和導(dǎo)電性能均提高。但提高抽拉速度,試樣強(qiáng)度和導(dǎo)電率均是先升后降,而塑性則先降后升。
[Abstract]:The high-strength and high-conductivity Cu-Cr-Zr alloy is widely used in integrated circuit lead frame, high-speed railway electrical contact line and aerospace and other fields. With the development of modern industrial technology, the requirement of high-strength and high-conductivity copper alloy is also higher and higher. It is necessary for us to develop new Cu-Cr-Zr alloy in time, and to study the cause and performance of the alloy. A trace rare-earth La and Y element are added on the basis of Cu-0.81Cr-0.12Zr alloy (mass percentage, the same below), the alloy ingot is prepared by adopting a vacuum induction melting method, the hot rolling is carried out after the homogenization annealing, and then the solid solution, the cold rolling and the aging treatment are carried out, The microstructure of the alloy in each process stage was analyzed by means of an optical microscope and a scanning electron microscope. The phase composition of the sample was analyzed by an X-ray diffractometer. The structure of the aging phase was analyzed by a high-resolution transmission electron microscope. The microhardness was measured by a digital-display hardness tester. The strength was measured by a universal mechanical testing machine and the conductivity was measured with a micro-ohm meter. The alloy thin strip specimens were prepared by means of the rapid solidification single-roll casting method, and the total supersaturated solid solution alloy was obtained, and the micro-hardness and the conductivity of the samples before and after the aging treatment were tested. In addition, a rod-like sample of Cu-0.81Cr alloy was prepared by liquid metal cooling and directional solidification, and the microstructure and mechanical and electrical properties of the alloy were investigated. The main conclusions are as follows: The phase composition of Cu-0.81Cr-0. 12Zr-0. 05La-0. 05Y ingot is not changed due to the addition of rare-earth, and the phases of Cu, Cr and Cu5Zr are all composed of Cu, Cr and Cu5Zr. Most of the Cr phases are in the form of Cr + Cu or in the grain boundary of Cu, and a small amount of Cr particles are distributed in the Cu matrix, and the Cu5Zr exists only at the Cu grain boundary. but the addition of rare earth elements can obviously refine the ingot structure. Cu-0.81Cr-0. 12Zr-0. 05La-0. 05Y ingot was annealed for 60 minutes at 1193 K temperature for 60 minutes, then cooled to room temperature for cold rolling at 1223 K temperature for 60 minutes, and the properties of different rolling-ratio cold-deformed alloys at different time after the series of temperature aging were investigated, and the cold deformation was found to be 60%. The microhardness of the samples treated with 773K aging treatment for 60 minutes was 186 HV and the conductivity was 81% IACS. The alloy is further subjected to cold deformation of 40%, then the alloy is aged for 30 minutes at 723K, the microhardness is increased to 203 HV, the conductivity is improved to 81.9% IACS, and the tensile strength and the elongation at this time are respectively 604 MPa and 8.5%. The precipitation of the precipitation phase and the recrystallization of the matrix Cu at 653K-698K and 743K-823K were carried out at a rate of 20K/ min by 60% cold-rolling of Cu-0.81Cr-0.12Zr-0.05La-0.05Y alloy at a rate of 20 K/ min. The microstrain of the cold-rolled Cu-0.81Cr-0.12Zr-0. 05La-0. 05Y alloy is higher than that of the pure copper, and the intensity of the (111) Cu diffraction peak in the XRD pattern decreases with the increase of the aging temperature, and (220) the intensity of the Cu diffraction peak is increasing. The Cu-0.81Cr-0.12Zr-0. 05La-0. 05Y alloy precipitates the Cu5Zr phase of the Cr-phase and the surface-centered cubic of the body-centered cubic in the aging process. In the best comprehensive performance, the partial precipitation phase is still in a co-lattice relationship with the matrix, in which the Nishiyama-Wassermann-bit directional relationship is presented between the Cr-out phase and the Cu matrix: (111) Cu// (110) Cr;[01 _ 1] Cu//[001] Cr;[2 _ 11] Cu//[1 _ 10] Cr. The fast-set Cu-0.81Cr-0.12Zr-0. 05La-0. 05Y alloy is a completely supersaturated solid solution, When the alloy is continuously heated at a rate of 20 K/ min, the heat release peak that reflects the desolvation and precipitation phase of the supersaturated solid solution starts at 655 K and ends at 688 K. The fast quenching strip has the best comprehensive performance after the time of the 773 K aging for 15 minutes: the microhardness reaches 215 HV and the conductivity is 70.6% IACS. The microstructure of the alloy after cold deformation of 60% is higher than 29HV, which shows that the hardening time is better than that of conventional solid-solution aging. The directionally solidified Cu-0.81Cr self-growing composite material is composed of a directionally arranged Cu-Cu branch (cell) crystal and a Cu + Cr eutectic reinforcement which is distributed on the grain boundary of the Cu-0. 81Cr self-growing composite material. Although the two phases in the eutectic structure are still non-oriented, the longitudinal distribution of the co-crystals along the primary Cu-Cu grain boundary in the directional solidification structure still significantly improves the strength, plasticity and electrical conductivity of the directional solidification alloy. the temperature gradient at the time of directional solidification is improved, the structure is refined, the continuity of the longitudinal direction of the sample is improved, and the mechanical and electrical conductivity of the sample can be improved. but the pulling speed is improved, the strength and the conductivity of the sample are firstly raised and then decreased, and the plasticity is firstly reduced.
【學(xué)位授予單位】：上海交通大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：TG146.11

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