Preparation and characterization of polyaniline/exfoliated graphite composite via a combination method of in situ polymerization and thermal expansion

Polyaniline/exfoliated graphite (PANI/EG) composite was prepared via a combination method of in situ polymerization and thermal expansion and characterized, using scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). In the in situ polymerization, PANI/graphite intercalation compounds (GIC) composite was synthesized by GIC and aniline. In the thermal expansion, PANI/EG composite was prepared by PANI/GIC composite. The characterization showed that the morphology of PANI/EG composite was analogous to foam and the surface of PANI/EG composite had many micro-apertures. When PANI/GIC composite was synthesized by 0.80 g of GIC and 2.00 g of aniline, PANI/GIC composite would be exfoliated to PANI/EG composite at 200 °C, which had 75.00 mL·g⁻¹ of the expansion volume and 0.01Ω⁻¹ cm⁻¹of the conductivity.     

Preparation of Nylon-6/flake graphite derivatives composites with antistatic property and thermal stability

Nylon-6/flake graphite (FG) composite, Nylon-6/graphene intercalation compounds (GIC) composite and Nylon-6/exfoliated graphite (EG) composite were prepared by FG, GIC, EG and caprolactam via in situ polymerization, and the volume resistivities of Nylon-6/flake graphite derivatives composites were also investigated. Meanwhile, the structure of Nylon-6/EG composite was characterized and the thermal stability of Nylon-6/EG composite was investigated as well. When the mass percents of FG, GIC and EG were 1%, 2–4% and 1%, the volume resistivities of flake graphite derivatives composites would reach 7.5 × 10⁶ Ω cm, 3.6 × 10⁸–1.4 × 10⁶ Ω cm and 2.3 × 10⁶ Ω cm. When the mass percent of EG increases from 0% to 9%, the thermal stability temperature of Nylon-6/EG composite would enhance from 70 to 196 °C. This shows that Nylon-6/flake graphite derivatives composites can have the antistatic property and thermal stability synchronously.     

剥离型纳米蒙脱土/聚酰亚胺复合材料的制备与表征

利用二苯基甲烷-4,4’-二异氰酸酯（MDI）与酸化的蒙脱土（MMT）表面的羟基进行反应制得了MMT-MDI;进一步利用己内酰胺（CPL）对MMT-MDI进行插层并对多余的异氰酸酯端基进行封端,制得了MMT-MDI-CPL。采用预聚体溶液插层法,利用聚酰胺酸（PAA）在二甲基乙酰胺（DMAC）溶剂中分别对MMT-MDI和MMT-MDI-CPL进行预聚体插层,制得了剥离型纳米MMT/聚酰亚胺（PI）复合材料。通过电感耦合等离子体发射光谱（ICP-OES）、FTIR、TG、XRD和SEM对改性MMT和纳米MMT/PI复合材料进行了表征。结果表明：MDI与MMT表面羟基反应而被成功接枝于MMT上;MDI对MMT的改性、CPL对MMT-MDI的插层和封端使MMT层间距得到逐步扩大;MMT/PI复合材料的XRD和断面SEM表明,MMT在PI基体中得到了充分剥离。     

Modeling,processing, and characterization of exfoliated graphite nanoplatelet-nylon 6 composite fibers

We present theoretical and experimental studies on the effects of platelet-like filler orientation on the mechanical properties of melt-spun exfoliated graphite nanoplatelet(xGnP)-nylon 6(PA6) composite fibers. In numerical studies, the Mori–Tanaka micromechanics model was employed to formulate analytical models to predict the mechanical properties of xGnP-PA6 composite fibers with varying xGnP orientations in a three-dimensional spatial domain. Simulation results showed that the predicted properties of xGnP-PA6 composite fibers were highly affected by xGnP orientation and were correlated with the measured properties of composite fibers treated with varying draw ratios. The tensile moduli of composite fibers at varying xGnP contents showed significant improvements, which is attributed to the drawing-induced alignment of PA6 molecular chains as well as the alignment of xGnPs. Both as-received and acid-treated xGnPs were incorporated in PA6, and mechanical test results suggested that acid-treated xGnPs provide stronger interfacial bonding with PA6.     

超声无皂乳液原位合成Pd-P(MMA-AMPS)复合微球及其表征

将超声波作用于含有2-丙烯酰氨基-2-甲基丙磺酸(AMPS)和甲基丙烯酸甲酯(MMA)的氯化钯水溶液中,在不加任何引发剂、乳化剂和还原剂的条件下,合成带有酰胺基、磺酸基等官能基团的Pd-P(MMA -AMPS)复合微球。考察了单体质量配比对复合微球形貌的影响,用XRD、TGA、FTIR、TEM和粒度分析仪等技术对样品进行表征,并探讨了合成反应机制。结果表明,超声辐射可实现Pd2+的还原与单体聚合的同步进行,并且金属钯与基体P(MMA - AMPS)共聚物之间存在一定的相互作用。优化条件下制得的复合微球,钯质量分数为20%左右,粒径约0.76μm,还原得到的钯粒子均匀分散于聚合物微球内。     

An exfoliated polyamide-6/layered double hydroxide nanocomposite via in situ intercalative polymerization between positively charged inorganic platelets

An exfoliated polyamide 6 (PA6)/layered double hydroxide (LDH) nanocomposite has been successfully prepared via an in situ intercalative polymerization procedure. The original LDH surface is hydrophilic. After an ion exchange reaction of LDH with sodium stearate (SS), the organic anions intercalated into the interlayer space of LDH, adopting a double-layer inclined structure, and the surface of the organic-modified LDH became hydrophobic. An exfoliated PA6/LDH nanocomposite has been obtained via in situ intercalative polymerization. Its microstructure was characterized by a combination of wide-angle X-ray diffraction (WAXD) and transmission electron microscopic (TEM) techniques. The positively charged inorganic platelets of LDH were dramatically exfoliated and homogeneously dispersed in the PA6 matrix.     

Preparation and electrical characterization of polyamide-6/chitosan composite nanofibers via electrospinning

We report on the preparation and electrical characterization of polyamide-6/chitosan composite nanofibers. These composite nanofibers were prepared using a single solvent system via electrospinning process. The resultant nanofibers were well-oriented and had good incorporation of chitosan. Current-voltage (I-V) measurements revealed interesting linear curve, including enhanced conductivities with respect to chitosan content. The electrical conductivity of the polyamide-6/chitosan composite nanofibers increased with increasing content of chitosan which was attributed to the formation of ultrafine nanofibers. In addition, the sheet resistance of composite nanofibers was decreased with increasing chitosan concentration.     

Preparation of silica/polyacrylamide/polyethylene nanocomposite via in situ polymerization

SiO₂/polyacrylamide (PAM) composite was prepared via the polymerization of acrylamide in the presence of silica sol in water/hexane emulsion, and pure SiO₂ was also prepared without the use of acrylamide in the same way. Field emission scanning electron micrographs (FESEM) showed that PAM covered the silica nanoparticles to form SiO₂/PAM nanospheres, which loosely agglomerated to form SiO₂/PAM secondary particles, while SiO₂ secondary particles were made up of tightly agglomerated silica nanoparticles. Metallocene catalyst was then immobilized over SiO₂ and SiO₂/PAM respectively to prepare supported metallocene catalyst for ethylene polymerization. Transmission electron micrographs (TEM) showed that support particles broke up to smaller particles and even nanoparticles in polyethylene (PE) matrix when the support particles were the fragile SiO₂/PAM secondary particles, which shows a novel way to prepare silica/polyacrylamide/polyethylene nanocomposite.     

Preparation and characterization of polyaniline/cerium dioxide (CeO2) nanocomposite via in situ polymerization

Crystalline ceria (CeO₂) nanoparticles have been successfully synthesized by a microwave-assisted solution method. Polyaniline (PANI)/cerium dioxide (CeO₂) nanocomposite was synthesized by in situ polymerization of aniline in the presence of CeO₂ nanoparticles. Characterization of CeO₂ and PANI/CeO₂ nanomaterials are carried out using various studies such as powder X-ray diffraction, infrared spectral and UV–Vis absorption spectral analyses, scanning electron microscopic and high-resolution transmission electron microscopic (HRTEM) studies and thermal analysis. The HRTEM of the images indicate that the CeO₂ nanoparticles were embedded in the PANI matrix forming the core–shell structure.     

原位合成羟基磷灰石/明胶复合材料及表征

以Ca(NO3)2、(NH4)2HPO4和明胶为起始原料,采用原位合成的方法,制备与自然骨成分和结构相似的羟基磷灰石/明胶复合材料(HA/Gel).采用各种分析手段对样品进行表征.红外结果表明HA/Gel中波数为1339cm-1的酰胺基团向低波数发生了红移;X射线衍射证明HA/Gel复合材料中的元机相主要为低结晶度、晶粒尺寸细小的羟基磷灰石;热重结果证明本试验制备的HA/Gel中Gel的含量达到15%左右;采用扫描电镜观察HA/Gel复合材料的微观形貌.扫描电镜观察发现HA颗粒定向分布在Gel连续相基体上,本试验结果证明HA与Gel形成键性结合,是一种颇有前途的骨组织替换材料.     

Preparation of low-density polyethylene/low-temperature expandable graphite composites with high thermal conductivity by an in situ expansion melt blending process

A facile strategy with the advantages of low cost and ease of mass production was presented to prepare low-density polyethylene (LDPE)/low-temperature expandable graphite (LTEG) composites with relatively high thermal conductivity by an in situ expansion melt blending process. LTEGs were expanded and delaminated into graphite multi-layers and graphite nanoplatelets during processing which synergistically created more thermo-conducting paths in the composites and hence led to great improvements in thermal conductivity. Thermal conductivity of the composite with 60 wt% of LTEG loading was increased by 23 times as compared to the pure LDPE, increasing from 0.47 to 11.28 W/mK. The incorporation of LTEG decreased the melting temperature and the degree of crystallinity of LDPE. Percolation threshold of both the electrical conductivity and rheological measurements was observed at about 8 vol% of LTEG loading. Moreover, the LDPE/LTEG composites showed better thermal stability compared to the pure LDPE.     

Preparation and mechanical properties of exfoliated CoAl layered double hydroxide (LDH)/polyamide 6 nanocomposites by in situ polymerization

Novel exfoliated nanocomposites based on polyamide 6 (PA6)/CoAl layered double hydroxide (CoAl-LDH) have been successfully prepared via in situ polymerization. X-ray diffraction (XRD) and transmission electron microscopy (TEM) results indicated that the inorganic nanoplatelets of CoAl-LDH were homogeneously dispersed in the PA6 matrix. Mechanical testing (by tensile tests and nanoindentation measurements) shows that, compared with neat PA6, the tensile modulus, the yield strength, and the hardness of the nanocomposites are substantially improved by about 100%, 75%, and 25%, respectively, with incorporating only 1 wt% CoAl-LDH. In addition, tensile fracture morphologies of neat PA6 and its nanocomposites are also compared and discussed.     

Structural characterization, thermal and mechanical properties of polyurethane/CoAl layered double hydroxide nanocomposites prepared via in situ polymerization

Dodecyl sulfate (DS), one kind of sulfate anion, was intercalated in the interlayer space between CoAl layered double hydroxide (CoAl-LDH) layers, and then polyurethane (PU) based nanocomposites were prepared by in situ intercalation polymerization with different amounts of the organo-modified CoAl-LDH. An exfoliated dispersion of CoAl-LDH layers in PU matrix was verified by the disappearance of the (0 0 3) reflection of the XRD results when the LDH loading was less than 2.0 wt%. Tensile testing indicated that excellent mechanical properties of PU/LDH nanocomposites were achieved. The weak alkaline catalysis of DS to polyurethane chains, combined with the dehydration and structural degradation of the LDH below 300 °C, accounted for the process of proceeded degradation as shown in TGA results. The real-time FTIR revealed that the as-prepared nanocomposites had a slower thermo-oxidative rate than neat PU from 160 °C to 340 °C, probably due to the barrier effect of LDH layers. These results suggested potential applications of CoAl-LDH as a promising flame retardant in PUs.     

Preparation and characterization of a nano apatite/polyamide6 bioactive composite

A novel biocomposite of nano-apatite (NA)/polyamide₆ (PA₆) was prepared with a co-solution method. The NA with the size of 10–30 nm in diameter and 70–90 nm in length was uniformly distributed into PA₆ matrix to form the composite. Molecular interaction and chemical bonding existed between NA and PA₆, which greatly improved the mechanical properties and integrity of the composite. It was found that the composite with a high NA content (around 65%) has good homogeneity and mechanical strength, which are close to the natural bone. An interconnected porous material with porosity of 80% and mean pore size of approximately 300 μm was prepared by an injecting foam method. When implanted into cortical bone, the composite combined directly with the natural bone without fibrous capsule tissue between implant and host bone. The results indicated that the NA/PA₆ composite has an excellent bioactivity.     

Preparation and characterization of novel polypyrrole-nanotube/polyaniline free-standing composite films via facile solvent-evaporation method

Polyaniline (PANI) is an important conducting polymer and has drawn much attention for its inexpensiveness and chemical stability in the conducting state but its conductivity is rather low. Another well-known conducting polymer is polypyrrole (PPy) with a much higher electrical conductivity but it is hard to prepare films using PPy alone due to its poor film-forming ability. In this work, novel polypyrrole-nanotube (PPy-NT)/polyaniline (PANI) composite films are prepared via a facile solvent-evaporation method. The influence of the PPy-NT content is examined on the film structure, morphology, electrical and mechanical properties. It is shown that PPy nanotubes (PPy-NTs) are uniformly distributed in the PANI matrix. The electrical conductivity is greatly enhanced by 10.2 times by the addition of 10 wt.% PPy nanotubes. Moreover, the mechanical ductility is significantly increased by the addition of PPy nanotubes.     

Study on the interface of phenolic resin/expanded graphite composites prepared via in situ polymerization

Phenolic resin/expanded graphite (EG) composites were synthesized via in situ condensation polymerization of the monomers in the presence of foliated graphite. SEM observation showed that the graphite flakes were well dispersed in the phenolic resin matrix. The electrical conductivity of the composites was investigated as a function of the foliated graphite fraction. The composites containing graphite sheets exhibited an electrical conductivity percolation threshold with 3.2 wt% graphite content in polymer matrix. Inverse gas chromatography (IGC) measurements were carried out to characterize the surface of the foliated graphite before and after condensation polymerization of phenolic resin using a series of both non-polar and polar acid–base probe gases. The data obtained indicated that the character of graphite surface changed after the polymerization of phenolic resin. The dispersive component of surface free energy decreased greatly. Before polymerization the graphite surface is predominantly acidic while the surface turns to basic after polymerization. The increased polarity of surface contributed to the stronger interactions between graphite and phenolic resin and the fine dispersion of expanded graphite in the matrix, and resulted in the low conductivity percolation threshold.     

膨胀石墨/纳米氧化锌/锌复合电极材料的超级电容器性能

以膨胀石墨为原料,与滚压振动磨预处理得到的纳米锌粉混合,超声分散24h制备膨胀石墨-纳米氧化锌及锌的复合电极材料(EG/ZnO/Zn)。采用X射线衍射仪(XRD)、场发射扫描电子显微(SEM)、场发射透射电子显微镜(TEM)、拉曼光谱分析仪(Raman),对材料的微观结构及成分表征。结果表明,复合材料中含锌和氧化锌,纳米锌粉颗粒和氧化锌纳米棒在膨胀石墨表面和层间分散良好,其中氧化锌纳米棒呈现出六方晶系纤锌矿结构,其直径大约为20nm。利用电化学循环伏安和恒电流充放电对材料进行电化学电容性能测试,表明经处理的复合电极材料在0.1A/g的电流密度下有明显的赝电容特性,比电容达147F/g,其赝电容来源不只是欠电位沉积的化学吸附,还有氧化还原反应。     

Preparation of sulfur-free exfoliated graphite at a low exfoliation temperature

Sulfur-free exfoliated graphite at a low exfoliation temperature was prepared from graphite intercalation compounds (GICs) synthesized chemically with different consumption of insertion reagents and oxidants. The effects of their consumption on the synthesis of GICs and of exfoliation temperature on exfoliation volume were studied. The exfoliation volume was 350 ml/g at exfoliation temperature of 200 °C in the best process condition. These results revealed a marked development of the pores in Exfoliated graphite.     

高导热石墨膜的制备及表征

将不同厚度杜邦聚酰亚胺(PI)薄膜进行压制炭化、石墨化处理得到PI石墨膜。采用扫描电镜、X射线衍射、、拉曼光谱等测试手段分析了PI薄在高温热处理过程中的结构演变。研究结果表明,50μm厚PI膜经3 000℃高温石墨化后能形成三维有序堆积的石墨层状结构和较为完整的石墨晶体,其石墨片层间距为0.336nm,层片堆积高度达到65.94nm,石墨化度高达93%,室温面向电阻率为0.48μ!·m,实测面向热导率达到了994 W/(m·K)。随着热处理温度的提高,PI膜微晶由无定型向有序类石墨结构转变,其结晶度和层片取向程度提高,石墨晶体逐渐完善。PI膜厚度越大,其类石墨晶体生长发育越困难,层片择优取向程度越低。