光学硅橡胶表面低透气性涂层的制备与性能
|
摘要
通过合成折射率与白炭黑相匹配的苯基乙烯基硅油和苯基含氢硅油,以白炭黑补强,固化后获得光学透明的苯基硅橡胶,然后以四甲基己二胺为催化剂,使喷涂在苯基硅橡胶表面的有机聚硅氮烷(OPSZ)实现低温固化及硅质转变,获得具有低气体渗透性的致密涂层,并对涂层的光学性能、透氧量、抗硫化性能进行了测试和表征。结果表明:OPSZ涂层表面连续、均匀、致密,无裂纹和空隙,涂层断面致密均匀,无缝隙和裂纹,当涂层厚度低于32μm时,涂层与硅橡胶间的粘接力良好;固化后的OPSZ显示出优异的透明度、透光性能和气体屏蔽性能;在400~800 nm范围内透光率>92%;当涂层厚度达到12μm以后,透氧量降至1.4 cm~3/m~2,并保持不变,涂覆涂层后的封装灯珠均显示良好的抗硫化能力,硫化后光通量维持率在99.9%以上。当w(四甲基己二胺)>5%,在室温、相对湿度50%条件下放置24 h实现了硅质转化,提高加热温度和相对湿度,可以有效地缩短硅质转化的时间。
Phenyl vinyl silicone oil and phenyl hydrogen silicone oil were prepared and had refractive index matching with that of fumed silica. Then optical transparent phenyl silicone rubber was obtained by using fumed silica as reinforcing fillers. Finally,organic polysilazane( OPSZ) was coated on the silicone rubber surface with tetramethyl hexamethylene diamine as a catalyst and the dense coating with low gas permeability was achieved,and this process realized low- temperature curing and siliceous transition. Optical performance,oxygen permeation flux,and anti- sulfuration were measured. The results showed that the OPSZ coating surface was continuous,uniform,dense and free of cracks and voids,meanwhile the coating section was dense,uniform,seamless,without cracks. The interface between the coating and the silicone rubber exhibited good adhesion when the coating thickness was less than 32 ~ 35 μm. The coatings possessed excellent transparency,light transmission and gas shielding properties. Light transmission was over 92% between 400 ~ 800 nm. When the coating thickness was more than 12 μm,the oxygen permeation flux decreased to 1. 4 cm~3/m~2 and remainedunchanged,lamps after coating had good anti- sulfuration ability,and the luminous flux maintained over 99. 9%. When w( tetramethyl hexamethylene diamine) was over 5%,the siliceous conversion was achieved under room temperature and 50% relative humidity for 24 h. In addition,the siliceous conversion time could be effectively shortened by increasing heating temperature and relative humidity.
Phenyl vinyl silicone oil and phenyl hydrogen silicone oil were prepared and had refractive index matching with that of fumed silica. Then optical transparent phenyl silicone rubber was obtained by using fumed silica as reinforcing fillers. Finally,organic polysilazane( OPSZ) was coated on the silicone rubber surface with tetramethyl hexamethylene diamine as a catalyst and the dense coating with low gas permeability was achieved,and this process realized low- temperature curing and siliceous transition. Optical performance,oxygen permeation flux,and anti- sulfuration were measured. The results showed that the OPSZ coating surface was continuous,uniform,dense and free of cracks and voids,meanwhile the coating section was dense,uniform,seamless,without cracks. The interface between the coating and the silicone rubber exhibited good adhesion when the coating thickness was less than 32 ~ 35 μm. The coatings possessed excellent transparency,light transmission and gas shielding properties. Light transmission was over 92% between 400 ~ 800 nm. When the coating thickness was more than 12 μm,the oxygen permeation flux decreased to 1. 4 cm~3/m~2 and remainedunchanged,lamps after coating had good anti- sulfuration ability,and the luminous flux maintained over 99. 9%. When w( tetramethyl hexamethylene diamine) was over 5%,the siliceous conversion was achieved under room temperature and 50% relative humidity for 24 h. In addition,the siliceous conversion time could be effectively shortened by increasing heating temperature and relative humidity.
引文
[1]Zhu Huaijun(朱淮军),Dai Zilin(戴子林),Tu Weiping(涂伟萍).A kind of transparent LED filament encapsulated silicone rubber:CN104164209[P].2015-10-07.
[2]Zhu Huaijun(朱淮军),Dai Zilin(戴子林),Tu Weiping(涂伟萍).Preparation of anti-fog transparent silicone rubber film used on car rearview mirror:CN104212377[P].2016-01-27.
[3]Koerner G,Schulze M,Weis J.Silicones:chemistry and technology[M].Vulkan-Verlag,Essen,1991.
[4]Kang D W,Yeo H G,Lee K S.Preparation and characterisation of liquid silicone rubber nanocomposite containing ultrafine magnesium ferrite powder[J].Journal of Inorganic and Organometallic Polymers.2004,14(1):73-84.
[5]Birkefeld A B,Eckert H,Pfleiderer B.A study of aging silicone breast implants using29Si,1H relaxation and DSC measurements[J].Biomaterials,2004,25(18):4405-4413.
[6]Gu Q G,Zhou Q L.Preparation of high strength and optically transparent silicone rubber[J].Eur Polym J,1998,34(11):1727-1733.
[7]Zhang J,Feng S Y.Effect of crosslinking on the conductivity of conductive silicone rubber[J].J Appl Polym Sci,2003,89(13):3471-3475.
[8]Tang Y,Tsing R.Rheological,extractive and thermal studies of the room temperature vulcanized polydimethylsiloxane[J].Polymer,1999,40(22):6135-6146.
[9]Kojima A,Hoshii S,Muto T.Characteristics of polysilazane compound and its application as coating for carbon material[J].J Mater Sci Lett,2002,21(10):757-760.
[10]Gnthner M,Kraus T,Dierdorf A,et al.Advanced coatings on the basis of Si(C)N precursors for protection of steel against oxidation[J].J Eur Ceram Soc,2009,29(10):2061-2068.
[11]Zhang Zongbo,Xiao Fengyan,Luo Yongming.Research progress in perhydropolysilazane coatings[J].Paint&Coatings Industry(涂料工业),2013,43(4):74-79.
[12]Lutz P,Andreas D,Hubert L,et al.Conversion of perhydropolysilazane into a Si-Oxnetwork triggered by vacuum ultraviolet irradiation:Access to flexible,transparent barrier coatings[J].Chemistry-A European Journal,2007,13:8522-8529.
[13]Frank B,Ulrich D,Andreas D,et al.Preparation of moisture curable polysilazane coatings:Part I.Elucidation of low temperature curing kinetics by FT-IR spectroscopy[J].Progress in Organic Coatings,2005,53:183-190.
[14]Martin G,Tobias K,Walter K,et al.Particle-filled PHPS silazanebased coatings on steel[J].International Journal of Applied Ceramic Technology,2009,6(3):373-380.
[15]Funayama O,Tashiro Y,Kamo A,et al.Conversion mechanism of perhydropolysilazane into silicon nitride-based ceramics[J].Journal of Materials Science,1994,29:4883-4888.
[16]Takahiro T,Koji H,Masuji Y,et al.Silica film coating method for veneering resin composite[J].Dental Materials Journal,2011,30(2):170-175.
[17]Tomoko K,Eisuke T,Hiromitsu K.Preparation of hot waterresistant silica thin films from polysilazane solution at room temperature[J].Journal of Sol-Gel Science and Technology,2004,31:257-261.
[18]Peng Z J,Fu X L,Zhu N,et al.Preparation and growth mechanism of clustered one-dimensional Si-Oxamorphous nanowires by catalytic pyrolysis of a polymer precursor[J].Journal of Non-Crystalline Solids,2009,355:2156-2159.
[19]Matteo M,Barbara D,Renzo B,et al.New protective coatings for ancient glass:Silica thin-films from perhydropolysilazane[J].Journal of Cultural Heritage,2008,9:143-145.
[20]Chiaming C,Minghsin Y,Hungju C,et al.Application of VUV irradiation to promote the wet etch resistance of PSZ-SOG film inside the gap[J].Microelectronic Engineering,2010,87:1927-1931.
[2]Zhu Huaijun(朱淮军),Dai Zilin(戴子林),Tu Weiping(涂伟萍).Preparation of anti-fog transparent silicone rubber film used on car rearview mirror:CN104212377[P].2016-01-27.
[3]Koerner G,Schulze M,Weis J.Silicones:chemistry and technology[M].Vulkan-Verlag,Essen,1991.
[4]Kang D W,Yeo H G,Lee K S.Preparation and characterisation of liquid silicone rubber nanocomposite containing ultrafine magnesium ferrite powder[J].Journal of Inorganic and Organometallic Polymers.2004,14(1):73-84.
[5]Birkefeld A B,Eckert H,Pfleiderer B.A study of aging silicone breast implants using29Si,1H relaxation and DSC measurements[J].Biomaterials,2004,25(18):4405-4413.
[6]Gu Q G,Zhou Q L.Preparation of high strength and optically transparent silicone rubber[J].Eur Polym J,1998,34(11):1727-1733.
[7]Zhang J,Feng S Y.Effect of crosslinking on the conductivity of conductive silicone rubber[J].J Appl Polym Sci,2003,89(13):3471-3475.
[8]Tang Y,Tsing R.Rheological,extractive and thermal studies of the room temperature vulcanized polydimethylsiloxane[J].Polymer,1999,40(22):6135-6146.
[9]Kojima A,Hoshii S,Muto T.Characteristics of polysilazane compound and its application as coating for carbon material[J].J Mater Sci Lett,2002,21(10):757-760.
[10]Gnthner M,Kraus T,Dierdorf A,et al.Advanced coatings on the basis of Si(C)N precursors for protection of steel against oxidation[J].J Eur Ceram Soc,2009,29(10):2061-2068.
[11]Zhang Zongbo,Xiao Fengyan,Luo Yongming.Research progress in perhydropolysilazane coatings[J].Paint&Coatings Industry(涂料工业),2013,43(4):74-79.
[12]Lutz P,Andreas D,Hubert L,et al.Conversion of perhydropolysilazane into a Si-Oxnetwork triggered by vacuum ultraviolet irradiation:Access to flexible,transparent barrier coatings[J].Chemistry-A European Journal,2007,13:8522-8529.
[13]Frank B,Ulrich D,Andreas D,et al.Preparation of moisture curable polysilazane coatings:Part I.Elucidation of low temperature curing kinetics by FT-IR spectroscopy[J].Progress in Organic Coatings,2005,53:183-190.
[14]Martin G,Tobias K,Walter K,et al.Particle-filled PHPS silazanebased coatings on steel[J].International Journal of Applied Ceramic Technology,2009,6(3):373-380.
[15]Funayama O,Tashiro Y,Kamo A,et al.Conversion mechanism of perhydropolysilazane into silicon nitride-based ceramics[J].Journal of Materials Science,1994,29:4883-4888.
[16]Takahiro T,Koji H,Masuji Y,et al.Silica film coating method for veneering resin composite[J].Dental Materials Journal,2011,30(2):170-175.
[17]Tomoko K,Eisuke T,Hiromitsu K.Preparation of hot waterresistant silica thin films from polysilazane solution at room temperature[J].Journal of Sol-Gel Science and Technology,2004,31:257-261.
[18]Peng Z J,Fu X L,Zhu N,et al.Preparation and growth mechanism of clustered one-dimensional Si-Oxamorphous nanowires by catalytic pyrolysis of a polymer precursor[J].Journal of Non-Crystalline Solids,2009,355:2156-2159.
[19]Matteo M,Barbara D,Renzo B,et al.New protective coatings for ancient glass:Silica thin-films from perhydropolysilazane[J].Journal of Cultural Heritage,2008,9:143-145.
[20]Chiaming C,Minghsin Y,Hungju C,et al.Application of VUV irradiation to promote the wet etch resistance of PSZ-SOG film inside the gap[J].Microelectronic Engineering,2010,87:1927-1931.