Preparation and characterization of multi‐walled carbon nanotubes/polymer gradient composite films

BACKGROUND: Recently, much work has focused on the efficient dispersion of carbon nanotubes (CNTs) throughout a polymer matrix for mechanical and/or electrical enhancement. However, there are still only few reports about gradient distribution of CNTs in polymer matrices. In the work reported here, CNTs embedded in a polymer film with a gradient distribution were successfully obtained and studied. RESULTS: For composite films with gradient distributions of CNTs, the upper surface behaves as an intrinsic insulator, while the lower one behaves as a semiconductor, or even as a conductor. It is also found that with an increase of 1 wt% CNTs, the resistance of the bottom surface decreases by 2–3 orders of magnitude, as compared with pure polyarylene ether nitrile; furthermore, when the proportion of CNTs increases up to 5 wt%, the resistance of the bottom surface shows only very little change. As a result, sufficient matrix conductivity of the bottom surface could be achieved at a lower filler concentration with CNTs in a gradient distribution. Meanwhile, the thermal stability, glass transition temperature and tensile properties of the matrix are maintained. CONCLUSION: There is considerable interest in such gradient composite films, which could be applied in the electrical engineering, electronics and aerospace fields, for their excellent mechanical properties, thermal stability and novel electrical properties. Copyright © 2008 Society of Chemical Industry     

Poly[ethylene‐co‐(acrylic acid)]‐based nanocomposites: Thermal and mechanical properties and their structural characteristics studied by Raman spectroscopy

Nanocomposites containing carbon nanotubes (CNTs) as nanofillers and poly[ethylene‐co‐(acrylic acid)] (PEAA) or a polymer miscible mixture of PEAA and poly(2‐ethyl‐2‐oxazoline) (PEOx) as a matrix were prepared by the solution‐evaporation method with minimal damage to nanotubes. CNTs were prepared by chemical vapor deposition (CVD) with ethanol as the source of carbon. Raman spectroscopy confirmed the presence of single walled carbon nanotubes (SWNTs). High resolution transmission electron microscopy (HRTEM) showed the formation of multi walled carbon nanotubes (MWNTs). Thermal and mechanical properties of the nanocomposites were studied by analyzing samples containing different amounts of CNTs. The degree of crystallinity (X_c) of the PEAA‐based nanocomposite containing a smaller amount of CNTs was larger (X_c = 17.0%) than both the one of pure PEAA (X_c = 14.6 %) and PEAA‐based nanocomposite containing higher amounts of CNTs (X_c = 15.0%). The Young's modulus, ultimate stress, deformation at break, and toughness obtained from unidirectional tensile tests of the CNTs (1 wt%)‐PEAA nanocomposite were higher than both the one of pure PEAA and CNTs (5 wt%)‐PEAA nanocomposite. When a polymer mixture of PEAA/PEOx (containing 80 wt% of PEAA) was used as a matrix, a better mechanical response was also detected for nanocomposite containing 1 wt% CNTs. The nanocomposites containing small amounts of CNTs prepared here have potential to be used as coatings of metal or glass surfaces expecting a better mechanical performance than the one of pure matrix. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Preparation and mechanical properties of waterborne polyurethane/carbon nanotube composites

Waterborne polyurethane (WBPU) and multiwalled carbon nanotubes (CNTs) composite films with 0–4.0 wt% CNTs were prepared by ultrasonic dispersion of carboxylic acid‐functionalized CNTs in WBPU followed by emulsion casting process. The elongations at break of the WBPU/CNTs composites increase with the incorporation of CNTs. The tensile strength and crystallinity of the nanocomposite films with lower CNTs contents (<2 wt%) increase obviously; while the tensile strengths of the composites with more CNTs (≥2 wt%) decrease, in contrast to the pure PU film. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations indicated that the CNTs are uniformly dispersed in the composites incorporated with lower CNTs contents (≤1.5 wt%). However, aggregation of CNTs increased with increasing CNTs content in the WBPU/CNTs composites, causing the macrophase separation. The dispersion state of the CNTs affects the crystallinity of the PU matrix and the phase separation of the composites, which are two key factors to influence the mechanical properties of the WBPU/CNTs composites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

微纳层叠共挤PP/PA6/CNTs原位微纤复合膜的制备及性能研究

采用双转子连续混炼挤出机与微纳层叠共挤出成型设备制备了聚丙烯/聚酰胺6/碳纳米管（PP/PA6/CNTs）复合材料和原位微纤复合膜,通过扫描电子显微镜（SEM）、流变仪、差示扫描量热仪（DSC）、万能拉伸试验机及电阻测试仪对其微观结构、流变性能、结晶性能、力学性能和导电性能进行了表征。结果表明,与共混相比,微纳层叠共挤出法使得分散相PA6/CNTs形成了微纤,微纤的形成不仅提升了复合膜的动态流变性能,并且增加了基体PP相的结晶度,提高了PA6相的结晶温度,提升了复合膜的结晶性能;当CNTs含量为0.5 %（质量分数,下同）时,复合膜的拉伸强度和断裂伸长率均达到最大值,分别为42.17 MPa和857.82 %,体积电阻率（R）下降到10⁴ Ω·cm,综合力学性能和导电性能达到最佳。     

Mechanical reinforcement of electrospun water‐soluble polymer nanofibers using nanodiamonds

Optimization of the mechanical properties is necessary in the applications of electrospun nanofibrous matrices. In this work, mechanical reinforcement of electrospun nanofiber membranes of water‐soluble polymer by the incorporation of commercial nanodiamonds (NDs) was studied. Through an ND/poly(vinyl alcohol) (ND/PVA) model system, it is demonstrated that 155% improvement of Young's modulus, 89% increase in tensile strength, and 336% elevation in energy to break are achieved by the addition of only 2 wt% ND. Fourier transform infrared spectroscopy results suggest the existence of molecular interactions between NDs and PVA matrix, which contributes to the effective load transfer from the polymer matrix to the fillers. However, higher level of ND addition (>2 wt%) aggravates the agglomeration of nanofillers in PVA matrix and offsets the reinforcing effect, as ND agglomerates may act as flaws in composite nanofibers. Furthermore, NDs have optimizing effect on the morphology of ND/PVA nanofibers through increasing the conductivity of the electrospinning solution. Therefore, ND nanofillers possess the potential to improve the mechanical performance of water‐soluble polymer‐based nanofiber membranes. POLYM. COMPOS., 34:1735–1744, 2013. © 2013 Society of Plastics Engineers     

Effect of nanofillers on the properties of flexible protective polymer coatings

Nanofillers with different size, shape, chemical structure, aspect ratio, and purity, including pristine montmorillonite (MMT‐Na) and hydrotalcite (HT) lamellar clays, and nonpurified single‐walled carbon nanotubes (SWNT) and fullerenes (FUL) were dispersed in a waterborne flexible acrylic coating. SEM and WAXD analysis of drawn‐down composite films containing 5 and 10 wt% fillers confirmed the random orientation of the MMT‐Na and HT platelets having intercalated or partially exfoliated structures. SEM analysis of composites containing SWNTs revealed the presence of clusters rather than single fibers and irregularly shaped carbonaceous impurities. Low aspect ratio, but well‐dispersed particles were observed in the FUL composites. Only the SWNT filler improved the thermal stability of the unfilled polymer; the presence of SWNT and MMT‐Na had a negligible effect on the glass transition temperature (T_g) of the coating. The presence of all nanofillers increased the tensile secant modulus of the polymer and decreased somewhat tensile strength and elongation at break to different degrees depending on type of filler and concentration. Some nanofillers significantly reduced the water vapor transmission rate of the unfilled matrix. Experimental data are discussed in terms of parameters known to affect mechanical and barrier properties including volume fraction, orientation, aspect ratio, dispersion, interfacial adhesion, and filler hydrophilicity. The results of this work indicate that it is possible to improve certain properties of acrylic protective coatings through the addition of low cost, unmodified nanoclays or by using nonpurified carbon allotropes, without a significant compromise of the strength and ductility of the polymeric matrix. POLYM COMPOS., 27:368–380, 2006. © 2006 Society of Plastics Engineers     

Thermal and ablative properties of binary carbon nanotube and nanodiamond reinforced carbon fibre epoxy matrix composites

The thermal and ablative properties of carbon nanotube (CNT) and nanodiamond (ND) reinforced carbon fibre epoxy matrix composites were investigated by simulating shear forces and high temperatures using oxyacetylene torch apparatus. Three types of composite specimens—(i) carbon fibre epoxy matrix composite (CF/Epoxy), (ii) carbon fibre epoxy matrix composite containing 0.1 wt-% CNTs and 0.1 wt-% NDs, and (iii) carbon fibre epoxy matrix composite containing 0.2 wt-% CNTs and 0.2 wt-% NDs—were explored. The ablative response of composites was studied through pre- and post-burnt SEM analysis and further related with thermogravimetric analysis, weight loss profile and thermal conductivity measurements. The novel nanofiller composites showed marked improvement in their thermal and ablative properties. A 22% and 30% increase in thermal conductivity was observed for composites containing 0.1 wt-% CNTs/0.1 wt-% NDs and 0.2 wt-% CNTs/0.2 wt-% NDs respectively. These nanofillers also improved the thermal stability of thermosetting epoxy matrix, and an increase of 13% and 20% was recorded in the erosion rate of composites containing 0.1 wt-% CNTs/0.1 wt-% NDs and 0.2 wt-% CNTs/0.2 wt-% NDs respectively. This improvement is due to the increased char yield produced by the increase in the loading of nanofillers, i.e. CNTs and NDs. Insulation index and insulation to density performance have also been improved due to increased thermal conductivity and char yield.     

Functional nano-fillers in waterborne polyurethane/acrylic composites and the thermal,mechanical, and dielectrical properties

Modification is mostly used to adjust and increase the performance of polymers by employing organic or inorganic fillers in composites. It is significant to investigate the functions of different fillers in polymer matrix. In this work, we prepared a series of composites by using polyurethane/acrylic dispersions as polymer matrix and nanofillers (cellulose nanocrystals, carbon nanotubes and aluminum oxide nanoparticles) as modifiers to study their micro-structure and applied performance. It is found that the different nanofillers can be dispersed in PUA homogenously, which are inclusive physically. Different nanofillers have a noticeable influence on the T_g for the acrylate copolymers and the T_g of the interphase between the acrylate and polyurethane. The CNTs significantly increases the elongation to 127.29%, and gives the highest dielectric response. We imply that the CNTs may be the most significant fillers to increase the mechanical and electrical properties.     

Using supercritical carbon dioxide in preparing carbon nanotube nanocomposite: Improved dispersion and mechanical properties

Improvements in carbon nanotube (CNT) dispersion and subsequent mechanical properties of CNT/poly(phenylsulfone) (PPSF) composites were obtained by applying the supercritical CO₂ (scCO₂)‐aided melt‐blending technique that has been used in our laboratory for nanoclay/polymer composite preparation. The preparation process relied on rapid expansion of the CNTs followed by melt blending using a single‐screw extruder. Scanning electronic microscopy results revealed that the CNTs exposed to scCO₂ at certain pressures, temperatures, exposure time, and depressurization rates have a more dispersed structure. Microscopy results showed improved CNT dispersion in the polymer matrix and more uniform networks formed with the use of scCO₂, which indicated that CO₂‐expanded CNTs are easier to disperse into the polymer matrix during the blending procedure. The CNT/PPSF composites prepared with scCO₂‐aided melt blending and conventional melt blending showed similar tensile strength and elongation at break. The Young's modulus of the composite prepared by means of conventional direct melt blending failed to increase beyond the addition of 1 wt% CNT, but the scCO₂‐aided melt‐blending method provided continuous improvements in Young's modulus up to the addition of 7 wt% CNT. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

High-performance epoxy nanocomposites via constructing rigid structured interphase with epoxy-rich graphene oxide

Epoxy resins, as the most important thermosetting matrix of carbon fiber reinforced polymer (CFRP) composites, are widely used in the structural field, but the highly intrinsic brittleness of epoxy resins greatly limits their application. Therefore, it is urgent to develop new method to prepare high-performance epoxy composites. In this research, GO riched with rigid short-chain structure epoxy group on its surface was synthesized by chemically grafting dopamine, hexachlorocyclotriphosphazene and glycidol successively. Then the modified nanofillers were incorporated into the epoxy matrix to prepare high-performance nanocomposites. The effect of epoxy-rich GO nanosheets as fillers on mechanical properties of aerospace grade epoxy was studied. The results revealed that the epoxy-rich GO could effectively optimize the performance of epoxy resins owing to forming the rigid structured interphase. The tensile strength and elongation at break of the nanocomposites were up to 113 MPa and 7.6% with 0.075 wt% additives, respectively, which greatly surpassed the value reported by the limited researches on strengthening epoxy with GO and its derivate nanofillers. Therefore, instructive idea and effective method were provided to obtain high-performance polymer nanocomposite matrix in this study.     

Mechanical reinforcement of chitosan using unzipped multiwalled carbon nanotube oxides

In this paper, unzipped multiwalled carbon nanotube oxides (UMCNOs), obtained by oxidation unzipping multiwalled carbon nanotubes (MWNTs) were used as novel nanofillers for mechanical reinforcement of chitosan (CS) matrix. The UMCNOs/CS nanocomposite films with different amounts of UMCNOs were fabricated by solution-casting the mixtures of UMCNOs and CS acetic acid aqueous dispersions. The structures and mechanical properties of the nanocomposite films were characterized by XRD, FT-IR, SEM, and tensile tests. The results demonstrated that UMCNOs could be homogeneously dispersed throughout the chitosan matrix. Compared to neat chitosan, the UMCNOs/CS nanocomposite films showed ～105.9% increase in tensile strength from 69.3 to 142.7 MPa, and ～165.3% increase in Young’s modulus from 2.6 to 6.9 Gpa with the incorporation of only 0.2 wt% of UMCNOs into the chitosan matrix.     

Study of nanoreinforced shape memory polymers processed by casting and extrusion

Multi‐walled carbon nanotubes (CNTs) and cellulose nanofibers (CNFs) reinforced shape memory polyurethane (PU) composite fibers and films have been fabricated via extrusion and casting methods. Cellulose nanofibers were obtained through acid hydrolysis of microcrystalline cellulose. This treatment aided in achieving stable suspensions of cellulose crystals in dimethylformamide (DMF), for subsequent incorporation into the shape memory matrix. CNTs were covalent functionalized with carboxyl groups (CNT‐COOH) and 4,4′‐methylenebis (phenylisocyanate) (MDI) (CNT‐MDI) to improve the dispersion efficiency between the CNT and the polyurethane. Significant improvement in tensile modulus and strength were achieved by incorporating both fillers up to 1 wt% without sacrificing the elongation at break. Electron microscopy was used to investigate the degree of dispersion and fracture surfaces of the composite fibers and films. The effects of the filler (type and concentration) on the degree of crystallinity and thermal properties of the hard and soft segments that form the PU sample were studied by calorimetry. Overall, results indicated that the homogeneous dispersion of nanotubes and cellulose throughout the PU matrix and the strong interfacial adhesion between nanotubes and/or cellulose and the matrix are responsible for the enhancement of mechanical and shape memory properties of the composites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Properties of nanofillers/crosslinked polyethylene composites for cable insulation

In this work, we report the effect of nanofillers and filler loading on mechanical, physical, dielectric, and thermal properties of the crosslinked polyethylene (XLPE) matrix. XLPE filled with 0.5–2% of zinc oxide (ZnO), aluminium oxide (Al₂O₃), and organoclay (OMMT) nanofillers prepared by melt mixing with a single screw extruder followed by hot press moulding. Nanocomposites were tested as per ASTM standard methods and characterized with tensile test, water absorption, linear rate of burning, dielectric breakdown strength, and thermal stability. Scanning electron microscopy (SEM) was used to examine the surface morphology of the nanocomposites. The results showed that addition of nanofillers improved tensile strength, elongation at break, Young's modulus, burning rate, dielectric breakdown strength, and decomposition temperature. However, water absorption increased with time due to the hydrophilic properties of nanofillers. In general, based on the properties measured Al₂O₃ exhibits the highest properties than those of ZnO and OMMT nanofillers. Addition of 1.5% of Al₂O₃ in XLPE matrix has led to the improvement in tensile strength, elongation at break, Young's modulus, burning rate, and dielectric breakdown strength as compared to the unfilled polymer. J. VINYL ADDIT. TECHNOL., 25:E147–E154, 2019. © 2018 Society of Plastics Engineers     

Significantly Strengthening Epoxy by Incorporating Carbon Nanotubes/Graphitic Carbon Nitride Hybrid Nanofillers

Novel hybrid nanofillers consist of carbon nanotubes (CNTs) and graphitic carbon nitride (g‐C₃N₄) are prepared for the enhanced mechanical properties of epoxy by improving the dispersion of CNTs. 2D planar structure, large surface area, and plentiful of surface reactive groups of g‐C₃N₄ efficiently resist the microcrack propagation, impede the thermal transfer, and provide chemical bonding with epoxy chains. The well‐dispersed CNTs by anchoring on g‐C₃N₄ surface promotes the efficient transfers of stress, and supply the stronger mechanical interlocking for interfacial bonding. The significantly enhanced mechanical properties of epoxy containing hybrid nanofillers are based on the synergistic effects between CNTs and g‐C₃N₄. Compared with neat epoxy, the tensile strength, tensile modulus, and storage modulus of epoxy containing 0.5 wt% hybrid nanofillers (CNTs: g‐C₃N₄ = 1: 9, w/w) below glass transition temperature (T_g) are increased by 37.65%, 29.36%, and 32.92%, respectively. Meanwhile, the T_g, onset decomposition temperature and char residue are also obviously raised.     

交联壳聚糖/蒙脱土复合膜的制备及性能研究

以壳聚糖（CS）为基质材料，蒙脱土（MMT）为填料，采用戊二醛（GA）交联改性并结合溶液插层法制备了交联壳聚糖/蒙脱土（CS/GA/MMT）复合膜。通过扫描电子显微镜、X射线衍射仪、红外光谱仪及热重分析仪对复合膜的结构进行了表征，考察了MMT用量对复合膜的吸水性能、水蒸气阻隔性能和力学性能的影响。结果表明，交联改性CS可提高CS膜的耐水性，CS/GA膜的吸水率较CS膜降低了9.6 %；MMT可提高复合膜的耐水性、水蒸气阻隔性能、力学性能和热稳定性；当MMT的用量为CS质量的5 %时，复合膜的各项性能较好，吸水率、水蒸气透过率和断裂伸长率较CS膜分别降低了37.3 %、36.7 %和41.9 %，且拉伸强度提高了160.5 %。     

Improved mechanical performance of solution-processed MWCNT/Ag nanoparticle composite films with oxygen-pressure-controlled annealing

A method for the synthesis of solution process-based MWCNT/Ag nanoparticle composite thin films as electrode or interconnect materials for flexible electronic devices is presented. The method produces homogeneously-dispersed CNT networks and increases the density of the Ag matrix, which are major factors in determining the mechanical performance of CNT/Ag films. By introducing nanometer-sized Ag particles as a matrix material, the agglomeration of CNTs is suppressed. In addition, the generation of pores during the synthesis procedure is effectively restrained by oxygen-pressure-controlled annealing. The elastic modulus of the pristine Ag films was observed to increase by 34% by adding 5 wt% CNTs. An improvement in the fatigue resistance of the CNTs under cyclic tensile deformation was confirmed. The normalized resistance change ((R ? R_o)/R_o) of the Ag films containing 5 wt% CNTs after fatigue testing was reduced by about 27% compared to that of the pristine Ag films. For industrial application the process has the advantage of relatively low-temperature processing without any high pressure compaction compared to the conventional powder metallurgy techniques normally used.     

马来酸酐接枝ABS的增容改性研究

研究了增容剂马来酸酐接枝ABS对PC／ABS合金、PA6／ABS合金及ABS／GF复合材料力学性能的影响。结果表明，该增容剂的加入明显提高了PC／ABS合金的冲击强度和断裂伸长率，使PA6／ABS合金的各项力学性能均明显提高，使ABS／GF复合材料的拉伸强度和断裂伸长率也有较大提高。     

Short glass fiber reinforced ABS and ABS/PA6 composites: Processing and characterization

In this study acrylonitrile‐butadiene‐styrene (ABS) terpolymer was reinforced with 3‐aminopropyltrimethoxysilane (APS)‐treated short glass fibers (SGFs). The effects of SGF concentration and extrusion process conditions, such as the screw speed and barrel temperature profile, on the mechanical properties of the composites were examined. Increasing the SGF concentration in the ABS matrix from 10 wt% to 30 wt% resulted in improved tensile strength, tensile modulus and flexural modulus, but drastically lowered the strain‐at‐break and the impact strength. The average fiber length decreased when the concentration of glass fibers increased. The increase in screw speed decreased the average fiber length, and therefore the tensile strength, tensile modulus, flexural modulus, and impact strength were affected negatively and the strain‐at‐break was affected positively. The increase in extrusion temperature decreased the fiber length degradation, and therefore the tensile strength, tensile modulus, flexural modulus, and impact strength increased. At higher temperatures the ABS matrix degraded and the mechanical strength of the composites decreased. To obtain a strong interaction at the interface, polyamide‐6 (PA6) at varying concentrations was introduced into the ABS/30 wt% SGF composite. The incorporation and increasing amount of PA6 in the composites broadened the fiber length distribution (FLD) owing to the low melt viscosity of PA6. Tensile strength, tensile modulus, flexural modulus, and impact strength values increased with an increase in the PA6 content of the ABS/PA6/SGF systems due to the improved adhesion at the interface, which was confirmed by the ratio of tensile strength to flexural strength as an adhesion parameter. These results were also supported by scanning electron micrographs of the ABS/PA6/SGF composites, which exhibited an improved adhesion between the SGFs and the ABS/PA6 matrix. POLYM. COMPOS. 26:745–755, 2005. © 2005 Society of Plastics Engineers     

Thermal,mechanical, and morphological investigation of injection molded poly(trimethylene terephthalate)/carbon fiber composites

Injection molded poly(trimethylene terephthalate) (PTT)/carbon fiber (CF) composites have been fabricated using a twin screw micro compounder. The effect of CF reinforcement on the thermal, mechanical, dynamic mechanical, and microscopic properties of the composite was investigated. Addition of 30 wt% of CF into PTT resulted in the significant enhancement of tensile (120%) and flexural (30%) strength compared to neat PTT. The rule of mixture was successfully employed for theoretical calculations of tensile modulus and the calculated values were compared with the experimental results. Similarly, CF reinforced (30 wt%) PTT composites exhibited an increase of more than a 150°C in the heat deflection temperature. Scanning electron microscopy analysis of the tensile fracture specimens revealed uniform distribution of the CFs with good polymer matrix and fiber adhesion. Overall, the results obtained indicate the enhancement of properties with increasing fiber content, confirming better fiber and polymer matrix compatibility. POLYM. COMPOS., 33:1933–1940, 2012. © 2012 Society of Plastics Engineers     

High erosion resistance thermoplastic polyurethanes composites fabricated via intercalation reinforced interfacial interaction

The weak interface and poor dispersion of carbon nanofillers in polymer matrix composites lead to a significant decrease in their performance, restricting the development of polymer nanocomposites. In this work, a highly facile strategy has been developed to improve the interfacial adhesion performance between graphene nanoplates (GNP) and thermoplastic polyurethanes (TPU) matrix via self-polymerization of dopamine. Then, single-walled carbon nanotubes (CNT), as reinforcing agent, were introduced into surface modified GNP solution to prepare the corresponding ternary composites. Scanning electron microscope images show that GNP and CNT formed 3-D interconnecting network-like architecture. The sample modified with three layers of nonwoven fabric decorated with 1.0 mg/mL nanomaterial exhibit a tensile strength 35% higher than that of the virgin TPU. Consequently, compared with virgin TPU, the erosion resistance and thermal conductivity are enhanced by 78% and 45%, respectively.