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Plasma Treatment and Polymerization of Textile Reinforcing Materials 纺织增强材料的等离子体处理和聚合
Pub Date : 2006-01-01 DOI: 10.2324/EJSM.2.25
Hudec Ivan, J. Michal, Krump Henrich, Cernak Mirko, S. Viera
In this paper different types of surface modification of polyester cords by low-temperature plasma at atmospheric pressure was studied.The first type cords were activated by pulse surface positive corona discharge generated in a plasma reactor or by coplanar dielectric surface barier discharge (DCSBD) in nitrogen or ambient air plasma at atmospheric pressure. The values of the static and dynamic adhesion of untreated cords and the plasma treated cords demonstrated possitive influence of plasma surface treatment on the adhesion of cords to rubber. The mechanical properties were not significantly affected by plasma treatment.The second type of plasma treatment involved the modification of cords by plasma polymerization in mixture of nitrogene with butadiene. The plasma layer homogenously coated the cords surface. The results shove, that values of static and dynamic adhesion for plasma polymerisation of treated cords are comparable with the standard chemical treatment based on resorcinol-formaldehyde latex (RFL).From the study of the surface properties of the plasma treated cords by SEM, AFM and XPS is evident that both chemical interactions and morphological changes of the surface cord fibres are responsible for the improved adhesion between treated reinforcing materials and rubber blend.
本文研究了常压低温等离子体对不同类型聚酯线的表面改性。第一种类型的线是在等离子体反应器中产生的脉冲表面正电晕放电或在氮气或大气等离子体中共面介质表面阻挡放电(DCSBD)激活的。未处理和等离子体处理的绳静态和动态粘附值表明,等离子体表面处理对绳与橡胶的粘附有积极的影响。等离子体处理对材料的力学性能无显著影响。第二类等离子体处理涉及在氮气和丁二烯的混合物中通过等离子体聚合修饰绳索。等离子体层均匀地覆盖在脐带表面。结果表明,处理后的脐带等离子体聚合的静态和动态粘附值与基于间苯二酚-甲醛乳胶(RFL)的标准化学处理相当。通过扫描电镜(SEM)、原子力显微镜(AFM)和XPS对等离子体处理后脐带的表面特性进行了研究,结果表明,化学相互作用和表面脐带纤维的形态变化是增强材料与橡胶共混物粘合性能提高的原因。
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引用次数: 2
Heat-Aging Effects on the Material Properties and Fatigue Life Prediction of Vulcanized Natural Rubber 热老化对硫化天然橡胶材料性能及疲劳寿命预测的影响
Pub Date : 2006-01-01 DOI: 10.2324/EJSM.2.7
C. Woo, W. Kim
The fatigue analysis and lifetime evaluation are very important in design procedure to assure the safety and reliability of the rubber components. Heat-aging process affects not only the material properties but also the fatigue life of vulcanized natural rubber. In this paper, the heat-aging effects on the material properties and fatigue life prediction of natural rubber were experimentally investigated. The stress-strain curves were obtained from the results of tensile test. The rubber specimens were heat-aged in an oven at the temperature ranging from 50°C to 100°C for a period ranging from 1 day to 90 days. Fatigue life prediction methodology of vulcanized natural rubber was proposed by incorporating the finite element analysis and fatigue damage parameter determined from fatigue test. Fatigue life tests were performed using the 3-dimensional dumbbell specimen, which were aged in different amounts. The Green-Lagrange strain at the critical location determined from the finite element method used for evaluating the fatigue damage parameter. Fatigue life prediction equation effectively represented by a single function using the Green-Lagrange strain.
疲劳分析和寿命评估是保证橡胶构件安全可靠运行的重要环节。热老化过程不仅影响材料性能,而且影响硫化天然橡胶的疲劳寿命。实验研究了热老化对天然橡胶材料性能和疲劳寿命预测的影响。根据拉伸试验结果得到了应力-应变曲线。橡胶试样在50 ~ 100℃的烘箱中热老化1 ~ 90天。提出了将有限元分析与疲劳损伤参数相结合的硫化天然橡胶疲劳寿命预测方法。采用不同老化量的三维哑铃试样进行疲劳寿命试验。采用有限元法确定临界位置的格林-拉格朗日应变,用于评估疲劳损伤参数。疲劳寿命预测方程用格林-拉格朗日应变有效地表示为单一函数。
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引用次数: 9
Degradation Analysis of NBR and Epichlorohydrin Rubber by New Micro Analysis Method 新型微分析法对丁腈橡胶和环氧氯丙烷橡胶的降解分析
Pub Date : 2006-01-01 DOI: 10.2324/EJSM.2.20
H. Katoh, R. Kamoto, J. Murata
The degradation analysis of NBR and Epichlorohydrin rubber was carried out by infrared micro spectroscopy (μ-IR) and micro sampling mass spectrometry (μ-MS) which gives information on the scission and crosslinking of rubber molecules. Samples were prepared by three different treatments, heat as well as ultra violet (UV) and electron beam (EB) irradiations.It was found for NBR vulcanizates that the heat treatment induced the oxidation, scission and crosslinking of rubber molecules. By the UV treatment, chain scission and crosslinking accompanied by a slight oxidation were induced. The EB treatment enhanced the crosslinking, however, the extent of oxidation was negligible. For Epichlorohydrin rubber vulcanizates, the heat treatment accelerated chain scission rather than crosslinking. On the other hand, the oxidation and crosslinking were induced by the UV and EB treatments.
采用红外微光谱(μ-IR)和微采样质谱(μ-MS)对丁腈橡胶和环氧氯丙烷橡胶进行了降解分析,揭示了橡胶分子的断裂和交联过程。样品经过三种不同的处理,加热,紫外线(UV)和电子束(EB)照射。研究发现,丁腈橡胶硫化胶的热处理引起了橡胶分子的氧化、断裂和交联。在紫外处理下,可诱导断链和交联,并伴有轻微的氧化反应。EB处理增强了交联,但氧化程度可以忽略不计。对于环氧氯丙烷橡胶硫化物,热处理加速了链断裂而不是交联。另一方面,UV和EB处理诱导了氧化和交联。
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引用次数: 4
Preparation and Properties of Clay/SEBS Intercalated Composites 粘土/SEBS插层复合材料的制备及性能研究
Pub Date : 2006-01-01 DOI: 10.2324/EJSM.2.1
T. Yamaguchi, E. Yamada
Clay/polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene triblock copolymer (SEBS) intercalated composites were prepared by melt-blending. The clays were a pristine montmorillonite (Mt) and three organically modified montmorillonites (organo-Mts) with different amounts of distearyldimethylammonium (D18) cation. The amounts of D18 were 50, 70 and 100% of the cation exchange capacity (denoted as D18Mt(50), D18Mt(70) and D18Mt(100), respectively). The clay/SEBS composites were characterized by field-emission scanning electron microscopy (FE-SEM), X-ray diffraction analysis (XRD). The dynamic mechanical analysis (DMA) and the tensile properties were also examined.The size of agglomerated clay particles decreased with the increasing amount of D18. The FE-SEM image of D18Mt(100)/SEBS revealed that the clay particles were dispersed at the sub-μm level (100–500 nm). The XRD patterns suggested that the SEBS chains were inserted into the interlayers of the organo-Mts. The DMA curves indicated that the addition of the organo-Mts produced an increase in the storage modulus in the rubbery plateau region, but a slight decrease in the glass transition temperature of the polystyrene domains. The tensile properties of the organo-Mt/SEBS composites were higher than those of the unmodified Mt/SEBS. D18Mt(100)/SEBS displayed an improved tensile modulus, tear strength and hardness compared to pure SEBS, without sacrificing the tensile strength and elongation at break.
采用熔融共混法制备了粘土/聚苯乙烯-b-聚(乙烯-共丁烯)-b-聚苯乙烯三嵌段共聚物(SEBS)插层复合材料。粘土是一种原始蒙脱土(Mt)和三种有机改性蒙脱土(organo-Mts),具有不同量的二硬脂基二甲基铵(D18)阳离子。D18的用量分别为阳离子交换容量的50%、70%和100%(分别记为D18Mt(50)、D18Mt(70)和D18Mt(100))。采用场发射扫描电镜(FE-SEM)、x射线衍射分析(XRD)对粘土/SEBS复合材料进行了表征。动态力学分析(DMA)和拉伸性能也进行了测试。随着D18添加量的增加,黏土颗粒团聚度减小。D18Mt(100)/SEBS的FE-SEM图像显示,粘土颗粒分散在亚μm级(100 - 500 nm)。XRD谱图表明,SEBS链插入到有机mts的中间层中。DMA曲线表明,有机mts的加入提高了橡胶平台区的储存模量,但降低了聚苯乙烯区域的玻璃化转变温度。有机Mt/SEBS复合材料的拉伸性能高于未改性Mt/SEBS。与纯SEBS相比,D18Mt(100)/SEBS在不牺牲拉伸强度和断裂伸长率的情况下,表现出更高的拉伸模量、撕裂强度和硬度。
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引用次数: 3
Structure-Properties of Acrylic Rubber/Epoxy Adhesive by Reaction-Induced Phase Decomposition 反应诱导相分解制备丙烯酸橡胶/环氧胶粘剂的结构与性能
Pub Date : 2006-01-01 DOI: 10.2324/EJSM.2.13
Tetsuro Iwakura, T. Inada, M. Kader, Takashi Inoue
The advancement in the miniaturization of electric devices requires high performance diebond adhesive films for semiconductor packages. The diebond film should have high thermal-stress resistance and good retention of adhesive properties. To achieve such performance and reliability, we choose a rubber-rich epoxy adhesive. In the present work, we investigated the influence of reactive site of acrylic rubber (ACM), cure agent and curing condition on the performance of diebond film. In the early stage of curing, ACM/epoxy/curing agent (e.g., DDM: diaminodiphenylmethane) system was a single-phase mixture. As the cure reaction proceeded, phase separation took place via the spinodal decomposition, induced by the increase in the molecular weight of epoxy. The reaction-induced spinodal decomposition was confirmed by the characteristic change in light scattering profile with curing time. Phase contrast microscopy and atomic force microscopy also revealed the formation of regularly phase-separated structure characteristic to the spinodal decomposition. The periodic distance of the structure varied in a wide range, from a few μm to ten nm. The higher amount of reactive site (glycidylmethacrylate) in ACM and the lower cure temperature rendered the shorter periodic distance. The shorter periodic distance yielded the higher adhesive strength. However, much shorter distance of 10 nm resulted in poor adhesive strength. The sub-μm structure seems to lead to optimum strength. The 10 nm structure material showed low thermal expansion and nice transparency.
随着电子器件小型化的发展,半导体封装需要高性能的二粘胶膜。二粘膜应具有较高的耐热性和良好的粘接性能。为了达到这样的性能和可靠性,我们选择了富含橡胶的环氧胶粘剂。本文研究了丙烯酸橡胶(ACM)的反应部位、固化剂和固化条件对二粘膜性能的影响。在固化初期,ACM/环氧树脂/固化剂(如DDM:二氨基二苯甲烷)体系为单相混合物。随着固化反应的进行,由于环氧树脂分子量的增加,通过spinodal分解发生相分离。光散射曲线随固化时间的特征变化证实了反应诱导的spinodal分解。相衬显微镜和原子力显微镜也发现了有规律的相分离结构的形成,这是spinodal分解的特征。该结构的周期距离变化范围很广,从几μm到十nm不等。ACM中活性位点(甲基丙烯酸缩水甘油酯)用量越高,固化温度越低,周期距离越短。周期距离越短,粘接强度越高。然而,10 nm的距离较短,导致粘接强度较差。亚μm结构可以获得最佳强度。10 nm结构材料热膨胀小,透明度好。
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引用次数: 9
Polymerization of 1,3-Butadiene with NiCl2 in Combination with Methylaluminoxane 1,3-丁二烯与NiCl2与甲基铝氧烷结合聚合的研究
Pub Date : 2006-01-01 DOI: 10.2324/EJSM.2.42
K. Endo, Y. Yamanaka
The polymerization of 1,3-butadiene (Bd) with NiCl2/methylaluminoxane (MAO) catalyst was investigated. The reaction mixture of NiCl2 and MAO was separated into soluble and insoluble part. Both parts initiated the polymerization of Bd to give a high cis-1,4-poly(Bd). The activity for the polymerization of the soluble part was higher than that of the insoluble part. The Mw/Mn of the polymer obtained with the soluble part was around 2.0, but that obtained with the insoluble part was 4.5. The polymerization of Bd with NiCl2 in combination with MAO depended on a particle size, i.e., surface area of NiCl2, and the activity for the polymerization with a small particle size of NiCl2 was higher than that with a large particle.
这两部分都引发了Bd的聚合,得到了高顺式1,4聚(Bd)。可溶部分的聚合活性高于不溶部分。可溶部分得到的聚合物的Mw/Mn约为2.0,而不溶部分得到的聚合物的Mw/Mn为4.5。
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引用次数: 0
Physical Gelation of Syndiotactic Polystyrene in the Presence of Poly(ethylene oxide) 聚环氧乙烷存在下顺规聚苯乙烯的物理凝胶化
Pub Date : 2006-01-01 DOI: 10.2324/EJSM.2.31
K. Senoo, S. Matsuda, S. Kohjiya
Syndiotactic polystyrene (s-PS) in dichloroethane (DCE) was gelated thermoreversibly in the presence of poly(ethylene oxide) (PEO). The effect of the dosage and molecular weight of coexistent PEO on the gelation has been investigated. The gelation temperature increased with increasing the composition ratio of PEO to DCE and the molecular weight of PEO. Wide angle X ray diffraction measurements revealed that an increase of the composition ratio of PEO to DCE in the gel led to change the crystal structure of s-PS from a helical conformation to a trans-zigzag one.When DCE was removed from the gel completely by drying under vacuum at 70°C for 24 hours, a novel polymer blend consisting of s-PS and PEO was obtained. Dynamic modulus analysis measurements revealed that it had a unique long rubbery plateau from a grass transition temperature (Tg) or a melting temperature (Tm) of PEO’s depending with their molecular weights to Tm of s-PS. It indicates that the crystallite of s-PS not only plays a role of the network junction in the polymer blend but also prevents the macroscopic phase separation between s-PS and PEO.
在聚环氧乙烷(PEO)存在下,以二氯乙烷(DCE)为原料制备了顺二规聚苯乙烯(s-PS)。研究了共存PEO的用量和分子量对凝胶化的影响。随着PEO与DCE的组成比和PEO分子量的增加,凝胶温度升高。广角X射线衍射测量表明,凝胶中PEO与DCE组成比的增加导致s-PS的晶体结构由螺旋构象转变为反之字形构象。在70°C真空干燥24小时后,将DCE从凝胶中完全去除,得到了一种由s-PS和PEO组成的新型聚合物共混物。动态模量分析表明,从PEO的草化温度(Tg)或熔化温度(Tm)到s-PS的Tm, PEO具有独特的长橡胶平台,这取决于PEO的分子量。结果表明,s-PS的结晶不仅在共混聚合物中起到了网络连接的作用,而且还阻止了s-PS与PEO的宏观相分离。
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引用次数: 0
The Main Mechanism and Cross-Linking Structure for Accelerated Sulfur Vulcanization 硫加速硫化的主要机理及交联结构
Pub Date : 2006-01-01 DOI: 10.2324/EJSM.2.47
W. Choi
The reactivities of hydrocarbon, the radical reactions through the allylic radicals, the results of model compound vulcanization, and the cross-link structures of vulcanizates are comprehensively discussed to understand the main reaction for accelerated sulfur vulcanization. Through this review, the author's view on the main mechanism and cross-linking structure for accelerated sulfur vulcanization are discussed.
从烃类的反应活性、烯丙基自由基的自由基反应、模型化合物的硫化结果以及硫化胶的交联结构等方面进行了综合讨论,以了解硫加速硫化的主要反应。通过综述,讨论了硫加速硫化的主要机理和交联结构。
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引用次数: 10
Poly(ethylene oxide)-Based Composite Electrolytes Filled with Periodic Mesoporous Silica for Solid State Ionics 固态离子用周期性介孔二氧化硅填充聚环氧乙烷基复合电解质
Pub Date : 2005-01-01 DOI: 10.2324/EJSM.1.14
Y. Tominaga, M. Morita, S. Asai, M. Sumita
Mesoporous silica (MPS) was used for poly(ethylene oxide) (PEO)-based solid polymer electrolytes as novel inorganic filler. For improvement in ionic conductivity in solid state, a room temperature ionic liquid (IL), 1-ethyl-3-methylimidazolium tetrafluoroborate, was introduced into periodic nano-tunnels of MPS, and the modified MPS (IL-MPS) was filled with PEO-LiBF4 electrolyte. Ionic conductivity of neat-MPS-filled composites was approximately 4-fold higher than that of the original electrolyte. On the other hand, the conductivity was more than 11-fold enhanced by addition of IL-MPS, to be more than 10−6 S/cm at 30°C and at least 10 wt% silica contents. The conductivity increased with increasing IL-MPS contents, to be a maximum value of approximately 3×10−6 S/cm at 30°C and at 40 wt%. Dynamic mechanical measurements for neat- and IL-MPS composites revealed that the addition of fillers improves storage modulus of PEO-based electrolytes at room temperature. The addition of IL-MPS was able to realize the improvement in both ionic conductivity and storage modulus.
介孔二氧化硅(MPS)作为新型无机填料用于聚环氧乙烷(PEO)基固体聚合物电解质。为了提高固态离子电导率,将室温离子液体(IL) - 1-乙基-3-甲基咪唑四氟硼酸盐引入到MPS的周期性纳米通道中,并将改性后的MPS (IL-MPS)填充到PEO-LiBF4电解质中。净mps填充复合材料的离子电导率约为原始电解质的4倍。另一方面,IL-MPS的加入使其电导率提高了11倍以上,在30°C和至少10 wt%二氧化硅含量下,电导率超过10−6 S/cm。电导率随着IL-MPS含量的增加而增加,在30°C和40% wt%时的最大值约为3×10−6 S/cm。对纯聚合物和IL-MPS复合材料的动态力学测量表明,填料的加入提高了peo基电解质在室温下的存储模量。IL-MPS的加入可以实现离子电导率和存储模量的提高。
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引用次数: 6
1,4-Cis Selectivity and Molecular Weight Control of Polymer in the Polymerization of 1,3-Butadiene with Metallosalen Complexes/Methylaluminoxane Catalysts 金属盐配合物/甲基铝氧烷催化剂聚合1,3-丁二烯时聚合物的1,4-顺式选择性及分子量控制
Pub Date : 2005-01-01 DOI: 10.2324/EJSM.1.8
K. Endo, Takahiro Kitagawa
1,4-Cis-selective and molecular weight control of the polymer in the polymerization of butadiene (Bd) with various metallosalen [metal=Co, Ni, Fe, V, Ti; salen=N,N′-bis(salicylidene)ethylenediamine] in combination with methylaluminoxane (MAO) was investigated. The activity for the polymerization of Bd was influenced by both substituents of the salen ligands and mixing order of reagents. The activity for the polymerization of Bd with metallosalen complexes activated by MAO in the presence of Bd was higher than that in the absence of Bd. By introducing the tert-butyl group in the aromatic ring of salen, the activity for the polymerization of Bd increased, but the microstructure of the poly(Bd) did not change significantly. Among the metallosalen complexes examined, N,N′-bis(3,5-di-tert-butylsalicylidene)ethylenediaminato Co(II) (1-Co) complex in combination with MAO gave the high molecular weight polymer with highest 1,4-cis content. Molecular weight control of the polymer was achieved by the polymerization of Bd with 1-Co/MAO catalyst.
丁二烯(Bd)与多种金属[金属=Co, Ni, Fe, V, Ti]聚合过程中聚合物的1,4-顺式选择性及分子量控制双酚a的聚合活性受两种配体取代基和试剂混合顺序的影响。
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引用次数: 2
期刊
E-journal of Soft Materials
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