稀土及过渡金属氧化物改性纳米碳酸钙/天然橡胶复合材料的结构与性能  

Structure and properties of rare earth oxide and transition metal oxide modified nano calcium carbonate/natural rubber composites

作　　者：林雅铃[1] 洪少颖[1] 王炼石[1] 周奕雨[1] 张安强[1] 

机构地区：[1]华南理工大学材料科学与工程学院高分子材料科学与工程系,广东广州510640

出　　处：《合成橡胶工业》2004年第6期363-367,共5页China Synthetic Rubber Industry

基　　金：国家自然科学基金资助项目 (5 9773 0 10 ) ;广东省自然科学基金资助项目 (970 5 5 4;0 3 13 66)

摘　　要：用镧、铈、钐、钬和镱稀土 (Ln)氧化物 (Ln2 O3 )及锌、钴和镍过渡金属 (TM)氧化物 (TMO)制备了稀土氢氧化物包覆纳米碳酸钙 [NCaCO3 -Ln(OH) 3 ]和过渡金属氢氧化物包覆纳米碳酸钙 [NCaCO3 -TM(OH) 2 ]。将二者分别加入 1 0 0份 (质量 ,下同 )天然胶乳 (NRL)中 ,保持体系的pH值约为 1 2 ,于 85℃下恒温搅拌 1h ,采用凝聚共沉法制备了稀土氧化物改性纳米碳酸钙 /天然橡胶复合材料 [NR/NCaCO3 -Ln(OH) 3 ]及过渡金属氧化物改性纳米碳酸钙 /天然橡胶复合材料 [NR/NCaCO3 -TM(OH) 2 ]。结果表明 ,所选用的Ln2 O3 与TMO对NCaCO3 均具有优良的改性作用 ,对硫化胶有显著的增强作用 ,其中以La2 O3 ,Sm2 O3 ,ZnO的改性效果为佳 ,且三者最佳用量依次为 0 5 0 ,1 0 0 ,2 5份。扫描电子显微镜分析表明 ,NCaCO3 -La(OH) 3 ,NCaCO3 -Sm(OH) 3 ,NCaCO3 -Zn(OH) 2 与NRL的界面结合牢固 ,并形成拉丝结构。动态力学分析表明 ,与未改性纳米碳酸钙填充天然橡胶 (NR/NCaCO3 )的硫化胶相比 ,NR/NCaCO3 -Sm(OH) 3 和NR/NCaCO3 -Zn(OH) 2 硫化胶的玻璃化转变温度稍有上升 ,内耗也略有增大。The oxides of rare earth (Ln) of La, Ce, Sm, Ho and Yb or oxides of transition metal (TM) of Zn, Co and Ni were used to prepare the hydroxides of Ln or TM modified nano calcium carbonate[NCaCO 3-Ln(OH) 3 or NCaCO 3-TM(OH) 2]. Then natural latex (NRL) was added into the reactor. The system reacted at 85 ℃ with stirring for 1 h to prepare NCaCO 3-Ln(OH) 3/natural rubber composite [NR/NCaCO 3-Ln(OH) 3] or NCaCO 3- TM(OH) 2 /NRL composite[NR/NCaCO 3- TM(OH) 2 ].The effects of the rare earth ions and transition metal ions on the mechanical properties of vulcanized rubber were studied. It was found that compared with unmodified NCaCO 3 filled natural rubber (NR/NCaCO 3), the mechanical properties of NR/NCaCO 3-Ln(OH) 3 or NR/NCaCO 3- TM(OH) 2 could be improved significantly, especially for the rubber containing the compound of La 3+ , Sm 3+ , Zn 2+ with dosage of 0.50, 1.00, 2.5 phr, respectively. The tensile fracture morphology of vulcanized rubber was analyzed by SEM. The results showed that NCaCO 3-La(OH) 3, NCaCO 3- Sm(OH) 3 and NCaCO 3-Zn(OH) 2 filled NRL had better polymer-filler interaction. The filament was observed on the surface of fracture, this phenomenon was not been reported. DMA analysis showed that compared with NR/NCaCO 3 vulcanizates, both the T g and the loss tangent of NR/NCaCO 3- Sm(OH) 3 and NR/ NCaCO 3 -Zn(OH) 2 increased.

关 键 词：天然胶乳 纳米碳酸钙 稀土氧化物 过渡金属氧化物 复合材料 硫化胶 力学性能 增强 

分 类 号：TQ332[化学工程—橡胶工业]