木质素补强乳聚丁苯橡胶研究进展

阐述了木质素补强乳聚丁苯橡胶的原理及方法,原理包括木质素可与橡胶发生接枝反应、木质素可与橡胶形成芳香氢键、木质素与金属离子形成木质素-金属螯合物,补强方法包括混炼工艺、共沉工艺等;综述了木质素补强乳聚丁苯橡胶的国内外研究进展,木质素可以很好地改善橡胶的物理力学性能,如提高胶料的硬度、拉伸强度、拉断伸长率、300%定伸应力、撕裂强度和耐热老化等性能。最后,对木质素在橡胶工业中的应用做了展望。     

碳纳米管对羟基磷灰石基复合材料力学性能的影响

将力学性能优良的碳纳米管(CNTs)与羟基磷灰石(HA)生物陶瓷相复合,发展CNTs/HA复合材料来应用于骨组织修复领域,有望解决HA生物陶瓷力学性能的不足.通过3种不同的制备方法,即通过表面活性剂将CNTs分散在HA基体中、通过酸碱中和反应将CNTs与HA共沉淀以及通过体外浸泡在CNTs上矿化生长HA等方法来获得CNTs/HA复合材料.深入研究CNTs的表面结构和分散状态对CNTs/HA复合材料力学性能的影响.结果表明,CNTs的添加改变了HA的脆性,导致复合材料抗压力学性能得到提高.但是,由于复合材料制备方法的不同,导致CNTs在HA基体中的分散状态、表面结构的完整性以及与HA的界面结合情况不同,导致其抗压力学性能不同.其中,通过表面活性剂将CNTs分散在HA基体中而获得复合材料的抗压力学性能表现最好,而CNTs与HA通过共沉淀法所获得复合材料的抗压力学性能表现最差.     

碳纳米管对羟基磷灰石基复合材料力学性能的影响

将力学性能优良的碳纳米管(CNTs)与羟基磷灰石(HA)生物陶瓷相复合,发展CNTs/HA复合材料来应用于骨组织修复领域,有望解决HA生物陶瓷力学性能的不足。通过3种不同的制备方法,即通过表面活性剂将CNTs分散在HA基体中、通过酸碱中和反应将CNTs与HA共沉淀以及通过体外浸泡在CNTs上矿化生长HA等方法来获得CNTs/HA复合材料。深入研究CNTs的表面结构和分散状态对CNTs/HA复合材料力学性能的影响。结果表明,CNTs的添加改变了HA的脆性,导致复合材料抗压力学性能得到提高。但是,由于复合材料制备方法的不同,导致CNTs在HA基体中的分散状态、表面结构的完整性以及与HA的界面结合情况不同,导致其抗压力学性能不同。其中,通过表面活性剂将CNTs分散在HA基体中而获得复合材料的抗压力学性能表现最好,而CNTs与HA通过共沉淀法所获得复合材料的抗压力学性能表现最差。     

氧化石墨烯纳米带-碳纳米管/TPU复合材料薄膜的制备及表征

将不同维度纳米填料同时复合,采用纵向氧化切割MWCNTs法制得不同含量比的氧化石墨烯纳米带-碳纳米管(GONRs-CNTs)2种维度纳米材料复合体,随后将上述填料加入到TPU基体中制得GONRsCNTs/TPU复合材料薄膜.采用FTIR、XRD、TG、XPS、TEM和FE-SEM研究了不同反应条件下所得GONRsCNTs复合体的结构及性能,并结合复合材料薄膜的氧气透过率和拉伸测试以及表面形貌观察,研究了GONRs与CNTs的协同作用、二者的含量比对TPU复合材料薄膜阻隔和力学性能的影响.研究表明,GONRs与CNTs的协同效应明显优于MWCNTs,同时当所加GONRs-CNTs复合体中GONRs与CNTs的含量比约为67∶33时,GONRs-CNTs/TPU复合材料薄膜的氧气透过率和拉伸强度相比纯TPU薄膜分别降低51.3%和提高29.3%,阻隔性能和力学性能均得到明显改善.     

改性木薯淀粉/橡胶复合材料的制备及性能研究

以木薯淀粉、马来酸酐、苯乙烯为原料,过硫酸钾为引发剂,通过溶液共聚合成了一系列苯乙烯改性淀粉树脂(SMS)。然后将改性淀粉同丁苯橡胶(SBR)、天然橡胶(NR)进行混炼、硫化模压成型,制得苯乙烯改性淀粉/丁苯橡胶/天然橡胶复合材料。采用红外光谱(IR)对苯乙烯改性淀粉接枝共聚物进行了结构表征。通过拉伸性能测试考察了不同苯乙烯含量的木薯淀粉接枝产物对丁苯橡胶/天然橡胶的力学性能的影响。结果表明,淀粉改性后,随着苯乙烯含量的增多,所得复合橡胶的拉伸强度与邵氏硬度均呈现先增加后降低的趋势。当苯乙烯用量为15%时所制得的苯乙烯改性淀粉/丁苯橡胶/天然橡胶复合材料的拉伸强度与邵氏硬度最大且优于未改性淀粉复合材料,其拉伸强度为2.0MPa,邵氏硬度为25.8HD。     

炭黑N134在不同橡胶基体中的分散及其混炼工艺调控

以炭黑N134作为填料,对比了异戊橡胶、丁苯橡胶及仿生橡胶3种体系下混炼工艺对硫化胶性能的影响,并针对仿生橡胶体系炭黑分散度低的问题,对混炼工艺进一步优化,从而提高分散度和动静态性能.结果表明,在所研究的密炼时间范围内,随着密炼时间的延长,异戊橡胶体系和丁苯橡胶体系的分散等级由原本的1级左右提升至6级以上.但延长密炼时间并未明显提升仿生橡胶体系的炭黑分散度.针对该问题引入塑炼和包辊工艺,仿生橡胶炭黑分散性明显提高.随炭黑分散等级的增加, 3种橡胶体系的伸张疲劳性能均得到了较大改善.其中仿生橡胶生胶经塑炼后,门尼黏度和重均分子量均明显下降,表明塑炼对于增强胶料的加工性能有明显作用.相同炭黑混炼时间下,随着塑炼时间的延长,硫化胶佩恩效应也增强,这主要是由于炭黑分散程度的提高使得炭黑与橡胶基体的有效接触面积增加,进而在一定程度上增加了界面结合胶的含量.     

木质素增强丁苯橡胶复合材料研究

采用木材水解木质素为原料,均匀溶解在碱性溶液中,与天然橡胶复合形成互穿网络结构,再通过共沉淀法制得一种木质素/天然橡胶复合物。采用该复合物部分代替商用橡胶补强剂——白炭黑,通过三段混炼法对丁苯橡胶进行混炼。结果表明,这种木质素/天然橡胶复合物对丁苯橡胶具有一定的补强作用,其拉伸强度及断裂伸长率均得到一定改善;而热机械性能研究发现,该复合物部分代替白炭黑后,橡胶材料的滚动阻力及耐寒性均得到改善,但抗湿滑性能有一定程度下降。     

橡胶-填料相互作用对丁苯橡胶/白炭黑复合材料性能的影响

本文研究了硅烷偶联剂原位改性白炭黑对溶聚丁苯橡胶(SSBR)性能的影响,结果表明,通过哈克转矩流变仪对含有偶联剂的SSBR/白炭黑混炼胶进行原位热处理后可明显减弱混炼胶的Payne效应,改善白炭黑在橡胶基体中的分散.原位热处理方法能够明显提高硫化胶的300%定伸应力,降低动态压缩温升,同时可使硫化胶在0℃附近具有较高的损耗因子(tanδ),60℃附近具有较低的tanδ.对不同聚合方式得到的丁苯橡胶,即溶聚丁苯橡胶与乳聚丁苯橡胶(ESBR)/白炭黑复合材料的力学性能及动态力学性能进行了研究,结果表明,白炭黑在SSBR2305中分散效果优于在ESBR1502中;采用偶联剂原位改性白炭黑可以使SSBR2305硫化胶获得与ESBR1502硫化胶相当的物理机械性能,更理想的动态力学性能,从而得到力学性能、抗湿滑性、滚动阻力及耐磨性更加均衡的理想轮胎材料.通过对具有不同偶联效率的SSBR/白炭黑体系的微观结构与性能研究发现,随偶联效率的增加,其结合橡胶含量增加,Payne效应减弱;高偶联效率的S-SBR具有较低的动态压缩温升及较好的耐磨性.     

亲水性炭黑-天然橡胶纳米复合材料的制备及性能

利用原位球磨法制备了聚苯乙烯磺酸钠表面修饰炭黑,粒径分析和离心沉降实验结果表明,改性炭黑在水中具有十分优异的分散稳定性。利用该改性炭黑通过胶乳混合法成功制备了亲水性炭黑-天然橡胶纳米复合材料。采用万能电子拉力机、扫描电子显微镜、结合橡胶含量分析和动态热机械分析等多种手段对该复合材料进行了测试和研究。结果表明,与未改性炭黑相比,改性炭黑在橡胶基体中的分散性明显改善,与基体的相互作用显著增强,材料的力学性能大幅提高,填料网络化程度明显减弱。     

钛酸钾晶须对热硫化硅橡胶性能的影响

研究了钛酸钾晶须对热硫化硅橡胶复合材料的硫化特性、力学性能及热稳定性的影响,通过扫描电镜观察了复合材料的断面及晶须在基体中的分散性。结果表明:钛酸钾晶须能促进硅橡胶的硫化,提高其最高扭矩;同时,钛酸钾晶须对硅橡胶具有一定的补强作用,拉伸强度、硬度等随晶须用量的增加而增大;钛酸钾晶须的引入,使硅橡胶复合材料的热稳定性明显提高,填充量为9vol%时,与纯硅橡胶相比,复合材料的热分解温度提高了65℃,Kissinger法求出填充量为12vol%的钛酸钾晶须/硅橡胶复合材料的热分解活化能为193.62kJ/mol,高于相同填充量的白炭黑/硅橡胶复合材料,具有较好的热稳定性。     

Oligoaniline assisted dispersion of carbon nanotubes in epoxy matrix for achieving the nanocomposites with enhanced mechanical,thermal and tribological properties

A critical challenge for initiating many applications of the carbon nanotubes (CNTs) is their dispersion in organic solvent or in polymer melt. In the present study, we described a novel strategy for fabricating carbon nanotubes (CNTs)-reinforced epoxy nanocomposite by utilizing aniline trimer (AT) as the noncovalent dispersant. Tensile testing showed that the tensile modulus of the CNTs-reinforced epoxy composites was considerably improved by adding a small amount of AT functionalized CNTs. Additionally, the as-prepared CNTs-epoxy nanocomposites exhibited superior tribological properties with much lower frictional coefficients and wear rates compared to those of neat epoxy resin. The well dispersed AT-functionalized CNTs in epoxy matrix played an important role in enhancing the mechanical properties, as well as acting as a solid lubricant for improving the tribological performance of epoxy/CNTs nanocomposite.     

Interfacial mechano-chemical grafting in styrene-butadiene rubber/halloysite nanotubes composites

SBR/unmodified HNT composites were prepared by open-mill mixing and vulcanization. The results showed that HNT could decrease the scorch and optimum cure time, and play a significant role in reinforcing SBR vulcanizates. Mechano-chemical grafting at the interface between HNT and SBR was investigated by using infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), solid-state ¹³C NMR spectra and bonded rubber content, etc. The results showed the shearing force during the mixing process can impel the grafting reaction of SBR onto the surfaces of HNT, which leads to interfacial chemical bonding between phenyl’s α-H of SBR and the surface groups of HNT with Si-OH or Al-OH. Thus, the mechanical properties of the composites were significantly enhanced.     

SBR composites reinforced with <Emphasis Type="Italic">N</Emphasis>-isopropyl-<Emphasis Type="Italic">N</Emphasis>′-phenyl-<Emphasis Type="Italic">P</Emphasis>-phenylenediamine-modified clay

SBR compounds including the N-isopropyl-N’-phenyl-p-phenylenediamine-modified clay(organoclay) were prepared.Effects of modified clay and antioxidant(IPPD) contents on mechanical and rheological properties of SBR composites were studied.FTIR results confirmed that the clay was chemically modified by IPPD and changed into an organoclay.X-ray diffraction(XRD) results confirmed the increase in interlayer distance of the clay due to the insertion of IPPD.Rheological and cure characteristics of SBR compounds were determined using RPA(Rubber Process Analyzer) and rheometer.Scorch time and cure time of SBR compounds decreased with introduction of the organoclay.Mechanical properties and heat aging resistance of the SBR composites were improved significantly by incorporation of the organoclay.     

Mechanical,acoustical and flammability properties of SBR and SBR-PU foam layered structure

In this work a layer structure from styrene butadiene rubber (SBR) composites and PU foam with improved flame retardancy property and high sound absorption coefficient at frequency range (200–500 Hz). Different types of flame retardants; iron (acrylic-co-acrylamide) as metal chelate (MC), magnesium hydroxide (MOH) and sodium tripolyphosphate (STP) were blended with SBR. The type and loading level of flame retardant had a great effect on filler dispersion and consequently on mechanical properties of SBR. MOH exhibited the best dispersion as indicated from scanning electron microscope (SEM), and SBR/MOH samples had almost the highest crosslink density (16.04*10⁻⁵ g⁻¹ mol) and the best mechanical properties where the tensile strength was improved by 32.7% at 40 phr MOH. Horizontal burning rate of SBR composites indicated that MC and MOH reduced the rate of burning of SBR at all loading levels. TGA data presented that the addition of flame retardants to SBR increased the maximum decomposition temperature in all composites. A double and triple layer structures of SBR composite and PU foam was designed. The effect of 2.5 cm air cavity on the sound absorption coefficient of SBR-PU foam layered structure was studied. The presence of air cavity behind the layered structure improved the sound absorption in the range of (200–500 Hz) better than the existence of it between the layers. The triple-layer structure gave higher sound absorption coefficient at lower frequencies than that obtained with the double-layer structure where it reached to ≥0.98 at 315 Hz.     

Relations between the aspect ratio of carbon nanotubes and the formation of percolation networks in biodegradable polylactide/carbon nanotube composites

The biodegradable polylactide composites containing carbon nanotubes (CNTs) with high aspect ratio (HAR) and low aspect ratio (LAR) were prepared by melt mixing. The physical properties of those two systems were characterized in terms of rheology, conductivity, and mechanical properties for establishing preliminary structure–property relations. Several viscoelastic models were then used to further describe the relations between aspect ratio and percolation network of CNTs. The results show that these two CNTs present different structural characteristics in the polylactide (PLA) matrix during melt mixing: the LAR CNTs are far stiffer than the HAR CNTs. At low loading levels, the former is dispersed as bent fibers or their small bundles, whereas the latter is dispersed as self‐entangled flocs, presenting far larger hydrodynamic radius than the former. At high loading levels, both are dispersed as flocs due to strong tube–tube interactions. However, the two CNTs show approximate average floc size and mesh size because they present same rigid length and effective aspect ratio. At identical loadings, therefore, the HAR CNTs have more total number of flocs than that of the LAR CNTs, forming network with more compact structure and imparting higher contributions to properties of the composites as a result. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 479–489, 2010     

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.     

聚氯乙烯/纳米水滑石复合材料的形态与力学性能

对由原位悬浮聚合制备的聚氯乙烯(PVC)纳米水滑石复合树脂加工得到的纳米复合材料的形态和力学性能进行了研究,并与直接熔融加工得到的PVC纳米水滑石复合材料进行比较.发现由前一方法得到的PVC纳米水滑石复合材料中纳米水滑石的分散性明显优于由后一方法得到的PVC纳米水滑石复合材料,水滑石以初级粒子形式存在,分散良好,无明显团聚体;与之对应,由前一方法得到的PVC纳米水滑石复合材料的力学性能也明显优于由后一方法得到的PVC纳米水滑石复合材料,当纳米水滑石含量小于5wt%时,复合材料的杨氏摸量、拉伸强度和缺口冲击强度均随水滑石含量增加而增大;纳米水滑石的引入可显著提高复合树脂的热稳定性;PVC纳米水滑石复合材料的储能和损耗模量略大于纯PVC材料,而损耗因子和玻璃化温度变化不大.     

Preparation and properties of natural rubber composites reinforced with pretreated carbon nanotubes

In order to achieve dramatic improvements in the performance of rubber materials, the development of carbon nanotube (CNT)‐reinforced rubber composites was attempted. The CNT/natural rubber (NR) nanocomposite was prepared through solvent mixing on the basis of pretreatment of CNTs. Thermal properties, vulcanization characteristics, and physical and mechanical properties of the CNT/NR nanocomposites were characterized in contrast to the carbon black (CB)/NR composite. Through the addition of the CNTs treated using acid bath followed by ball milling with HRH (hydrated silica, resorcinol, and hexamethylene tetramine) bonding systems, the crystallization melting peak in differential scanning calorimetry (DSC) curves of NR weakened and the curing rate of NR slightly decreased. Meanwhile, the over‐curing reversion of CNT/NR nanocomposites was alleviated. The dispersion of the treated CNTs in the rubber matrix and interfacial bonding between them were rather good. The mechanical properties of the CNT‐reinforced NR showed a considerable increase compared to the neat NR and traditional CB/NR composite. At the same time, the CNT/NR nanocomposites exhibited better rebound resilience and dynamic compression properties. The storage modulus of the CNT/NR nanocomposites greatly exceeds that of neat NR and CB/NR composites under all temperature regions. The thermal stability of NR was also obviously improved with the addition of the treated CNTs. Copyright © 2008 John Wiley & Sons, Ltd.