功能化石墨烯及其復(fù)合材料的制備與性能研究
發(fā)布時(shí)間：2019-06-06 03:56
【摘要】：石墨烯是由碳原子以正六邊形組成的蜂窩狀單層二維片層材料,具有優(yōu)異的電學(xué)性能、光學(xué)性能、熱導(dǎo)性能、阻隔性能、量子霍爾效應(yīng)、室溫鐵磁效應(yīng)等,已經(jīng)成為當(dāng)前研究的熱點(diǎn)。目前制備石墨烯的方法有很多,大多都條件苛刻難以實(shí)現(xiàn),氧化還原法制備石墨烯具有操作簡單、成本低廉、產(chǎn)率高以及可大規(guī)模生產(chǎn)等優(yōu)點(diǎn)而被廣泛使用。無論是氧化石墨烯還是石墨烯都具有優(yōu)異綜合性能和超高比表面積,因此使它們成為制備高性能復(fù)合材料的理想填料。但是石墨烯在基體體系中分散和團(tuán)聚是限制其廣泛應(yīng)用的關(guān)鍵問題。本論文為解決這些問題,從提高填料與基體之間界面的相互作用出發(fā),在石墨烯的表面引入活性官能團(tuán),并用這些功能化的石墨烯作為填料制備聚合物復(fù)合材料。主要研究內(nèi)容如下:(1)通過氧化還原法制備氧化石墨烯和石墨烯,再利用其表面的含氧基團(tuán)(羥基、羧基、羰基、環(huán)氧基)進(jìn)行共價(jià)鍵修飾。首先是氨基化修飾,用對苯二胺溶液和氧化石墨烯溶液按10:1(固含量比)混合,90℃反應(yīng)24h,然后還原離心分離,得到氨基功能化石墨烯;其次用接枝法在氨基化石墨烯表面接上磁性納米粒子得到磁功能化石墨烯;以上兩種功能化石墨烯都可在有機(jī)溶劑中重新分散。(2)通過機(jī)械共混的方法制備氨基功能化石墨烯硅橡膠復(fù)合材料。利用氨基化石墨烯可重新分散在有機(jī)溶劑中的特點(diǎn),將其與室溫硫化硅橡膠(RTV-Silicone Rubber)在四氫呋喃(THF)中混合制備復(fù)合材料。石墨烯的加入大大提升了硅橡膠力學(xué)強(qiáng)度、熱穩(wěn)定性能、電性能和氣體阻隔性能,由于氨基的引入,使石墨烯與硅橡膠之間有了很好的結(jié)合作用,當(dāng)填料含量為0.5%時(shí),拉伸強(qiáng)度和斷裂伸長率分別提升164.7%、122.6%;當(dāng)填料含量為1.5%時(shí),熱穩(wěn)定性大幅度提升,熱分解起始溫度較硅橡膠提升10~16℃,到600℃時(shí)失重率只降低了14%;當(dāng)填料含量為1%時(shí)使硅橡膠體積電阻從1016?降低到107?,降低9個(gè)數(shù)量級。功能化石墨烯的加入也使體系的氣體阻隔性能提升,填料含量為0.7%時(shí),透氣系數(shù)減小為RTV硅橡膠的2/3,即阻隔性能在硅橡膠的基礎(chǔ)上提升了33.3%。(3)通過溶液共混法制備氨基功能化石墨烯聚乳酸復(fù)合材料和磁性石墨烯聚乳酸復(fù)合材料。用XRD、SEM、DSC表征了復(fù)合材料的結(jié)構(gòu)形貌和分散情況,也研究了復(fù)合材料的熱穩(wěn)定性能、電性能和氣體阻隔性能。XRD和SEM分析表明,功能化石墨烯在聚乳酸體系中分散性較好,沒有出現(xiàn)團(tuán)聚現(xiàn)象,功能化石墨烯片被聚乳酸分子鏈包覆,相界面模糊;復(fù)合材料形貌粗糙,純聚乳酸形貌光滑平整;DSC分析表明,聚乳酸復(fù)合材料的玻璃化轉(zhuǎn)變溫度隨著功能化石墨烯的加入量增多依次升高,純聚乳酸的Tg為56.2℃,當(dāng)功能化石墨烯含量為0.5%時(shí),Tg達(dá)到62.4℃;電性能和透氣性能分析表明,純聚乳酸的電導(dǎo)率在10~(-17)S·m~(-1)附近,隨著功能化石墨烯的加入,電導(dǎo)率開始逐漸上升。當(dāng)填料含量為0.1%時(shí),電導(dǎo)率達(dá)到了10~(-13)S·m~(-1),含量為2%時(shí),電導(dǎo)率為10~(-8)S·m~(-1),較聚乳酸提升了9個(gè)數(shù)量級。當(dāng)填料含量為0.03%時(shí),透氣系數(shù)減小到2.42×10~(-12) cm~(3)·cm/cm~(2)·s·Pa。(4)為深入研究填料在基體體系中的分散情況,初步建立了聚合物大分子鏈群帶取向模型和二維石墨烯在聚合物中取向角測定模型。
[Abstract]:Graphene is a cellular single-layer two-dimensional sheet material consisting of carbon atoms in a regular hexagon, and has excellent electrical properties, optical properties, thermal conductivity properties, barrier properties, quantum Hall effect, room temperature iron magnetic effect, and the like, and has become the hot spot of the current research. At present, the method for preparing the graphene has many advantages, most of which are difficult to realize, and the preparation of the graphene by the oxidation reduction method has the advantages of simple operation, low cost, high yield and large-scale production and the like. Both the graphene oxide and the graphene have excellent comprehensive performance and super-high specific surface area, so that the graphene oxide and the graphene are the ideal filler for preparing the high-performance composite material. However, that dispersion and agglomeration of the graphene in the matrix system is a key problem to limit the wide application of the graphene. In order to solve these problems, the active functional group is introduced into the surface of the graphene from the interaction of the interface between the filler and the matrix, and the functionalized graphene is used as a filler to prepare the polymer composite material. The main contents of the study are as follows: (1) The graphene oxide and the graphene are prepared by the oxidation reduction method, and the oxygen-containing group (hydroxyl group, the base group, the phenyl group and the epoxy group) on the surface of the graphene are used for covalent bonding modification. firstly, amination modification is carried out, the p-phenylenediamine solution and the graphene oxide solution are mixed according to a ratio of 10:1 (solid content ratio), the reaction is carried out at 90 DEG C for 24 hours, and then the centrifugal separation is carried out to obtain the amino-functionalized graphene; Secondly, the magnetic nano particles are connected with the surface of the aminated graphene by a grafting method to obtain the magnetic functionalized graphene; and the two functional graphene can be re-dispersed in the organic solvent. And (2) preparing the amino-functional graphene silicon rubber composite material by a mechanical blending method. The characteristics of the re-dispersion of the aminated graphene in the organic solvent were redispersed, and the composite was prepared by mixing it with room temperature vulcanized silicone rubber (RTV-Silicone Rubber) in tetrahydrogen peroxide (THF). the addition of the graphene greatly improves the mechanical strength, the thermal stability, the electrical property and the gas barrier performance of the silicon rubber, The tensile strength and the elongation at break are respectively increased by 164.7% and 122.6%, when the content of the filler is 1.5%, the thermal stability is greatly improved, the initial temperature of the thermal decomposition is increased by 10-16 DEG C from the silicone rubber, and the weight loss rate is only reduced by 14% when the content of the filler is 1%; and when the content of the filler is 1%, the volume resistance of the silicon rubber is increased from 1016? Down to 107? And is reduced by 9 orders of magnitude. The addition of the functionalized graphene also improves the gas barrier performance of the system, and when the content of the filler is 0.7%, the air permeability coefficient is reduced to 2/3 of the RTV silicone rubber, that is, the barrier property is improved by 33.3% on the basis of the silicon rubber. And (3) preparing the amino-functional graphene polylactic acid composite material and the magnetic graphene polylactic acid composite material by a solution blending method. The structure and dispersion of the composites were characterized by XRD, SEM and DSC. The thermal stability, electrical property and gas barrier properties of the composites were also studied. The results of XRD and SEM show that the dispersion of the functionalized graphene in the polylactic acid system is good, no agglomeration phenomenon occurs, the functionalized graphene sheet is coated by the polylactic acid molecule chain, the phase interface is fuzzy, the morphology of the composite material is rough, the appearance of the pure polylactic acid is smooth and flat, and the DSC analysis shows that, the glass transition temperature of the polylactic acid composite material is increased in sequence with the addition of the functionalized graphene, the Tg of the pure polylactic acid is 56.2 DEG C, when the content of the functionalized graphene is 0.5 percent, the Tg is up to 62.4 DEG C, and the electrical property and the air permeability can be analyzed, The conductivity of the pure polylactic acid is about 10 ~ (-17) S 路 m ~ (-1), and with the addition of the functionalized graphene, the conductivity starts to increase gradually. When the content of the filler is 0.1%, the conductivity is 10 ~ (-13) S 路 m ~ (-1), the content is 2%, the conductivity is 10 ~ (-8) S 路 m ~ (-1), and the polylactic acid is increased by 9 orders of magnitude. When the content of the filler is 0.03%, the air permeability coefficient is reduced to 2.42-10-(-12) cm-(3) 路 cm/ cm-(2) 路 s 路 Pa. (4) In order to study the dispersion of the filler in the matrix system, the orientation model and the orientation angle measurement model of the two-dimensional graphene in the polymer are preliminarily established.
【學(xué)位授予單位】：上海工程技術(shù)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：O613.71;TB33
本文編號：2494048
[Abstract]:Graphene is a cellular single-layer two-dimensional sheet material consisting of carbon atoms in a regular hexagon, and has excellent electrical properties, optical properties, thermal conductivity properties, barrier properties, quantum Hall effect, room temperature iron magnetic effect, and the like, and has become the hot spot of the current research. At present, the method for preparing the graphene has many advantages, most of which are difficult to realize, and the preparation of the graphene by the oxidation reduction method has the advantages of simple operation, low cost, high yield and large-scale production and the like. Both the graphene oxide and the graphene have excellent comprehensive performance and super-high specific surface area, so that the graphene oxide and the graphene are the ideal filler for preparing the high-performance composite material. However, that dispersion and agglomeration of the graphene in the matrix system is a key problem to limit the wide application of the graphene. In order to solve these problems, the active functional group is introduced into the surface of the graphene from the interaction of the interface between the filler and the matrix, and the functionalized graphene is used as a filler to prepare the polymer composite material. The main contents of the study are as follows: (1) The graphene oxide and the graphene are prepared by the oxidation reduction method, and the oxygen-containing group (hydroxyl group, the base group, the phenyl group and the epoxy group) on the surface of the graphene are used for covalent bonding modification. firstly, amination modification is carried out, the p-phenylenediamine solution and the graphene oxide solution are mixed according to a ratio of 10:1 (solid content ratio), the reaction is carried out at 90 DEG C for 24 hours, and then the centrifugal separation is carried out to obtain the amino-functionalized graphene; Secondly, the magnetic nano particles are connected with the surface of the aminated graphene by a grafting method to obtain the magnetic functionalized graphene; and the two functional graphene can be re-dispersed in the organic solvent. And (2) preparing the amino-functional graphene silicon rubber composite material by a mechanical blending method. The characteristics of the re-dispersion of the aminated graphene in the organic solvent were redispersed, and the composite was prepared by mixing it with room temperature vulcanized silicone rubber (RTV-Silicone Rubber) in tetrahydrogen peroxide (THF). the addition of the graphene greatly improves the mechanical strength, the thermal stability, the electrical property and the gas barrier performance of the silicon rubber, The tensile strength and the elongation at break are respectively increased by 164.7% and 122.6%, when the content of the filler is 1.5%, the thermal stability is greatly improved, the initial temperature of the thermal decomposition is increased by 10-16 DEG C from the silicone rubber, and the weight loss rate is only reduced by 14% when the content of the filler is 1%; and when the content of the filler is 1%, the volume resistance of the silicon rubber is increased from 1016? Down to 107? And is reduced by 9 orders of magnitude. The addition of the functionalized graphene also improves the gas barrier performance of the system, and when the content of the filler is 0.7%, the air permeability coefficient is reduced to 2/3 of the RTV silicone rubber, that is, the barrier property is improved by 33.3% on the basis of the silicon rubber. And (3) preparing the amino-functional graphene polylactic acid composite material and the magnetic graphene polylactic acid composite material by a solution blending method. The structure and dispersion of the composites were characterized by XRD, SEM and DSC. The thermal stability, electrical property and gas barrier properties of the composites were also studied. The results of XRD and SEM show that the dispersion of the functionalized graphene in the polylactic acid system is good, no agglomeration phenomenon occurs, the functionalized graphene sheet is coated by the polylactic acid molecule chain, the phase interface is fuzzy, the morphology of the composite material is rough, the appearance of the pure polylactic acid is smooth and flat, and the DSC analysis shows that, the glass transition temperature of the polylactic acid composite material is increased in sequence with the addition of the functionalized graphene, the Tg of the pure polylactic acid is 56.2 DEG C, when the content of the functionalized graphene is 0.5 percent, the Tg is up to 62.4 DEG C, and the electrical property and the air permeability can be analyzed, The conductivity of the pure polylactic acid is about 10 ~ (-17) S 路 m ~ (-1), and with the addition of the functionalized graphene, the conductivity starts to increase gradually. When the content of the filler is 0.1%, the conductivity is 10 ~ (-13) S 路 m ~ (-1), the content is 2%, the conductivity is 10 ~ (-8) S 路 m ~ (-1), and the polylactic acid is increased by 9 orders of magnitude. When the content of the filler is 0.03%, the air permeability coefficient is reduced to 2.42-10-(-12) cm-(3) 路 cm/ cm-(2) 路 s 路 Pa. (4) In order to study the dispersion of the filler in the matrix system, the orientation model and the orientation angle measurement model of the two-dimensional graphene in the polymer are preliminarily established.
【學(xué)位授予單位】：上海工程技術(shù)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：O613.71;TB33
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