用煤沥青和造纸黑液中的木质素制备电磁屏蔽材料的中试研究
|
摘要
本中试试验采用造纸废液中的木质素和中温煤沥青为原料,通过添加适量镍、钙催化剂催化碳化制备电磁屏蔽材料,并用XRD、SEM等检测手段对碳化产物进行表征。
造纸废液经酸析、除硅后得到木质素,并对此木质素用FT-IR、TG进行表征,后在木质素中添加不同含量镍、钙催化剂并进行催化碳化。实验表明:在Ni8wt%、Ca6wt%、碳化温度为900℃的实验条件下木质素可以生成具有完善层状结构的石墨结晶碳。
将原煤沥青(CTP)使用四氢呋喃萃取分离得到四氢呋喃可溶物(THFS)和四氢呋喃不溶物(THFI)两部分。并对添加了适量镍、钙催化剂的CTP、THFS、THFI进行催化碳化,得出了THFI、碳化温度、镍、钙催化剂添加量对THFS碳化产物的Lc值、d_(002)值的影响规律。实验结果表明:当钙添加量为1.6wt%时,随着镍添加量的增加,碳化产物中结晶碳的Lc值随之增加; 当保持镍添加量为7wt%增加钙含量,Lc值随之增加,但钙添加量超过1.6wt%时,Lc值反而有所下降; 碳化温度从700℃上升到900℃,碳化产物结晶碳Lc值也趋于增加。
由小试实验可知:当碳化产物中结晶碳尺寸(Lc值)达到60 ?以上时制备得到的电磁屏蔽材料的EMS性能就可超过实际应用标准(30dB),故本中试试验预期可得到具有良好电磁屏蔽性能的电磁屏蔽材料。
In this pilot-scale study, lignin from black liquor of papermaking and medium pitch which used as the raw materials were carbonized to produce electromagnetic shielding material after loading nickel and calcium. The crystal structure of chars was checked with XRD and SEM.
Lignin was obtained from black liquor of papermaking by two step process (sulphur dioxide, silica removal), which was analyzed by FT-IR、TG. Then lignin was carbonized by loading various amounts of nickel and calcium. The results revealed that, optimal condition were Ni8wt%, Ca6wt%, 900℃ carbonisation temperature in the pilot-scale study.
The coal tar pitch was separated into two fractions (THF-insoluble, THFI; THF-soluble, THFS) by solvent exaction using tatrahydrofuran (THF). The coal tar pitch (CTP) and its two fractions ( THFI and THFS) were carbonized, which reveals that The effects of THFI, carbonization temperature, the amount of nickel, and the type and amount of calcium on the crystallite sizes (Lc) of various chars with nickel and calcium loading. The results showed that Lc for the chars with 1.6wt% calcium increased with increasing amount of nickel loaded; Lc for the chars with an equal loading of 7wt% nickel increased with increasing amount of calcium added and then decreased and that, with an equal co-loading of 7 wt% nickel and 1.6 wt% calcium, also increased with increasing carbonisation temperature, from 700 to 900 ℃.
The present study demonstrated that the EMS capacities exceeded a practical standard of EMS capacities when Lc of chars exceeded 60 ?, so the EMS materials with excellent EMS capacities would be obtained.
造纸废液经酸析、除硅后得到木质素,并对此木质素用FT-IR、TG进行表征,后在木质素中添加不同含量镍、钙催化剂并进行催化碳化。实验表明:在Ni8wt%、Ca6wt%、碳化温度为900℃的实验条件下木质素可以生成具有完善层状结构的石墨结晶碳。
将原煤沥青(CTP)使用四氢呋喃萃取分离得到四氢呋喃可溶物(THFS)和四氢呋喃不溶物(THFI)两部分。并对添加了适量镍、钙催化剂的CTP、THFS、THFI进行催化碳化,得出了THFI、碳化温度、镍、钙催化剂添加量对THFS碳化产物的Lc值、d_(002)值的影响规律。实验结果表明:当钙添加量为1.6wt%时,随着镍添加量的增加,碳化产物中结晶碳的Lc值随之增加; 当保持镍添加量为7wt%增加钙含量,Lc值随之增加,但钙添加量超过1.6wt%时,Lc值反而有所下降; 碳化温度从700℃上升到900℃,碳化产物结晶碳Lc值也趋于增加。
由小试实验可知:当碳化产物中结晶碳尺寸(Lc值)达到60 ?以上时制备得到的电磁屏蔽材料的EMS性能就可超过实际应用标准(30dB),故本中试试验预期可得到具有良好电磁屏蔽性能的电磁屏蔽材料。
In this pilot-scale study, lignin from black liquor of papermaking and medium pitch which used as the raw materials were carbonized to produce electromagnetic shielding material after loading nickel and calcium. The crystal structure of chars was checked with XRD and SEM.
Lignin was obtained from black liquor of papermaking by two step process (sulphur dioxide, silica removal), which was analyzed by FT-IR、TG. Then lignin was carbonized by loading various amounts of nickel and calcium. The results revealed that, optimal condition were Ni8wt%, Ca6wt%, 900℃ carbonisation temperature in the pilot-scale study.
The coal tar pitch was separated into two fractions (THF-insoluble, THFI; THF-soluble, THFS) by solvent exaction using tatrahydrofuran (THF). The coal tar pitch (CTP) and its two fractions ( THFI and THFS) were carbonized, which reveals that The effects of THFI, carbonization temperature, the amount of nickel, and the type and amount of calcium on the crystallite sizes (Lc) of various chars with nickel and calcium loading. The results showed that Lc for the chars with 1.6wt% calcium increased with increasing amount of nickel loaded; Lc for the chars with an equal loading of 7wt% nickel increased with increasing amount of calcium added and then decreased and that, with an equal co-loading of 7 wt% nickel and 1.6 wt% calcium, also increased with increasing carbonisation temperature, from 700 to 900 ℃.
The present study demonstrated that the EMS capacities exceeded a practical standard of EMS capacities when Lc of chars exceeded 60 ?, so the EMS materials with excellent EMS capacities would be obtained.
引文
[1]汝强等,电磁屏蔽理论及屏蔽材料的制备,包装工程,[J],2004:(5)
[2]王锦成,电磁屏蔽材料的屏蔽原理及研究现状,化工新型材料,[J]2002,30(7):16～18
[3]黄福祥等,电磁屏蔽材料,材料导报,[J]1997,11(3):18～21
[4]Sadchikov VV, Amorphous materials in electromagnetic shielding,[J] stal’1997(4)66～69
[5]施东梅等,新型电磁屏蔽材料研究动态,化工新型材料,[J],2001,29(10)20～22
[6]shacklette LV, EMI shielding of intrinsically conductive polymer, J Vinyl Techn,[J],1992,14(2):118～122
[7]湖北省电磁兼容学会,电磁兼容原理及应用,国防工业出版社,1996
[8]Huang J C, Adv polym technol, 1995,14(2):137
[9]宋月贤,电磁屏蔽用高导电聚苯胺薄膜的制备及电磁屏蔽特性研究,[博士学位论文],西安,西安交通大学,2001
[10]谭松庭等,金属纤维填充聚合物复合材料的导电性能和电磁屏蔽性能,材料工程,[J],1999:(12):6～9
[11]李勇,电磁屏蔽与电磁涂料的应用,化学与粘合,[J],2004(4):189～194
[12]Chi-Yuan Huang, Jui-Fen pai. Optimum conditions of electrolyses nickel plating on carbon fibers for EMI shielding effectiveness of ABS composites, European polymer journal,[J],1998,34(2):261～271
[13]吴行等,多层复合型电磁屏蔽涂料的研究,功能材料,[J],2001,31(4):365～367
[14]毕海峰等,电磁屏蔽材料的发展,产业用纺织品,[J],2001,(6):7～9
[15]杜仕国,施东梅,邓辉,金属填充聚合物屏蔽 EMI 材料,包装工程,[J],2000,21(4):19～21
[16]Yan-Lin, Nickel and copper coated carbon fiber, Materials sci, [J], 1996,(34):5781～5786
[17]张光敏,阎康平,本征导电高分子材料的进展,电子元件与材料,[J],1999,(8):41～53
[18]贾向明,杨其,李光宪等,本征导电高分子材料与复合材料的研究,化学世界,[J],2004,610～613
[19] 陈 婉 , 梁 成 浩 , 谢 阳 , 本 征 导 电 聚 合 物 开 发 的 最 新 进 展 , 电 化 学 ,[J],2001,7(4):376～402
[20]Dong shaojun, Che guanli, Xie yuangwu, chemically modified electrodes , [M],Beijing, science press,1995
[21]杜仕国,王保平,曹营军,导电高分子材料的电磁屏蔽效能分析,复合材料,[J],2001,6(11):19～21
[22]谭松庭,章明秋,曾汉明,屏蔽 EMI 用导电性高分子复合材料,材料工程,[J],1998(5):6～9
[23]吴瑞文,林云,林展如等,屏蔽电磁干扰高分子复合材料的研究,功能材料,[J],2002,33(5):492～494
[24]S.Courric and V.H.Than, the electromagnetic properties of poly derivatives, polymer,[J], 1998,39(12):2339～2408
[25]李宏建,彭景翠,填充炭黑/石墨的导电硅橡胶的研究,功能材料,[J],2000,31(2):221～222
[26]马宏才,张梅,电磁屏蔽技术探讨,山东纺织科技,[J],2003,(3):52～54
[27]D.D.L.Chung electromagnetic interference shielding effectiveness of carbon materials, [J],2001,39:279～285
[29]Olive DA, Radford DW, integrating EMI shielding into composite structure. Samper, [J],1997,33(1):51～57
[30]Luo X, Chung DDL, electromagnetic interference shielding reaching 30dB using flexible graphite, carbon 1996,34(10):1293～1297
[31]关正辉,石墨层间化合物的特性及应用前景,甘肃科技,[J],2002,18(10):48～49
[32]李侃社,邵水源,严兰英等,聚苯胺/石墨导电复合材料的制备与表征,高分子材料科学与工程,[J],2002,18(10):92～95
[33]陈晓梅,全成子,聚丙烯/石墨导电复合材料的制备与表征,中国塑料,[J],2001,15(9):40～43
[34]曾祥云,李家俊,师春生,碳纤维在电磁功能复合材料中的应用,材料导报,[J],1998,12(2):64～67
[35]徐荣华,阎家旺,黄士峰等,碳纤维-水泥基导电复合材料的导电性能研究,济南大学学报,[J],2004,18(2):103～105
[36]陈耀庭,周明义,王国全等,碳纤维/聚合物复合材料的导电性及电磁屏蔽性能的研究,塑料科技,[J],1997,(6):4～7
[37]武书彬编,造纸工业水污染控制与治理技术,化工工业出版社
[38]秦毅恒等,造纸黑液酸析法回收木质素,环境污染与治理,1999:(21)
[39]黄立新,韩磊,王占军等,造纸提取黑液污染零排放新工艺研究,中国工程科学,2001,3(10):72～76
[40]高洁等著,纤维素科学,科学出版社,1998
[41]亢树新,刘峰良,造纸黑液的综合利用技术,科技情报开发与技术,[J],2004,14(11):206～207
[42]肖瑞华,煤焦油化工学,北京:冶金工业出版社,2002
[43]许斌,潘立慧,炭材料用煤沥青的制备、性能和应用,湖北科学技术出版社,2002
[44] Wang G.H, Li Y.C, nickel-catalyzed carbonization of coal tar pitch to produce electromagnetic shielding material [C], proceedings of the world engineers’ convention 2004,shanghai, 2004,256-262
[45]Guanghui Wang, Guanghua Wang, nickel-catalyzed carbonization of lignite to produce crystallized carbon for electromagnetic shielding [C], The 29th internet technical conference on coal unutilized & fuel systems ,Florida, USA,2004,
[46]李勉军等,木质素灰分测定,闽江学院学报,[J],2002,23(2):70～71
[47]U.Swietlik,S, S,.Jasiennko, carbonization and graphitization processes of pitch from coal liquid and its fractions, carbon, [J],1993,31(3):461～466
[2]王锦成,电磁屏蔽材料的屏蔽原理及研究现状,化工新型材料,[J]2002,30(7):16～18
[3]黄福祥等,电磁屏蔽材料,材料导报,[J]1997,11(3):18～21
[4]Sadchikov VV, Amorphous materials in electromagnetic shielding,[J] stal’1997(4)66～69
[5]施东梅等,新型电磁屏蔽材料研究动态,化工新型材料,[J],2001,29(10)20～22
[6]shacklette LV, EMI shielding of intrinsically conductive polymer, J Vinyl Techn,[J],1992,14(2):118～122
[7]湖北省电磁兼容学会,电磁兼容原理及应用,国防工业出版社,1996
[8]Huang J C, Adv polym technol, 1995,14(2):137
[9]宋月贤,电磁屏蔽用高导电聚苯胺薄膜的制备及电磁屏蔽特性研究,[博士学位论文],西安,西安交通大学,2001
[10]谭松庭等,金属纤维填充聚合物复合材料的导电性能和电磁屏蔽性能,材料工程,[J],1999:(12):6～9
[11]李勇,电磁屏蔽与电磁涂料的应用,化学与粘合,[J],2004(4):189～194
[12]Chi-Yuan Huang, Jui-Fen pai. Optimum conditions of electrolyses nickel plating on carbon fibers for EMI shielding effectiveness of ABS composites, European polymer journal,[J],1998,34(2):261～271
[13]吴行等,多层复合型电磁屏蔽涂料的研究,功能材料,[J],2001,31(4):365～367
[14]毕海峰等,电磁屏蔽材料的发展,产业用纺织品,[J],2001,(6):7～9
[15]杜仕国,施东梅,邓辉,金属填充聚合物屏蔽 EMI 材料,包装工程,[J],2000,21(4):19～21
[16]Yan-Lin, Nickel and copper coated carbon fiber, Materials sci, [J], 1996,(34):5781～5786
[17]张光敏,阎康平,本征导电高分子材料的进展,电子元件与材料,[J],1999,(8):41～53
[18]贾向明,杨其,李光宪等,本征导电高分子材料与复合材料的研究,化学世界,[J],2004,610～613
[19] 陈 婉 , 梁 成 浩 , 谢 阳 , 本 征 导 电 聚 合 物 开 发 的 最 新 进 展 , 电 化 学 ,[J],2001,7(4):376～402
[20]Dong shaojun, Che guanli, Xie yuangwu, chemically modified electrodes , [M],Beijing, science press,1995
[21]杜仕国,王保平,曹营军,导电高分子材料的电磁屏蔽效能分析,复合材料,[J],2001,6(11):19～21
[22]谭松庭,章明秋,曾汉明,屏蔽 EMI 用导电性高分子复合材料,材料工程,[J],1998(5):6～9
[23]吴瑞文,林云,林展如等,屏蔽电磁干扰高分子复合材料的研究,功能材料,[J],2002,33(5):492～494
[24]S.Courric and V.H.Than, the electromagnetic properties of poly derivatives, polymer,[J], 1998,39(12):2339～2408
[25]李宏建,彭景翠,填充炭黑/石墨的导电硅橡胶的研究,功能材料,[J],2000,31(2):221～222
[26]马宏才,张梅,电磁屏蔽技术探讨,山东纺织科技,[J],2003,(3):52～54
[27]D.D.L.Chung electromagnetic interference shielding effectiveness of carbon materials, [J],2001,39:279～285
[29]Olive DA, Radford DW, integrating EMI shielding into composite structure. Samper, [J],1997,33(1):51～57
[30]Luo X, Chung DDL, electromagnetic interference shielding reaching 30dB using flexible graphite, carbon 1996,34(10):1293～1297
[31]关正辉,石墨层间化合物的特性及应用前景,甘肃科技,[J],2002,18(10):48～49
[32]李侃社,邵水源,严兰英等,聚苯胺/石墨导电复合材料的制备与表征,高分子材料科学与工程,[J],2002,18(10):92～95
[33]陈晓梅,全成子,聚丙烯/石墨导电复合材料的制备与表征,中国塑料,[J],2001,15(9):40～43
[34]曾祥云,李家俊,师春生,碳纤维在电磁功能复合材料中的应用,材料导报,[J],1998,12(2):64～67
[35]徐荣华,阎家旺,黄士峰等,碳纤维-水泥基导电复合材料的导电性能研究,济南大学学报,[J],2004,18(2):103～105
[36]陈耀庭,周明义,王国全等,碳纤维/聚合物复合材料的导电性及电磁屏蔽性能的研究,塑料科技,[J],1997,(6):4～7
[37]武书彬编,造纸工业水污染控制与治理技术,化工工业出版社
[38]秦毅恒等,造纸黑液酸析法回收木质素,环境污染与治理,1999:(21)
[39]黄立新,韩磊,王占军等,造纸提取黑液污染零排放新工艺研究,中国工程科学,2001,3(10):72～76
[40]高洁等著,纤维素科学,科学出版社,1998
[41]亢树新,刘峰良,造纸黑液的综合利用技术,科技情报开发与技术,[J],2004,14(11):206～207
[42]肖瑞华,煤焦油化工学,北京:冶金工业出版社,2002
[43]许斌,潘立慧,炭材料用煤沥青的制备、性能和应用,湖北科学技术出版社,2002
[44] Wang G.H, Li Y.C, nickel-catalyzed carbonization of coal tar pitch to produce electromagnetic shielding material [C], proceedings of the world engineers’ convention 2004,shanghai, 2004,256-262
[45]Guanghui Wang, Guanghua Wang, nickel-catalyzed carbonization of lignite to produce crystallized carbon for electromagnetic shielding [C], The 29th internet technical conference on coal unutilized & fuel systems ,Florida, USA,2004,
[46]李勉军等,木质素灰分测定,闽江学院学报,[J],2002,23(2):70～71
[47]U.Swietlik,S, S,.Jasiennko, carbonization and graphitization processes of pitch from coal liquid and its fractions, carbon, [J],1993,31(3):461～466