Halloysite nanotubes/polystyrene (HNTs/PS) nanocomposites via in situ bulk polymerization

Serials of halloysite nanotubes/polystyrene (HNTs/PS) nanocomposites with different contents of organo-modified halloysite nanotubes (organo-HNTs) were successfully prepared by the in situ bulk polymerization of styrene with the organo-HNTs as macromonomers. The percentage of grafting (PG%) of more than 230% was achieved, calculated from the results of the thermogravimetric analysis (TG). The TG results also showed that the thermal stabilities of the HNTs/PS nanocomposites prepared via the bulk polymerization were better than the pure polystyrene. And the maximum thermal degradation temperature of the nanocomposites increased with the increasing of the amount of the HNTs fillers added.     

Understanding the effect of filler shape induced immobilized rubber on the interfacial and mechanical strength of rubber composites

Styrene butadiene rubber (SBR) composites with silica, halloysite nanotubes (HNTs) and montmorillonite (MMT) were prepared and the interfacial and mechanical properties were compared to understand the reinforcing behaviours of these fillers based on the results of SEM, DSC, DMA, etc. Due to the formation of interparticle domain, HNTs immobilized more rubber approaching their surface than silica and MMT. Interestingly, only tightly immobilized rubber chains made contribution to the enhancement of interfacial and mechanical strength of SBR composites. This was because the tightly immobilized rubber acted as a bridge in the filler-rubber interface and induced the formation of stretched rubber chains linked filler network when the composites were loaded in tension, while loosely immobilized rubber were easy to slip off from filler surface, causing the separation between filler and bulk rubber. Therefore, silica with more tightly immobilized rubber approaching its surface showed better reinforcing effect on rubber than HNTs and MMT.     

Structure-property relationships in polyamide 12/halloysite nanotube nanocomposites

Polyamide 12 (PA12) nanocomposites based on halloysite nanotubes (HNTs) were obtained using a batch internal mixer or a twin-screw mini-compounder. In order to analyze the influence of HNTs dispersion on nanocomposite properties, morphological analysis (SEM and TEM) was combined with rheological and thermo-mechanical experiments. The linear viscoelastic properties and the dynamic storage modulus were expectedly found to increase with increasing HNT loading. Higher enhancements were observed for PA12/HNTs nanocomposites obtained by twin-screw mini-compounding. This finding was related to the better degree of dispersion and alignment of the silicate nanotubes throughout the matrix. Thermal stability was also improved by the halloysite nanotubes presumably by an entrapment mechanism of the volatile products inside the hollow tubular structure. DSC measurements further highlighted a nucleation effect of HNTs on the nanocomposites. In view of these results, halloysite nanotubes are promising candidates in the field of PA nanocomposites for structural applications.     

聚环氧乙烷/埃洛石纳米管复合材料的热稳定性和燃烧性质

采用熔融共混法制备了聚环氧乙烷(PEO)/埃洛石纳米管(HNTs)复合材料,重点研究了HNTs含量对PEO/HNTs复合材料的微观结构、热稳定性及燃烧性质的影响。结果表明,在熔融共混条件下,不同含量的表面未经任何处理的HNTs以纳米尺度均匀分散于PEO基体中;随着HNTs含量的增加,复合材料的热稳定性显著增加。氧指数和水平燃烧测试结果均表明随着HNTs含量的增加,复合材料的阻燃能力有较大提高。     

Thermal stability and flame retardant effects of halloysite nanotubes on poly(propylene)

Naturally occurred halloysite nanotubes (HNTs) with hollow nanotubular structures were used as a new type filler for poly(propylene) (PP). Nanocomposites based on PP and HNTs were prepared by melt blending. Scanning electronic microscopy (SEM) results suggested HNTs were dispersed in PP matrix evenly at nanoscale after facile modification. Thermal stability of the nanocomposites was found remarkably enhanced by the incorporation of HNTs. Cone calorimetric data also showed the decrease of flammability of the nanocomposites. Entrapment mechanism of the decomposition products in HNTs was proposed to explain the enhancement of thermal stability of the nanocomposites. The barriers for heat and mass transport, the presence of iron in HNTs, are all responsible for the improvement in thermal stability and decrease in flammability. Those results suggested potential promising flame retardant application of HNTs in PP.     

Thermal behaviors and mechanical properties of halloysite nanotube-reinforced poly(lactic acid) nanocomposites

Poly(lactic acid)/halloysite nanotubes (PLA/HNTs) nanocomposites were prepared using melt compounding followed by compression molding. N,N′-ethylenebis(stearamide) (EBS) was used to improve the dispersion of HNTs and toughen the PLA nanocomposites. The thermal properties of PLA/HNTs nanocomposites were assessed by using differential scanning calorimeter and thermogravimetric analyzer (TG). The TG measurements were performed at both nitrogen and oxygen atmosphere. The mechanical properties of PLA/HNTs were characterized through tensile and impact tests. The morphological properties of the PLA/HNTs nanocomposites were investigated by using transmission electron microscopy and field emission scanning electron microscopy. The degree of crystallinity of PLA nanocomposites was increased slightly by the addition of EBS. The decomposition process of PLA/HNTs depends on the atmosphere reaction during TG test as well as the amount of EBS. The best mechanical properties of PLA/HNTs nanocomposites expressed by the impact strength and elongation at break were achieved by the addition of 5 mass% of EBS.     

Towards scalable production of polyamide 12/halloysite nanocomposites via water‐assisted extrusion: mechanical modeling,thermal and fire properties

In this study, polyamide 12 (PA12)/untreated halloysite nanotubes (HNTs) nanocomposites are prepared in a semi‐industrial scale extruder using a non‐traditional “one step” water‐assisted extrusion process. A morphological study is carried out using a combination of scanning electron microscopy and transmission electron microscopy analyses to evaluate the influence of water injection and filler content on the quality of clay dispersion. The use of water injection slightly improves the nanoscale dispersion at low HNTs content (<8 wt.%), while this effect is more pronounced at higher filler loading (16 wt.%). A mechanism explaining the physico‐chemical action of water during extrusion is proposed. The materials are characterized with respect to their mechanical, thermo‐mechanical, thermal and fire properties. A strong correlation is found between nanostructure and physical properties; the more uniform dispersion of the clay nanotubes, the higher mechanical reinforcement, thermal stability and fire retardancy of PA12 nanocomposites. Tensile tests results are interpreted in terms of three mechanical models: the Halpin–Tsai's model for stiffness and the interfacial strength model and the Pukanszky's equation for yield strength. Linear fits of the experimental data confirm that the superior reinforcement of nanocomposites prepared using water injection results from improved clay dispersion and better interfacial adhesion between PA12 and HNTs. In view of these promising results, the proposed direct melt compounding method could be easily scaled‐up towards the production of PA12–HNTs nanocomposites at an industrial scale. Copyright © 2013 John Wiley & Sons, Ltd.     

Effects of halloysite nanotube orientation on crystallization and thermal stability of polypropylene nanocomposites

The polypropylene/halloysite nanotubes (PP/HNTs) nanocomposites were prepared via water-assisted injection molding (WAIM) and compression molding (CM). HNTs were highly oriented in WAIM parts due to the strong shear effect; whereas HNTs were randomly oriented in the CM one. The orientation of HNTs had little influence on their nucleating efficiency for the PP. However, the HNTs selectively induced α-form crystal at high cooling rates; whereas they showed β-nucleating activity at low cooling rates. Thermal analyses revealed that the HNTs delayed thermal degradation onset in the initial degradation stage, whereas they sped up the thermal degradation in the main volatilization stage at the contents of 5 and 8 wt%. The simultaneous thermogravimetric analyses and differential scanning calorimetry measurements revealed that, at a low content, the direct stabilizing effect of HNTs on PP contributed largely to the increased thermal stability of the WAIM PP/HNTs nanocomposites rather than their barrier and entrapment effect on the volatile products.     

Chemical modification of carbon fiber with diethylenetriaminepentaacetic acid/halloysite nanotube as a multifunctional interfacial reinforcement for silicone resin composites

In the present research, a multifunctional hierarchical reinforcement was prepared by chemical modification of carbon fibers (CFs) with halloysite nanotubes (HNTs) by the bridging diethylenetriaminepentaacetic acid (DTPA) for improving interfacial microstructures and properties of composites. Surface structures and groups of modified HNTs and CFs were characterized systematically. The uniform distributions of the introduced DTPA and HNTs helped to increase fiber polarity, surface energy, and wettability. As a consequence, significant enhancements of interfacial properties and hydrothermal aging resistance of composites were achieved, and interfacial reinforcing mechanisms have also been studied. Moreover, the storage modulus showed a 17.95% improvement, and the glass transition temperature was enhanced by 17°C by dynamic mechanical analysis testing.     

Influence of maleic anhydride grafted ethylene propylene diene monomer (MAH-g-EPDM) on the properties of EPDM nanocomposites reinforced by halloysite nanotubes

Ethylene propylene diene monomer grafted with maleic ahydride (MAH-g-EPDM) was prepared by peroxide-initiated melt grafting of MAH onto EPDM using a HAAKE internal mixer at 180 °C and 60 rpm for 5 min. The effect of MAH-g-EPDM compatibilizer on the interactions, and tensile and morphological properties of halloysite nanotubes (HNTs) filled EPDM nanocomposites was investigated. The tensile properties of the nanocomposites were influenced by two major factors. The hydrogen bonding between MAH-g-EPDM and HNTs, which was confirmed by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), as well as the formation of EPDM-rich and HNT-rich areas, are the dominant effects on the tensile strength of the nanocomposites at low and high HNT loading, respectively. It was found that the cure time (t₉₀), maximum torque (M_H) and minimum torque (M_L) of the compatibilized nanocomposites were increased after adding MAH-g-EPDM. The reinforcement mechanism of the compatibilized and un-compatibilized EPDM/HNT nanocomposites was also investigated based on morphological observations of the nanocomposites.     

Sustainable nanocomposites based on halloysite nanotubes and pectin/polyethylene glycol blend

This study was focused on the preparation and characterization of biofilms based on pectin/polyethylene glycol 20000 (PEG) blend and halloysite nanotubes (HNTs). The obtained blends loaded with a natural nanoclay are proposed as sustainable alternative to the polymers produced from non-renewable resources such as fossil fuels. Properties of technological interest have been monitored and they were correlated to the structural features of the nanocomposites. It turned out that the wettability of the films can be tuned by changing the composition and the distribution of HNTs into the material as well as the surface roughness. The tensile properties of the blend are enhanced by the presence of the nanoclays. The PEG crystallinity is reduced by the nanoparticles and preserved if a certain amount of pectin is added.     

Aging properties of styrene-butadiene rubber nanocomposites filled with carbon black and rectorite

To better understand the effect of rectorite and carbon black (CB) on the aging performance of styrene-butadiene rubber (SBR), SBR/CB, SBR/CB/rectorite and SBR/rectorite nanocomposites with the same total filler loading were prepared. The microstructure of the three SBR nanocomposites was characterized by XRD, TEM and SEM. After thermal aging, oxygen-containing molecules were found to be formed in the SBR nanocomposites, as verified by FTIR analysis. The SBR/rectorite nanocomposite showed the highest aging coefficient and the lowest change rate of tensile strength and stress at 100% strain among the three SBR nanocomposites, indicating that the introduction of nano-dispersed rectorite layers can enhance the thermal aging resistance of the nanocomposites. For the SBR/CB/rectorite nanocomposite, the addition of CB helped to improve the interfacial compatibility between the filler and matrix, resulting in the best crack resistance as the aged SBR/CB/rectorite nanocomposite always demonstrated the least cracks on the surface during either stretching or bending experiments.     

Free Volume of Montmorillonite/Styrene‐Butadiene Rubber Nanocomposites Estimated by Positron Annihilation Lifetime Spectroscopy

Summary: The size and concentration of free‐volume holes of two kinds of montmorillonite (MMT)/styrene‐butadiene rubber (SBR) nanocomposites were investigated by positron annihilation lifetime spectroscopy (PALS). Strong interfacial interaction caused an apparent reduction of the free‐volume fraction of rubber probably by depressing the formation of free‐volume holes in the interfacial region. Interfacial interaction in MMT/SBR nanocomposites was weaker than that in SBR filled with carbon black.

Dependence of normalized o‐Ps intensity of four kinds of composites on filler volume fraction.     

New hybrid materials based on double‐functionalized linseed oil and halloysite

A series of hybrid systems which combine double‐functionalized linseed oil (methacrylated epoxidized linseed oil) and 2 types of functionalized halloysite (methacrylated halloysite and epoxidized halloysite) was designed in the current study. The curing of the new formulated oil‐clay mixtures was performed via 2 different mechanisms under the influence of the temperature: free‐radical and anionic polymerization. The effect of the functionalized clay tubes against the oil‐based macromonomer reactivity, representing the focus of this study, was monitored by differential scanning calorimetry and Fourier transform infrared spectrometry, concluding that both types of halloysite nanotubes (HNTs) exhibit significant influence on the building of methacrylate/epoxy networks. The effect of the HNTs on the methacrylated epoxidized linseed oil network properties was studied by dynamic mechanical analysis and thermogravimetric analysis, and the morphology of the synthesized hybrids was investigated by scanning electron microscopy. The results suggested that the designed oil‐based hybrid performance is determined by the presence of the both HNT molecules.     

改性埃洛石材料的制备及其对亚甲基蓝吸附行为的研究

使用硅烷偶联剂KH550改性埃洛石纳米管获得改性材料HNTs-APTS,并对其吸附亚甲基蓝的行为进行研究。利用傅立叶变换红外光谱仪(FTIR)、X-衍射仪(XRD)对改性前后的埃洛石进行表征。考察了吸附时间和温度对吸附过程的影响,并采用Lagrange准二级动力学方程、Langmuir等温线方程及Freundlich等温线方程对实验数据进行拟合。结果表明,KH550成功负载到埃洛石表面;改性后材料的吸附能力大大提高。改性埃洛石对亚甲基蓝的吸附约在60 min达平衡,最大吸附容量为21.66 mg/g。其吸附过程符合准二级动力学方程,热力学较好地符合Langmuir等温线方程,且吸附过程为自发吸热,升高温度有利于吸附的进行。改性材料可重复再生6次,具有良好的再生性能,可在工业处理亚甲基蓝废水中使用。     

埃洛石纳米流体制备及提高驱油采收率的研究

随着对石油的需求量持续增长,国内大多数二次采油已接近尾声,三次采油已是大势所趋,而化学驱是一种常用的三次开采的方法。本文研究了采用包覆改性埃洛石纳米管方法,通过溶胶凝胶法合成HNTs/SiO2复合颗粒。通过红外光谱分析了表征产品的结构,证实HNTs和SiO2不是简单的物理混合,而是发生了化学键合的作用。通过对不同浓度的样品的接触角测定,发现当浓度为0.05wt%时HNTs/SiO2发生了润湿反转,由亲油状态变为亲水状态;并通过沉降时间观察、zeta电位测定,结果表明产物中包覆硅层会影响HNTs/SiO2分散性。浓度为0.05wt%时,改性埃洛石纳米流体可提高原油采收率最大,高达28.18%。     

Thermal and flammability properties of polyethersulfone/halloysite nanocomposites prepared by melt compounding

This paper presents a study of polyethersulfone (PES)/halloysite nanotube (HNTs) nanocomposites prepared by melt compounding either through a simple extrusion process or via a water-assisted extrusion procedure. Scanning and transmission electron microscopy techniques are combined with rheological measurements to assess the influence of polymer end groups (–Cl or –OH) and water injection on the HNTs dispersion state. A morphological transition form microcomposite to nanocomposite is achieved when replacing –Cl chain ends of PES by –OH groups, especially when water is injected during processing. By a combination of Soxhlet extraction and thermogravimetric analysis, we show that some PES(OH) chains are covalently bonded onto the aluminosilicate surface during extrusion. A mechanism describing the physico-chemical action of water is presented. The best system in terms of clay dispersion has been retained to characterize PES-HNTs nanocomposites with respect to their thermo-mechanical, thermal and fire (mass loss calorimetry and UL-94) properties. Dynamic mechanical analysis shows a significant enhancement in the storage modulus of halloysite-based nanocomposites when compared to the unfilled matrix. The improved thermal and thermo-oxidative stability of PES in presence of HNTs is mainly attributed to the labyrinth effect provided by individually dispersed nanotubes, which is reinforced during the decomposition process by the formation of a protective charred ceramic surface layer. The mechanism of action of HNTs for fire retardancy of PES presumably arises from a synergistic effect between physical (i.e. ceramic-like structure formation and mechanical reinforcement of the intumescent char) and chemical (i.e. charring promotion) processes taking place in the condensed phase. According to this study, the straightforward and cost-effective melt compounding route could pave the way for future development of high-performance nanoscale polymeric materials combining enhanced thermal properties and excellent flame retardant behaviour.     

Gold nanoparticles stabilized by modified halloysite nanotubes for catalytic applications

A highly sustainable prototype of a flow system based on gold nanoparticles (4.2 nm) supported on thiol‐functionalized halloysite nanotubes (HNTs) was developed for catalytic applications. The catalytic performances were evaluated using the reduction of 4‐nitrophenol to 4‐aminophenol as a model system. Under the best experimental conditions (0.0001 mol%, 1.97 × 10^?8 mg of Au nanoparticles), an impressive apparent turnover frequency value up to 2 204 530 h^?1 was achieved and the halloysite‐based catalyst showed full recyclability even after ten cycles. The high catalytic activity confirms the importance of the use of HNTs as support for Au nanoparticles that can exert a synergistic effect both as medium for transfer of electrons from borohydride ions to 4‐nitrophenol and by modulating interfacial electron transfer dynamics. With the application of flow technology, the obtained heterogeneous HNT@Au catalyst was fully recovered and reused for at least one month.     

The synergistic reinforcing effects of halloysite nanotube particles and polyolefin elastomer-grafted-maleic anhydride compatibilizer on melt and solid viscoelastic properties of polylactic acid/ polyolefin elastomer blends

The effect of halloysite nanotube (HNTs) particles and polyolefin elastomer-graft-maleic anhydride (POE-g-MA) in the polylactic acid (PLA) and polyolefin elastomer (POE) blend with a constant weight percentage composition have been studied using the scanning electron microscopy, rheometry, dynamic mechanical thermal analysis (DMTA) as well as the thermogravimetric testing. Through these, it was found that the simultaneous presence of POE-g-MA and HNT significantly improves the melt and solid viscoelastic properties and thermal stability of PLA/POE. This improvement is attributed to the increased interactions and improved interfacial adhesion between the present components. The microscopic images of PLA/POE-g-MA/POE (80/8/12) blend containing 4 wt% HNT showed a microstructure similar to the interconnected morphology due to the enhanced compatibility and better dispersion of nanoparticles. The rheological behavior was significantly changed for the PLA/POE blend containing POE-g-MA and 4 wt% HNT. This dramatic increase in the rheological properties was consistent with the morphological results. Only one glass transition temperature was observed in the DMTA plot of PLA/POE-g-MA/POE blend, which was a sign of a homogeneous, fully compatible system. In addition, a very strong reinforcing effect of HNT particles was observed in the presence of POE-g-MA for the nanocomposites. Finally, the thermogravimetric analysis showed a completely different trend for thermal degradation of PLA/POE-g-MA/POE nanocomposite containing 4 wt% HNT, which could be an indication of microstructural development.     

A robust combination of dysprosium vanadate/halloysite nanotubes: the electrochemical system for dimetridazole detection

Dimetridazole (DMD) is one of the significant antibiotic drugs of nitroimidazoles derivates that have attracted increasing attention in the medical field due to its pharmacological and toxicological activity. The development of high-performance sensors for continuous monitoring of DMD in food and environments is receiving increasing attention. Herein, an electrochemical platform was designed based on a dysprosium vanadate/halloysite nanotubes (DyV/HNTs) nanocomposite for the detection of DMD. The DyV/HNTs nanocomposite was examined by various spectroscopic and analytical techniques. The DyV/HNTs based electrochemical sensor reveals a distinctly higher electrocatalytic response to the reduction of DMD due to the good physiochemical properties compared to other electrodes. The DyV/HNTs based electrochemical sensor for DMD covered two linear ranges of 0.001–0.54 and 0.54–188 μM with a detection limit of 0.9 nm through the amperometric method, which is better than those previously reported. Furthermore, selectivity, stability, repeatability, and reproducibility studies were performed. Moreover, the fabricated DyV/HNTs sensor was successfully applied for the reliable discrimination of DMD in biological and water samples with satisfactory recovery values. The results indicated that this DyV/HNTs nanocomposite may be a promising electrochemical sensing platform for the determination of DMD.