工程科学学报，第38卷，第1期：102107,2016年1月 Chinese Journal of Engineering,Vol.38,No.1:102-107,January 2016 DOI:10.13374/j.issn2095-9389.2016.01.014:http://journals.ustb.edu.cn 凝胶注模制备的铝铜坯体脱脂过程及动力学 袁海英，贾成厂，张新新，Bekouche Karima,王召利 北京科技大学材料科学与工程学院，北京100083 ☒通信作者，Email:jiache@126.com 摘要通过凝胶注模工艺，采用非水基凝胶体系，成功地制备铝铜坯体.通过扫描电镜观察脱脂前聚合物完全包裹粉末颗 粒，脱脂后金属坯体中聚合物完全脱除.通过反应机理得出聚合物三维网络结构的化学式.采用热分析手段、热重和红外连 用系统分析金属坯体的脱脂过程，根据Coats-Redfern方法对非等温热失重率曲线的数据进行动力学研究，建立动力学方程. 在不同的升温速率下聚合物脱脂反应级数为1，活化能在79.86~108.63kJ·ml范围内，指前因子反应指数在10-10？ mim',活化能的结果表明反应对温度和动力学比较敏感.脱脂主要分为两个阶段，在240~350℃主要是聚合物链段的分解， 在350~470℃主要是聚合物网状结构的解聚和解交联反应，同时脱脂阶段主要产生C02、C0、N0,和H,0挥发性气体. 关键词凝胶注模：铝铜合金：脱脂：动力学 分类号TF125.2 Thermal degradation mechanism and kinetics of aluminum-copper green bodies prepared by gelcasting YUAN Hai-ying,JIA Cheng-chang,ZHANG Xin-xin,Bekouche Karima,WANG Zhao-li School of Materials Science and Technology,University of Science and Technology Beijing,Beijing 100083,China Corresponding author,E-mail:jiachc@126.com ABSTRACT Aluminum-copper green bodies were successfully prepared by a non-aqueous gelcasting system.Scanning electron mi- croscopy observations showed that the powder particles were completely wrapped by the polymer before degreasing,and the polymer in the metal body was completely removed after degreasing.A three-dimensional network polymer structure was obtained by the reaction mechanism.The degreasing process of the metal body was investigated by means of differential scanning calorimetry,thermogravime- try-derivative thermogravimetry and thermogravimetry-Fourier transform infrared spectroscopy.The kinetic equations and parameters were gotten according to Coats-Redfern method for non-isothermal weight loss curves.The results indicate that at different heating rates the reaction order is 1,the activation energy and pre-exponential factor are ranging from 79.86 to 108.63 kJ.mol-and 10 to 107 min,respectively.The activation energy reaction is sensitive to temperature and dynamics.The degreasing process is divided into two stages:a slight weight loss over a wide temperature range of 240-350 C is due to the random chain scission and the main weight loss around 380 to 425 C is attributed to depolymerization of monomers from the main chains and decrosslinking of the network polymer.The emissions of CO,,CO,NO,and H,O are identifled during the degreasing process. KEY WORDS gelcasting;aluminum-copper alloys;degreasing:kinetics 作为一种新型成型方法，凝胶注模将传统陶瓷工 利用催化剂及引发剂使悬浮体中的有机单体的聚合反 艺和聚合物化学有机结合起来，制备可近净尺寸、形状 应交联和桥接形成三维网状结构的聚合物，使液态悬 复杂和高可靠性的陶瓷和金属零部件-).它主要是 浮液转变成固态坯体，从而将粉末颗粒包裹固定 收稿日期：2014-10-08 基金项目：国家自然科学基金资助项目(51274041)工程科学学报，第 38 卷，第 1 期: 102--107，2016 年 1 月 Chinese Journal of Engineering，Vol． 38，No． 1: 102--107，January 2016 DOI: 10． 13374 /j． issn2095--9389． 2016． 01． 014; http: / /journals． ustb． edu． cn 凝胶注模制备的铝铜坯体脱脂过程及动力学 袁海英，贾成厂，张新新，Bekouche Karima，王召利 北京科技大学材料科学与工程学院，北京 100083  通信作者，E-mail: jiachc@ 126． com 摘 要 通过凝胶注模工艺，采用非水基凝胶体系，成功地制备铝铜坯体． 通过扫描电镜观察脱脂前聚合物完全包裹粉末颗 粒，脱脂后金属坯体中聚合物完全脱除． 通过反应机理得出聚合物三维网络结构的化学式． 采用热分析手段、热重和红外连 用系统分析金属坯体的脱脂过程，根据 Coats--Ｒedfern 方法对非等温热失重率曲线的数据进行动力学研究，建立动力学方程． 在不同的升温速率下聚合物脱脂反应级数为 1，活化能在 79. 86 ～ 108. 63 kJ·mol － 1 范围内，指前因子反应指数在 106 ～ 107 min － 1，活化能的结果表明反应对温度和动力学比较敏感． 脱脂主要分为两个阶段，在 240 ～ 350 ℃主要是聚合物链段的分解， 在 350 ～ 470 ℃主要是聚合物网状结构的解聚和解交联反应，同时脱脂阶段主要产生 CO2、CO、NO2和 H2O 挥发性气体． 关键词 凝胶注模; 铝铜合金; 脱脂; 动力学 分类号 TF125. 2 Thermal degradation mechanism and kinetics of aluminum--copper green bodies prepared by gelcasting YUAN Hai-ying，JIA Cheng-chang ，ZHANG Xin-xin，Bekouche Karima，WANG Zhao-li School of Materials Science and Technology，University of Science and Technology Beijing，Beijing 100083，China  Corresponding author，E-mail: jiachc@ 126． com ABSTＲACT Aluminum--copper green bodies were successfully prepared by a non-aqueous gelcasting system． Scanning electron mi￾croscopy observations showed that the powder particles were completely wrapped by the polymer before degreasing，and the polymer in the metal body was completely removed after degreasing． A three-dimensional network polymer structure was obtained by the reaction mechanism． The degreasing process of the metal body was investigated by means of differential scanning calorimetry，thermogravime￾try--derivative thermogravimetry and thermogravimetry--Fourier transform infrared spectroscopy． The kinetic equations and parameters were gotten according to Coats--Ｒedfern method for non-isothermal weight loss curves． The results indicate that at different heating rates the reaction order is 1，the activation energy and pre-exponential factor are ranging from 79. 86 to 108. 63 kJ·mol － 1 and 106 to 107 min － 1，respectively． The activation energy reaction is sensitive to temperature and dynamics． The degreasing process is divided into two stages: a slight weight loss over a wide temperature range of 240 － 350 ℃ is due to the random chain scission and the main weight loss around 380 to 425 ℃ is attributed to depolymerization of monomers from the main chains and decrosslinking of the network polymer． The emissions of CO2，CO，NO2 and H2O are identifled during the degreasing process． KEY WOＲDS gelcasting; aluminum--copper alloys; degreasing; kinetics 收稿日期: 2014--10--08 基金项目: 国家自然科学基金资助项目( 51274041) 作为一种新型成型方法，凝胶注模将传统陶瓷工 艺和聚合物化学有机结合起来，制备可近净尺寸、形状 复杂和高可靠性的陶瓷和金属零部件［1--3］． 它主要是 利用催化剂及引发剂使悬浮体中的有机单体的聚合反 应交联和桥接形成三维网状结构的聚合物，使液态悬 浮液转变成固态坯体，从而将粉末颗粒包裹固定［4--5］．