RFL 浸胶和橡胶的粘合机理待续

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ADHESION OF RFL-TREATED CORDS TO RUBBER
NEW INSIGHTS INTO INTERFACIAL PHENOMENA
RFL浸胶帘线与橡胶的粘合
对粘合界面的最新认识

Chapter 1 Introduction: cord-rubber composites
A brief introduction is given about the importance of cord-rubber composites. The example of a car-tyre shows that the cords carry all the loads that a tyre is subjected to; this is illustrated by a comparison between bias and radial tyres. The adhesion between cords and rubber is very important with regard to safety as well as durability of tyres. In this chapter, the objective of the project is defined and a description of the setup of the thesis is outlined.
第一章简介帘线-橡胶的复合体
本节简单介绍了帘线-橡胶复合体的重要性：比如，汽车轮胎，帘线承载轮胎的所有负荷，帘线与橡胶之间的粘合力对轮胎的使用寿命、安全性能非常重要，本章将简述项目的目标和本论文的结构。

1.1 INTRODUCTION  引言
Cord-rubber composites can be found in every day life. Examples of applications are car- and bicycle tyres, high-pressure hoses and conveyor belts. Some essential under-the-hood applications are made of cord-rubber composites as well: timing belts, V-belts and radiator hoses are examples. By far the largest of all these examples is the car tyre. The application of cords in tyres is essential because the cords prevent large deformations of the rubber material when excessive forces are applied. These forces are caused by the air pressure of the tyre, and by accelerating, breaking and cornering of the car. The network of cords that provides the tyre with its strength and its shape is called the carcass. There are two types of carcass constructions in use, thereby dividing virtually all tyres in two categories: radial and bias tyres, Figure 1.1.1
帘线和橡胶的复合体在日常生活中到处可见，比如汽车和自行车轮胎、高压胶管和橡胶输送带，包括汽车发动机室用的重要同步带、V带和散热水管等等。目前应用最大的就是汽车轮胎。在轮胎转向、加速、刹车时，轮胎会出现受力过大的情况，轮胎中的帘线可以避免轮胎中橡胶因受力增大出现大幅度变形。帘线的网状结构，给轮胎提供了强度以及外形。根据轮胎的骨架结构，轮胎分为两大类：斜交轮胎和织物轮胎。见图1.1.1
1.1.1 Bias tyre construction 斜交轮胎
The oldest tyre construction is called bias or cross ply: Figure 1.1A. A bias tyre has a casing which is made of stacked reinforcing layers of cords, called plies, crossing over each other at an angle of 30¡ã to 40¡ã to the centre line of the tyre. These stacked plies reinforce both the tread and the sidewall and must therefore resist the forces caused by cornering, accelerating and breaking, but also maintain the shape of the tyre. Because of the required flexibility of the tyre sidewall, the all-sided reinforcement causes the tread to deform as well when driving over obstacles. This causes rapid wear, lower traction and higher fuel consumption compared to more recent radial tyres.
老式的轮胎结构称做斜交轮胎，如图1.1A所示斜交轮胎类似于用帘子布做成的一个罩盖，每层帘子布相互之间交叉排放，与轮胎的中心线形成一个30-40度的夹角。层叠起来的帘子布不仅要增强轮胎的胎体，同时要增强轮胎的胎侧，在能够抵抗转向、制动、加速的力量的同时，以保持轮胎的形状不变，由于轮胎的胎侧需要柔软性，因此轮胎通过障碍时，胎侧就会造成胎体的变形，从而造成轮胎的快速磨损，牵引力下降，能耗上升。而子午线轮胎就不会出现这种情况。
1.1.2 Radial tyre construction 子午线轮胎
The first commercial tyre with radial belt construction was produced by Michelin in 1948: the ¡®Michelin X¡¯. A schematic reproduction of a radial tyre carcass is shown in Figure 1.1B. Textile cords are placed at 90¡ã to the direction of travel from bead to bead, designed to hold the air pressure and carry the load of the car. These cords are flexible and large deflections are allowed to absorb obstacles on the road for comfort. However, positioning the reinforcing cords in this direction, there is insufficient stabilisation of the circumference of the tyre, and the control and steering properties would be completely unacceptable. Therefore, additional plies of high modulus cords, usually steel, are placed at an angle of 16¡ã to 25¡ã underneath the tread. These plies are designed to carry the load caused by accelerating, breaking and cornering. The radial tyre separates the functions of the tread and the sidewall, where the bias tyre compromises the two.
子午线轮胎是米其林在1948年最先应用在商业轮胎上的。图1.1B所示是子午线轮胎的结构图，纺织材料的帘线和轮胎运动方向成90度夹角，用于承受气压和汽车的重量。这些帘线有更好的柔软性，更大的变形能力，吸收道路上障碍，乘坐舒适。但这样方向布置的帘线，轮胎圆周方向的稳定性就差，其操控性能是无法接受。所以，因此通常采用钢丝一类的高模量帘线，和带束成16-25度的夹角，这些帘线承受转向、制动、加速所产生的负荷，子午线轮胎将带束层和胎体层功能的帘线分开，而斜交轮胎则是合并在一起的用一种帘线。
1.1.3 Safety issues regarding tyres
A proper reinforcement of a tyre is essential, not only for comfort and handling, but the tyre is also an important part of the car regarding safety. Even under extreme conditions, low tyre pressure, hot weather or during an emergency break, the tyres must remain intact since it represents the connection between the car and the road. Actually, with modern porous asphalt (Dutch: ¡°ZOAB¡±) road coverage, the real contact surface between tyre and road is of the size of a large postal stamp.2 This clearly illustrates the sensitivity of this technology for safety.
轮胎必须得到正确的增强，不仅是为了舒适性和可操纵性，同时轮胎也是汽车的一个重要的安全部件，由于轮胎将汽车和道路之间连接部件，即使遇到很恶劣的环境，气压不足，高温天气，紧急刹车，轮胎必须保持完好，实际上，在如今的槽面柏油路面上，轮胎和道路之间接触就像一个大邮戳的图章，这说明这一技术对安全的敏感性。
In 2001, certain types of Firestone tyres installed on Ford Explorer SUV¡¯s, separated causing the vehicles to tumble. In the USA, this caused 174 deaths, more than 700 injuries and around 6000 complaints of tyre blow-outs at highway speeds.3 Most of the accidents happened in the warm southern states.4 For both Ford and Firestone the financial damage was enormous, because of the lawsuits involved5 and the need to recall nearly 20 million tyres and more than 100.000 cars6, 7: see the newspaper article in Figure 1.2. Firestone blamed Ford for advising a too low tyre pressure and Ford blamed Firestone for using dried-out rubber, resulting in insufficient adhesion between the tyre tread and the rest of the tyre.
2001年，菲尔斯通安装在福特开拓者SUV上的轮胎爆裂，造成汽车出现翻滚，在美国，造成174人死亡，700多人受伤，6000多起投诉在高速公路上轮胎爆裂。绝大多数事故发生在温暖的南方省份，由于诉讼包括需要召回2000万条轮胎和10万辆汽车，造成福特和菲尔斯通的绝大的财务损失，详见图1.2所示的报纸新闻，菲尔斯通抱怨福特建议的轮胎胎压太低，而福特抱怨菲尔斯通干硬的橡胶，导致轮胎帘线和轮胎其他部分的粘合力不够。
The Ford/Firestone incident illustrates the importance of tyres regarding vehicle safety and thereby the importance of good adhesion between all the tyre parts. Because the reinforcing cords carry all the loads where the tyres are subjected to, sufficient adhesion between rubber and cords is therefore indispensable to transfer the loads from rubber to cord effectively; not only for the new tyre, but throughout its whole life, which may last more than 10 years under often adverse conditions.
福特和菲尔斯通的事故，说明了轮胎的重要性，以及轮胎各个部件粘合的重要性。由于帘线承受轮胎的所有负荷，因此橡胶和帘线之间的有效粘合是有效地将负荷从橡胶传递给帘线过程中必不可少的。这不仅仅针对新轮胎而言，需确保轮胎高达10多年在恶劣环境下的使用寿命。
Figure 1.2 Article in the New York Times from May 21st 2001

1.2 AIM OF THE RESEARCH IN THIS THESIS 本论文的研究目的
Textile cords used in rubber applications are commonly treated with a so-called Resorcinol Formaldehyde Latex (RFL) dip. Despite the relevance of good adhesion between cords and rubber, and although this system dates back as far as 19388 and is still commonly used for rubber reinforcement till today, the mechanism by which the adhesion is obtained has remained unclear. The level of knowledge of adhesion between RFL-treated cords and rubber today is empirical rather than scientific. With new and stronger fibre materials introduced in recent years, in particular aramid fibres, it was considered appropriate to revisit the fibre-rubber adhesion technology to obtain more fundamental knowledge of the physical and chemical processes involved in the adhesion between RFL-treated cords and rubber.
橡胶制品中的帘子线通常是进行间苯二酚/甲醛/胶乳，称做RFL浸胶处理的。这一浸胶方式，可以追溯到1938年，而且至今依然用于橡胶骨架材料的处理上。其粘合机理，至今依然不是十分清晰。有关RFL处理后的帘线与橡胶的粘合的知识，依然是经验推断多于科学分析。如今新型高强度材料的开发，特别是芳纶纤维，需要我们来回顾以往的有关纤维和橡胶粘合的知识，获得包括RFL浸胶处理的帘线与橡胶之间粘合在内的有关物理、化学处理过程的基础知识。
1.3 STRUCTURE OF THIS THESIS  本论文的结构
A literature survey on cord-rubber composites is presented in Chapter 2. The focus is on research published on the standard RFL treatment and the double dip treatment used for aramid and polyester cords to enhance the adhesion with rubber compounds.
第二章将简述有关已经发表的的帘线橡胶复合体的论文，重点是已经发表的关于标准的RFL处理，以及用于提高与橡胶粘合力的，芳纶和聚酯帘线双浴浸胶的相关研究。
In Chapter 3, a study is described regarding the influence of rubber curatives in the rubber compound on vulcanisates properties, as well as on the adhesion to RFL-treated aramid cords. The amounts of the rubber curatives are varied using an experimental setup obtained by Design of Experiments.
第三章，研究描述橡胶硫化组分对硫化特性以及与RFL处理的芳纶帘线粘合力影响，橡胶硫化组分的用量的变化，将根据试验设计确定。
A Scanning Electron Microscope coupled to an Energy Dispersive X-ray spectrometer (SEM-EDX) is used to analyse the interfaces between rubber compound and RFL-dip, as reported in Chapter 4. The technique SEM-EDX is a local elemental analysis and, because the amount of rubber curatives is varied in the rubber, the distribution of the atoms sulphur and zinc through this interface is of particular interest.
在第四章，报告了用扫描电子显微镜和能量衍射X射线分光光度机对RFL浸胶层和橡胶界面的分析。扫描电镜技术仅仅是局部的基本分析，由于橡胶组分在橡胶中的分散不均匀，硫和锌原子在界面上的分布也有特别的兴趣。
Several attempts to change the atomic sulphur distribution in the RFL-rubber interface and to measure the effect on the adhesion are described in Chapter 5.
第五章，描述了对改变硫原子在RFL-橡胶界面的分布的尝试，来测定粘合力的效果。
The influence of the type of latex used in the RFL formulation, on the adhesion to several rubber compounds, is the subject of Chapter 6. The influence of vinylpyridine as co-monomer in the latex is studied.
第六章的主题是RFL配方中的不同种类胶乳对几种橡胶的粘合力影响，研究了吡啶作为胶乳中的共单体的影响
Chapter 7 deals with a model compound vulcanisation study with squalene as a model. The physical interaction between model compounds and ground RFL powder at different stages of vulcanisation is determined.
第七章研究了
The exact migrating species, as well as the moment the formation of these species takes place during vulcanisation of real rubber systems are described in Chapter 8 because these species turn out to be the crucial players in adhesion development.
在实际橡胶的硫化中发生实际迁移的物质以及这些物质形成过程在第八章进行了描述，因为这些物质在形成粘合过程中起到十分关键的作用
In Chapter 9 this thesis is completed by summarising and evaluating the results.
第九章，是本论文的总结和结果的评估
REFERENCES  参考文献
1. T. French, "Tyre Technology". 1988, New York: Adam Hilger.
2. Private communication Continental Tyres, Hannover, Germany.
3. J. Hadley, Safety remains an issue with tyres, in "Seattle Post-Intelligencer". 2001, June4.
4. Website available from: [url]http://nhsta.dot.gov.[/url]
5. J. Vertuno, Firestone to pay $6.5 million to woman's family, in "Seattle Post-Intelligencer". 2001, August 20.
6. K.N. Gilpin, Firestone to recall 3.5 million more SUV tires, in "The New York Times". 2001, October 1.
7. K. Bradsher, After a century, Firestone halts tire sales to Ford, in "The New York Times". 2001, May 21.
8. W.H. Charch, N.Y. Buffalo, and D.B. Maney, (US2128635) DuPont, 1938.
Chapter 2 Literature survey:
第二章  文献回顾
The present chapter provides an overview of literature published on fibre/rubber composites. A brief history of fibres used in rubber applications is given, but the emphasis is on the adhesion between fibre materials and rubber compounds. Extra attention is given to the standard RFL-treatment and the double dip treatment used for aramid and polyester fibres to enhance the adhesion with rubber compounds. Some alternatives to the RFL- treatment are described: fibre surface roughening, adhesion promoter additives to the rubber compound, impregnated fibre plasma treatment.
本节是已发表的关于纤维和橡胶复合体的研究文献的回顾，简单介绍了橡胶行业中应用纤维的历史，其重点纤维材料和橡胶之间的粘合，特别关注了对芳纶和聚酯纤维进行标准的RFL处理和双浴浸胶处理来提高与橡胶的粘合力。同时介绍了几种替代RFL处理的方法，比如纤维表面的粗糙化处理，在橡胶中添加粘合促进剂，纤维的等离子处理。
2.1 INTRODUCTION 概述
Fibre reinforced rubber compounds play a crucial role in (high-pressure) hoses, transmission belts, conveyor belts and tyres. Until about 1890, only natural fibres were available. Just before the end of the 19th century the first synthetic fibres based on cellulose were developed. Cellulose is an insoluble substance and in order to make this soluble, several derivations were tried. The first attempt was nitration, but cellulose nitrate proved to be more useful as guncotton than as a fibre. Cooper rayon and viscose rayon followed1; the latter became the first large-volume synthetic fibre material. These cellulose yarns are considered to be half-synthetic, because the raw material is still a natural polymer: cellulose. DuPont developed the first fully synthetic fibre Nylon. 66 or Polyamide 66; it was commercially introduced in 1936 (Carothers). A few years later, Polyamide 6 (Schlack, 1941) and Polyester (Whinfield & Dickson, 1942) were introduced. The development of ¡°advanced fibres¡± took place around 1970. Most of these fibres were produced from fully aromatic polymers with high temperature stability. Eventually, this led to the discovery of the liquid-crystalline behaviour of PPTA (paraphenylene terephthalamide), the first super-strong fibre. The companies DuPont and Akzo Nobel started a patent conflict in 1979. The patents of DuPont2-5 as well as the patent of Akzo Nobel6 were necessary to produce this fibre. In 1988, the two companies reached a compromise. Nowadays, the PPTA fibre of DuPont is called Kevlar.. Akzo sold its fibre division and the PPTA fibre is now owned by Teijin; the brand name is Twaron.. The second super-strong fibre was gelspun polyethylene (Dyneema. of DSM, 1979).
在胶管、传动带、输送带和轮胎中，纤维增强的橡胶体，起到十分关键的作用。在1890年之前，仅仅只有天然纤维可以使用。在19世纪末叶，开发出第一种基于纤维素的人造纤维。纤维素是一种不能溶解的物质，为了将其溶解，进行了多种试验，最先是进行硝化处理，硝化的结果是更多地使用作为火棉。而不是用作纤维。随后是铜氨纤维以及粘胶纤维，后者成为大规模的人造纤维材料，纤维素纤维只能作为一种半合成纤维，因为其原料依然是一种天然的纤维素。杜邦最先开发了全合成的纤维-锦纶66，1936年开始商业化生产，过后不久，锦纶6在1941年，聚酯在1942年开始生产，到1970年才开始有更先进的纤维出现，绝大多数是由芳香族聚合体生产的，在高温下，具有良好的稳定性。这是由于发现了PPTA具有液态结晶的特性，一种超强的纤维。杜邦和阿克苏.诺贝尔之间由此引起了专利纠纷，杜邦的专利，以及阿克苏.诺贝尔的专利是生产这种纤维必不可少的，在1988年，两公司相互妥协，如今杜邦生产的PPTA纤维称做凯夫拉(KEVLAR)，而阿克苏的品牌名则为特万龙（TWARON）,阿克苏已经将其PPTA纤维业务部门卖给的日本的帝人公司，另一种高强度纤维是胶液纺的聚乙烯纤维。
The types of fibres used for reinforcing rubber are listed in Table 2.1, together with the year the fibre was invented and the year it was introduced in tyre reinforcement.
在橡胶中用作增强材料的纤维如表2.1所示，包括纤维的发明时间和用作轮胎增强的时间
Table 2.1 Types of fibres produced throughout history for tyre reinforcement
表2.1 历史上用于轮胎增强的各种纤维
Type of fibre year of invention Introduction in tyre reinforcement7
种类发明年份用于轮胎增强年份
Cotton app. 7000 years ago 1900
棉纱约7000年前
Viscose rayon 1885 1938
人造丝
Polyamide 66 1935 1947
锦纶66
Polyamide 6 1938 1947
锦纶
Polyethylene terephthalate 1941 1962
聚酯
Aromatic polyamide2-6 1969 1974
对位芳纶
Gelspun polyethylene 1979 -
高强聚乙烯

Table 2.2 Type of fibres used in tyres13
表2.2轮胎中使用的几种纤维
Tyre type Tyre part Standard    High performance Ultra high performance    Racing Run flat    Ultra light
(>300 km/h)
Carcass PET Rayon PET Rayon    Rayon Aramid PEN
胎体帘线
Rayon Aramid Rayon Rayon & steel PET Rayon Aramid

Belt Steel Steel Aramid Steel PEN Aramid Steel Aramid
带束层
Capply    no Polyamide Aramid Polyamide Aramid Polyamide Aramid Polyamide Aramid Polyamide Aramid
冠盖层
Chafer no Polyamide Aramid Polyamide Aramid Aramid Polyamide Aramid
子口
Bead Steel Steel Steel Steel Aramid Steel Steel Aramid
胎圈

Figure 2.1 Cross section of a tyre, indicating the areas important for fibre reinforcement
图2.1为轮胎的横截面，说明了轮胎的需用纤维增强的的各个重要部位

In Table 2.2, the types of fibres used in various parts of tyres are listed. In Figure 2.1, a cross section of a tyre is shown with the description of the various tyre parts. The types of fibres used in tyres are limited to polyamide, rayon, polyester, aramid and steel, because these materials are sufficiently temperature-resistant to survive the vulcanisation step in tyre manufacturing without weakening or complete disintegration. There is a large variety between these fibres in price and performance, hence the change in type of reinforcement with increasing demands. The main properties of the fibres are listed in Table 3.3.
表2.2列举了轮胎不同部位所用的纤维种类，图2.1为为轮胎的横截面，说明了轮胎的各个部位，轮胎中所用的纤维局限于锦纶、聚酯、人造丝、芳纶和钢丝，因为这些材料有足够的耐热性能能够承受轮胎硫化过程的高温，不会造成纤维的损伤，甚至完全分解，
Table 3.3 Properties and performance of several types of fibres
表3.3 几种纤维的性能特点
Rayon Polyamide 6 Polyamide 66 Polyester Aramid
粘胶锦纶6 锦纶66 聚酯芳纶
Density (kg/m3) 1520 1140 1140 1380 1440
密度
Moisture content* (%) 12-14 4 4 0.4 1.2-7
回潮率
Decomp. temp (¡ãC) 210 - - - 500
分解温度
Melting temp. (¡ãC) - 255 255 285 -
熔点
Glass transition temperature (¡ãC) - 50 57 69 >300
玻璃化温度
E-mod (cN/tex) 600-800 300 500 850 4000
模量
Tensile strength (MPa) 685-850 850 850 1100 2750
断裂强度
* measured at 65% relative humidity at 20¡ãC 在相对湿度为65%下检测的数值

The properties of Rayon were significantly improved between the 1930¡¯s and the 1970¡¯s. This was realised by making the Rayon denser and more uniform in structure. A major disadvantage of Rayon is its sensitivity to moisture. In moist conditions, its loss in strength is significant.
粘胶在1930年至1970年期间，由于密度提高和结构上更加均匀，性能有了极大的提高。粘胶的主要缺点是对湿度敏感，在高湿度的环境下，强度会大幅度下降。
Polyamide 6 is mostly used in automobile tyres in India and South America; polyamide 66 is used on a larger scale. For rubber reinforcement, polyamide 6 and polyamide 66 have the disadvantage of a low melting point and a low modulus. Therefore, they cannot be used in the carcass but only as a capply, above or around the steel belt.
锦纶6主要用于印度和南美洲的汽车轮胎，锦纶66用途最为广泛。在橡胶增强材料中，锦纶6和锦纶66存在熔点低（原文如此）和模量低的缺点。因此不能用作轮胎骨架，仅仅用作冠盖，用于包覆带束层的钢丝或放置在带束层的钢丝上。
Polyester fibres have a high modulus and a high tensile strength and are the single most important reinforcing material for tyres. However, there are two problems involved in using polyester for reinforcing rubber. The first problem is that polyester is chemically rather inert and it is therefore more difficult to obtain a sufficient level of adhesion to rubber compared to rayon and polyamide. The second problem is the thermal shrinkage. Various grades of polyester are available with varying shrinkage/modulus ratios.
聚酯纤维，具有较高的模量和强度，是重要的轮胎增强材料，但聚酯在使用中有两个问题，第一个问题是聚酯的化学惰性，因此与锦纶粘胶相比，很难获得足够的和橡胶的粘合力，第二问题是热收缩，不同等级的聚酯具有不同的收缩/模量比
Aramid fibres have a very high modulus and tensile strength. However, this is coupled to a very low value of elongation at break. The major disadvantage of this low elongation occurs when aramid is used in several layers. When flat, each layer contributes its own share of strength, but upon bending the outer layer causes a compression deformation of the inner layers: aramid performs poorly under compression. The elongation at break of an aramid fibre can be improved by applying a large twist factor. Next to this, there is the problem of poor adhesion, similar to polyester.
芳纶纤维模量、强度很高，但其与断裂伸长很低相连，这种低伸长使芳纶不适合多层使用，当平面场合，每层才可以共同承受受力，如果弯曲，外层能导致内层压缩变形：而芳纶不耐压缩。芳纶的断裂伸长可以用施加较大的捻系数进行改善，与聚酯一样，存在粘合力低的问题。

2.2 STANDARD ADHESIVE TREATMENTS OF FIBRES 纤维标准的粘合处理
When using fibres in combination with rubber, good adhesion is essential especially for high safety products such as tyres. The adhesion between untreated fibres and rubber is always low, because there is a significant difference in modulus and polarity between the reinforcing fibres and the rubber matrix. The type of adhesive treatment is dependent on the type of fibre used. In the case of cotton, one of the first fibres used in rubber, the only adhesive treatment necessary is drying the fibre. Cotton fibres are not smooth; filaments are sticking out of the surface of the fibre. These filaments are anchored in the rubber matrix. The frictional forces that need to be overcome to pull or strip the fibre out of the rubber result in a significant adhesion.
当需用纤维和橡胶相结合，尤其是像轮胎这样安全性能要求高的产品，必须要有良好的粘合力。未经处理的纤维，和橡胶的粘合力一般较低，这是因为其模量以及增强纤维和橡胶之间的极性差异很大。粘合力的处理方式依据所用的县委种类而定，如果是棉纤维，这是橡胶中使用的第一种纤维，所需的粘合力处理仅仅是将纤维干燥而已，因为棉纤维的表面不是光滑的，单纤维是伸出的，这些单纤维可以和橡胶起到铆接作用。克服将纤维剥离或拉出的摩擦力就形成了足够强的粘合力。
The (semi) man-made fibres such as regenerated cellulose and polyamide have a smooth surface; therefore, there is no interlocking of filaments. Furthermore, the mechanical properties of these fibres are higher compared to cotton and therefore a higher strength of the adhesion is required. This resulted in the Resorcinol Formaldehyde Latex treatment invented by W.H. Charch and D.B. Maney.14 For polyester fibres, the RFL-treatment alone is not sufficient due to the lack of polar and hydrogen bonding groups in its chemical structure. In case of aramid fibres, the bulky aromatic groups sterically hinder the amide functionalities. Therefore, both polyester and aramid fibres are treated with a predip before being treated with a standard RFL-dip. An outline of the RFL-treatment is schematically depicted in Figure 2.2. In the following part this RFL-scheme will be elaborated in more detail.
再生纤维素纤维的半人造纤维和锦纶表面光滑，因此没有这种联锁的单纤维，而且这些纤维的机械强度比棉纤维高许多，因此需要更高的粘合强度，W.H. Charch和D.B. Maney发明了RFL处理。对于聚酯纤维的化学结构，由于缺乏极性，和氢键粘合基团，单一的RFL处理是不够的，而芳纶纤维，大量的芳香族基团在空间结构上，阻碍了氨基的功能。因此，聚酯纤维和芳纶纤维.需要进行预浸胶处理后才能进行标准的RFL粘合处理。图2.2描述了RFL处理的示意图，本文将更详细地说明RFL处理。

Figure 2.2 Schematic representation of the various fibre treatments, including RFL-treatment and the adhesion to rubber compounds
图2.2 不同的纤维处理方法，包括RFL处理和橡胶的粘合

2.2.1 RFL composition RFL的组分
The RFL-dip is an emulsion of a rubber latex in a solution of resorcinol and formaldehyde in water. If latex alone would be applied to the cords, it would provide an interaction with the rubber matrix of the compound but not with the fibre itself; furthermore, the latex layer would have weak mechanical properties. By adding resorcinol and formaldehyde, the dip layer increases in polarity and mechanical properties.
RFL浸胶液是一种由橡胶胶乳和间苯二酚与甲醛的水溶液混合的胶乳。如果仅仅是处理橡胶胶乳，其可以提供与橡胶之间的粘合力，但不能粘合纤维，而且胶乳层的机械特性低。添加间苯二酚和甲醛后，浸胶层的极性增加，机械性能得到提高
The preparation of a RFL-dip takes place in two stages. First, an aqueous solution of resorcinol and formaldehyde is matured for several hours at room temperature. By adding sodium hydroxide, this mixture becomes basic. During the maturation process, some degree of condensation takes place. Second, the resin solution is added to a mixture of latex and water. The amount and ratio of latex and water can be varied to achieve the desired RFL-dip. A typical RFL formulation is given in Table 2.4; a RFL-dip has a typical solid content of around 20 wt% and a pH of around 10.
RFL浸胶液的调配分两个步骤，首先，将间苯二酚水溶液和甲醛在室温下，熟化反应几个小时，添加氢氧化钠，这种混合物是碱性的。在熟化反应过程中，会发生一定程度的缩聚。其次，树脂溶液添加到水稀释的胶乳中，胶乳和水的比率可以进行调整，来获得所需的RFL浸胶液。一种典型的RFL配方见表2.4，RFL浸胶液的典型固含量在20%，PH值在10左右。

Table 2.4 typical RFL formulation
表2.4 典型的RFL配方
Dry parts/100 parts of dry latex 固含量/100分胶乳固含量
Resin solution
Resorcinol 间苯二酚 11.2
Formaldehyde 甲醛 6.3
Sodium hydroxide 氢氧化钠 0.7
Total 合计 18.2
Final RFL-dip RFL浸胶液
VP-latex VP胶乳 100
Resin solution 18.2
total 合计 118.2
Instead of formaldehyde and resorcinol, often penacolite is used. Penacolite is the linear polymer of the two monomers; it is acid polymerised with a molecular weight of around 300 g/mol. When the dip is prepared, extra formaldehyde and sodium hydroxide or ammonium hydroxide are added to obtain the required pH and formaldehyde/resorcinol ratio for the three-dimensional resin network formation. The major advantage of using penacolite is that the maturation of the resin solution is no longer required. Several studies have shown that the structure of the cured RFL consists of a continuous resin phase and dispersed latex particles.15, 16 A visualisation of the morphology is shown in Figure 2.3.
通常用penacolite（一种预缩聚树脂的商品名）替代甲醛和间苯二酚，penacolite是一种甲醛和间苯二酚的线形聚合体，是在酸性聚合，摩尔分子量在300g/摩尔。在调配浸胶液中，需要添加甲醛以及添加氢氧化钠或氨水，调整PH值和甲醛和间苯二酚比，从而反应形成三维网状结构的树脂。使用penacolite的最大优点就是不再需要树脂的熟化反应，某些研究显示，浸胶热处理后的RFL是由连续的树脂相和散布的乳胶粒子组成的。

Figure 2.3  Proposed RFL morphology
图2.3 可能的RFL形态

2.2.2 The dipping parameters 浸胶参数
A general scheme for a dipping process unit is given in Figure 2.4. In this picture, the cord is moving from the right to the left. When a feed roll is empty, the entry accumulator is used to gain time to attach a new feed roll. Before entering the impregnator bathes and after the ovens, series of rolls are present. These rolls have a relative velocity between each other, allowing application of a certain stress on the cord during dipping and drying. After the cord has passed an impregnator bath, the amount of dip on the cord (dip pickup) is regulated by the so-called pickup control system. This is mostly a squeeze roll unit, but can also be a vacuum unit or a beater. The second dipping unit functions similar to the first one. The exit accumulator works the opposite way as the entry accumulator, as a buffer for the rebatch unit. Parameters that are adjusted during the dipping process are: cure temperature of the predip, cure temperature of the RFL-dip, tensile forces on the cord when passing the ovens and residence times in the ovens. The residence times in the ovens can be adjusted either by changing the speed of the cord or by adjusting the number of loops which the cord makes through the ovens.
图2.4所示是浸胶机的浸胶流程图，图帘布的生产流程是从右到左，储布架在布卷用完时，可以释放储存的坯布，从而获得时间，进行新布卷接头。在浸胶槽前和烘箱后，各有一组滚筒，控制其相对速度，就能在浸胶和干燥中给帘布施加一定的张力，帘线经过浸胶后，浸胶量由称做附胶量控制系统进行调节，通常是一组挤压辊，也可以是真空吸胶系统或拍打系统。第二浴的功能和一浴的功能基本相同，出布储布架的功能和入口初储布架的功能正好相反，为换卷提供缓冲时间。浸胶过程中的浸胶参数由：一浴浸胶的热处理温度、RFL的热处理温度、浸胶张力在烘箱中的停留时间等等，在烘箱中的停留时间可以通过调整浸胶速度或者在烘箱中的走布道数进行调节。
All these parameters need optimisation for every type of reinforcing fibre, the type of RFL and the type of rubber to adhere to. It is therefore not surprising that the knowledge of cord to rubber adhesion to date is very pragmatic rather than scientific.
不同种类的纤维材料，不同的RFL配方以及橡胶种类，这些参数需要进行优化。所以不用惊讶，帘线与橡胶的粘合依靠更多的是实际经验，而非科学分析。

Figure 2.4 General layout of a fabric treatment unit for a two dip system17
图2.4，二浴浸胶系统示意图

Many RFL variables such as formaldehyde to resin ratio, resin to latex ratio, dip pickup, acidity of the dip, cure time and temperature of the dip and environmental aspects such as UV and ozone attack were investigated and their influence on the adhesion reported in a variety of papers.18-28 The references reported here only represent a selection of the most useful articles.
在多篇论文18-28研究了RFL中甲醛和间苯二酚的比率、树脂和乳胶比率、附胶量、浸胶液的PH值、浸胶热处理时间和温度，以及环境状况，比如紫外线、臭氧对RFL的破坏对粘合的影响，参考文献中所列的论文是部分最有用的论文。
Formaldehyde to resorcinol ratio: - Formaldehyde and resorcinol react in a similar manner as in the formation of Bakelite.29 The reactions take place in a basic environment. The reaction scheme is depicted in Scheme 2.1.
甲醛和间苯二酚的比率：甲醛和间苯二酚的反应和酚醛胶木板的反应是相似的，反应是在碱性环境下进行的。反应过程如流程图2.1所示。

Scheme 2.1 Reaction of formaldehyde and resorcinol in a basic environment
流程图2.1，甲醛和间苯二酚在碱性环境下的反应过程

Increasing the amount of formaldehyde increases the rate and amount of methylol formation. Due to this methylol functionality, reaction can take place with another resorcinol molecule according to the scheme. Increasing the formaldehyde to resorcinol ratio increases both the degree of condensation and the degree of branching. The concentration, the maturation time and temperature of the resin solution, as well as the curing time and temperature of the RFL-dip influence the rate of condensation.
增加甲醛的用量，将增加羟甲基的形成，由于羟甲基的功能，可以和另外一个间苯二酚的分子之间进行反应，如反应过程图所示，增加甲醛和间苯二酚的比例，可以增加缩聚程度和分支数量，树脂的浓度、熟化反应时间和温度，浸胶浸胶的热处理时间和温度，将影响缩聚程度。
The influence of the formaldehyde to resorcinol ratio of the RFL-dip on the adhesion to rubber compounds has been the subject of various review articles in the 1950¡¯s and 60¡¯s. All studies indicate an optimum in formaldehyde and resorcinol ratio as shown in Figure 2.5. Porter22 studied the effect, using a styrene butadiene (SBR) rubber compound containing N-tert-butyl-benzothiazole sulphenamide (TBBS), tetramethyl thiuram disulphide (TMTD) and sulphur as curatives. He found that the optimum amount of formaldehyde relative to resorcinol is 2 to 1 for all three fibres: polyester, polyamide and Rayon. The research of Miller and Robison23 was based on butyl rubber reinforced with rayon fibres. Dietrick24 used polyamide in a Natural Rubber (NR) compound using mercapto benzothiazole disulphide (MBTS) and sulphur as curatives. The results of Solomon30 were published in an educational book without the type of fibre or rubber being mentioned. The rate of methylol formation, molecular weight and the network structure of the RF-resin varies with the formaldehyde to resorcinol ratio.20, 21 In Figure 2.6, the mechanical properties of the RFL-dip are depicted as a function of formaldehyde/resorcinol ratio.21, 31 The optimum in tensile strength in Figure 2.6 occurs at a ratio of 1, unlike the optima shown in Figure 2.5, where the maximum of rubber-cord adhesion lies at 2. Takeyama21 and Miller & Robison23 explained this difference by an increase in methylol concentration when more formaldehyde is added, following Scheme 2.1. The methylol functionality increases the interaction on the fibre/predip side of the dip by, for example, hydrogen bonds.
RFL浸胶液中的甲醛/间苯二酚比对粘合力的影响是上世纪50年代到60年代的重点研究内容，所有论文所认为的最佳的甲醛/间苯二酚比率见图2.5，PORTER研究了丁苯（SBR）橡胶，采用TBBS和TMTD作为促进剂，硫磺作为硫化剂，发现，对于聚酯，锦纶和人造丝，甲醛和间苯二酚的最佳比例为2比1，MILLER和Robison的研究了用人造纤维增强的丁基橡胶；Dietrick研究了采用MBTS促进剂和硫磺硫化的天然橡胶和锦纶的粘合；Solomon在一本教科书中得出的结果，但没有提及纤维和橡胶的种类。羟甲基的形成量，RF树脂的摩尔分子量以及网状结构，是随甲醛和间苯二酚分子量变化而变化的。在图2.6所示，RFL的机械性能是甲醛/间苯二酚比率的函数，图2.6所示，拉伸强度最高，是其比率为1的时候，与图2.5所示的最佳点不同，与橡胶的最佳粘合强度在其比率为2。

Figure 2.5 Effect of resin composition on pullout force
图2.5，树脂配方对H抽出力的影响

Figure 2.6 Mechanical properties of the RFL-dip as a function of resin composition20, 21
图2.6 机械性能是RFL树脂组分的函数
Resin to latex ratio: - The influence of the amount of resin versus latex on the adhesion is reported in the same publications as the influence of resin composition. If only the latex would be applied on the cord, the bonding force would be very low due to lack of interaction with the fibre. In Figure 2.7, the pullout force is plotted versus the resin content in the dip. According to all publications, the pullout force increases significantly when resin is added to the latex in the dip. Only in the work of Porter, an optimum is observed in the pullout values at 20 parts resin per 100 parts of dry latex. Hupj¨¦18 found an optimum in peel force at a resin content of 15 parts. Figure 2.8 shows a strong drop in peel force for RFL-dips containing a large amount of resin. Takeyama21 claims that a too high resin content results in a dip which is too stiff and has poor flex properties. Furthermore, he stipulates a lack of interaction with the rubber phase.
树脂和胶乳的比率：树脂和胶乳的比率变化对粘合力的影响，在对树脂组分研究的论文中，同样进行了报告，如果是帘线仅仅浸胶胶乳，由于与纤维之间缺少相互反应，粘合力是非常低的。在PORTER的报告中，发现最佳的H抽出力为固含量为树脂20份，胶乳100；Hupj¨¦发现剥离力为树脂含量为15份的时候，图2.8所示，RFL中含有大量的酚醛树脂是，剥离力却大幅度下降。Takeyama解释说是由于树脂含量过高。浸胶层太硬，缺乏柔性所致，此外，他认为也是与橡胶缺乏相互反应所造成的。

Figure 2.7 Effect of resin to latex ratio of the RFL-dip on pullout force
图2.7树脂与胶乳比率对抽出力的影响

Figure 2.8 Effect of resin to latex ratio of the RFL-dip on the peel force18
图2.8 树脂与胶乳比对剥离力的影响

Type of rubber latex: - The most commonly used latex is based on a terpolymer of styrene, butadiene and vinylpyridine, the so-called VP-latex. The structural formula of VP-latex is given in Figure 2.9. It is empirically believed that vinylpyridine monomer is indispensable to obtain sufficient rubber adhesion. However, the reason for this is unknown.
浸胶胶乳的种类：最常用的胶乳是一种由苯乙烯、丁二烯和乙烯基吡啶组成的三元共聚体，称做VP胶乳，VP胶乳的结构式如图2.9所示，经验表明，乙烯基吡啶对获得有效的粘合力来说是必不可少的。然而其原因不清。
Wootton32 reported that a blend of 80% VP-latex with 20% SBR-latex results in an optimum adhesion for Rayon tyre cord. However, for polyamide the use of only VP-latex was beneficial. The adhesion was measured to a NR compound. No explanation was given for these observations.
Wootton 研究表明，80%的胶乳和20%的丁苯对人造丝帘子布而言，是最佳的粘合，对于锦纶，则就只能用VP胶乳，粘合力试验所用的是天然橡胶，没有对上述结果进行解释。
Porter19, 22, 33 investigated the adhesion of RFL-dipped polyester and polyamide with varying VP-monomer contents. The VP-content was varied by mixing a copolymer of 70% butadiene and 30% VP with SBR-latex and by copolymerising different amounts of the VP-monomer in the latex. The adhesion was measured to a SBR-compound with TBBS, TMTD and sulphur as curatives. All the results indicated that a VP-content of 15 wt% in the latex was the optimum value that resulted in the highest adhesion.
Porter研究分析了聚酯和锦纶用VP单体含量不同的RFL浸胶后，VP的含量通过将70%的丁苯与30%的共聚物和丁苯混合以及胶乳中添加不同数量的VP单体来进行调节的。粘合力是与用TBBS、TMTD和硫磺的硫化体系的丁苯橡胶进行的。所有的结果表明，VP含量在15%是最佳的，可以获得最高的粘合力。
Hupj¨¦18 explained the choice of the tyre industry for the more expensive VP-latex by the fact that higher dip-cure temperatures can be used for VP-latex than for SBR-latex. Furthermore, VP has a better interaction with the resorcinol formaldehyde resin component of the RFL-dip.
Hupj¨¦解释了在轮胎行业选择价格昂贵的VP胶乳，是由于与丁苯胶乳相比，VP胶乳可以承受更高的浸胶热处理温度，此外VP与RFL树脂有良好的相互反应。
Takeyama34 claimed that for a NR/SBR compound the use of VP-latex was preferred over the use of NR- or SBR-latex, or a mixture thereof. However, due to the high modulus of the VP-terpolymer, the fatigue properties of a RFL-dip containing VP-latex were worse.
Takeyama解释了在NR/SBR橡胶中，VP胶乳比使用NR胶乳和SBR胶乳或其混合胶乳粘合力更好，但由于VP胶乳的高模量，因此采用VP胶乳浸胶的耐疲劳性能会变差。
Solomon35 gave three possible reasons for the good performance of the VP-latex: (1) vulcanised VP-latex shows high strength; (2) the polarity of the VP-monomer is high, thereby increasing the interaction with the fibre; and (3) the VP-monomer improves the interaction with the resorcinol formaldehyde (RF) resin. The last was verified by Xue.36 He found that 2-ethylpyridin undergoes hydrogen bonding with the RF-resin. 4-ethylpyridin can also react with the RF-resin forming cyclic amide structures.
Solomon给出了VP胶乳具有高性能的3个原因，1、硫化后的VP胶乳的强度高，2、VP单体的极性高，所以提高了与纤维的相互反应能力，3、VP单体改善了与树脂的相互反应程度。Xue发现2-乙基吡啶与RF树脂有氢键连接，4-乙基吡啶和RF树脂可以反应生成环状的氨基结构。

Figure 2.9 Structural formula of styrene-butadiene-vinypyridine latex; standard composition: a and c: 15 wt%, b: 70 wt%
图2.9 苯乙烯、丁二烯和乙烯基吡啶胶乳结构式

Dip pickup: - The amount of dip on the cord after the dipping process is called dip pickup. The dip pickup influences the adhesion as shown in Figures 2.10 and 2.11. The adhesion increases as a function of dip pickup and reaches a saturation point. In practice, a dip pickup of around 7 wt% is preferred.21 The exact mechanism by which the dip pickup influences the adhesion is not given by any author.18, 22-24, 30
附胶量：帘子线浸胶后的浸胶量称做附胶量，附胶量对粘合力的影响见图2.10，2.11。粘合力随附胶量增加而增加，并达到一个饱和峰值，在实际生产过程中，附胶量在7%左右较好，没有一位作者对附胶量影响粘合的激励进行描述

Figure 2.10 Pullout force versus dip pickup according to Porter22 and Miller & Robison23
图2.10，Porter和 Miller & Robison 的附胶量与抽出力的关系

Figure 2.11 Pullout force versus dip pickup according to Dietrick24, Solomon30 and Hupj¨¦18
图2.11 Dietrick, Solomon and Hupj¨¦的附胶量和抽出力的关系
Initial pH of the dip: - In Figure 2.12, the influence of initial pH of the resorcinol formaldehyde resin on the pullout force of a polyamide fibre in a NR compound is shown.24 Two types of catalyst were used: ammonium hydroxide and sodium hydroxide. The optimum adhesion is achieved by using sodium hydroxide at a pH between 8 and 9. When using ammonium hydroxide, the resulting adhesion is less sensitive to pH. The same results are obtained by Porter22 for polyester, polyamide and rayon fibres. Solomon reported an optimum in pH at a value of around 9.7 using NaOH as catalyst.30
浸胶液的初始PH值：图2.12所示是RF树脂的初始PH值对锦纶纤维和天然橡胶粘合力之间抽出力的影响，采用了两种催化剂，氢氧化铵和氢氧化钠，在PH为8-9，采用氢氧化钠催化，可以获得最好的粘合力，采用氢氧化铵，粘合力对PH值不是十分敏感。Porter对聚酯、锦纶和人造丝的试验，获得了相同的结论。Solomon则在采用NaOH作为催化剂，PH为9.7时，粘合效果最好。

Figure 2.12 Influence of initial pH of the resin solution on the H-pullout force according to Dietrick24
图2.12，Dietrick的树脂溶液初始PH值对H抽出力的影响

Cure time and temperature of the RFL-dip: - Takeyama21 and Hupj¨¦25 investigated the influence of cure time and temperature of the RFL-dip on the adhesion to rubber. Takeyama published Figure 2.13 in a review article and did not mention the type of rubber or fibre used. According to Figure 2.13, an increasing temperature results in a shorter optimum cure time. The cure time also becomes more critical with increasing temperature because the graphs in Figure 2.13 become narrower. The obtained adhesion remains on the same level for all temperatures.
浸胶热处理时间和温度：Takeyama21 and Hupj¨¦25研究了RFL浸胶热处理温度和时间对与橡胶粘合力的影响。图2.13为Takeyama总结论文中所发表的，没有说明所用的纤维和橡胶种类。根据图2.13，增加温度就会缩短最佳的热处理时间。增加热处理温度后，如图2.13所示，最佳的热处理时间区间将会变窄，热处理时间长短就变得十分重要的关键因素。
Hupj¨¦ investigated the effect of cure time and temperature of the RFL on the adhesion of dipped polyester in a NR/SBR blend. In Figure 2.14, the opposite is shown compared to Figure 2.13: the optimum cure time at a temperature of 245¡ãC is higher than that at a temperature of 230¡ãC. The obtained level of adhesion at 245¡ãC is lower than that for 230¡ãC. The temperature used for rayon varies around 160¡ãC, polyamide between 200 and 230¡ãC and for polyester and aramid fibres even higher temperatures can be used, because these are temperature-stable fibres.
Hupj¨¦研究了RFL浸胶的聚酯与NR/SBR混炼胶粘合，浸胶热处理温度和时间对粘合力的影响，如图2.14所示，其结论和图2.13相反，最佳的热处理时间在245度时比230度长。但在245度时的粘合力比230度时低，人造丝的浸胶温度在160度左右，锦纶在200度左右，聚酯230度左右，芳纶可以用更高的温度，因为芳纶市一中热稳定性好的材料。
The explanations for the dependence of adhesion on cure time and temperature vary widely. Explanations are based on the mechanical properties of the dips, the presence of methylol groups and oxidative breakdown of the dip layer.
对粘合力大小与热处理温度及时间的关系，有各种各样的解释。主要是依据浸胶层机械性能、羟甲基的存在、以及浸胶层的氧化破坏来进行解释的。

Figure 2.13 Effect of cure time and temperature of the RFL-treatment on the adhesion according to Takeyama21
Takeyama的热处理时间与温度对粘合力的影响

Figure 2.14 Effect of cure time and temperature of the RFL-treatment on the adhesion according to Hupje25
Hupje的热处理时间与温度对粘合力的影响

Environmental aspects: - The properties of the RFL-layer are influenced to a large extent when the treated fibre is exposed to ozone, humidity, UV light or heat.28, 37 After vulcanising the exposed fibre to a rubber compound, the adhesion is detoriated to a large extent, not because of cohesive failure in the RFL-dip itself, but rather at the surface and the interface between RFL and rubber, due to lack of reactive sites in the latex where vulcanisation can take place.
环境影响：当浸胶后的纤维暴露在臭氧、潮湿、紫外线或受热的情况下，浸胶层受到极大影响。硫化这种暴露过的浸胶后的纤维，和橡胶的粘合力会有大幅度下降，不仅仅是由于RFL自身的分解破坏，而且主要是由于RFL浸胶层的表面以及与橡胶界面的胶乳中缺乏可反应活性成分，和胶乳是发生硫化的地方。
2.2.3 Predips 预浸胶
Polyester and aramid do not contain as many reactive functional groups as rayon or polyamide; therefore, a standard RFL-dip would not result in sufficient adhesion.38, 39 Several attempts were made to develop two-step dipping processes in which the second step is a standard RFL-dip. First, highly active isocyanates in an organic solvent were used as a predipping step. In order to be able to use an aqueous solution, DuPont40 developed a phenol blocked isocyanate system with a small amount of epoxy to improve film formation. This system is called Hylene.
聚酯和芳纶不想人造丝和锦纶有许多活性反应的功能基团，因此标准的RFL浸胶是不能获得有效的粘合力的。因此进行了多种二步法浸胶的尝试，其中第二步依然进行标准的RFL浸胶。首先，第一步，采用溶剂型的高活性反应的异氰酸酯进行预浸胶，为了能够使用水性的材料，杜邦开发了一种苯酚封闭的异氰酸酯浸胶体系，夹入少量的环氧树脂，改善浸胶膜的形成。这个体系称做Hylene
The two types of reaction products between isocyanate and aramid according to Hepburn41 are shown in Scheme 2.2. The remaining isocyanate functionality can react further with the next layer: the RFL-dip.
图2.2所示为Hepburn的异氰酸酯和芳纶反应生成的两种物质，剩余的异氰酸酯可以进一步和后续的RFL浸胶层继续反应。

Scheme 2.2 Two types of products of the reaction of isocyanate with aramid fibre
示意图2.2 异氰酸酯和芳纶纤维反应生成的两种物质

Another predip that is frequently used for aramid and polyester is an epoxy dip, based on the reaction of glycerol with epichlorohydrin, Scheme 2.3.32
芳纶和聚酯常用的另外一种预浸胶方式就是浸渍环氧树脂，，依靠丙三醇和表氯醇的反应，如示意图2.3所示

Scheme 2.3 Reaction of glycerol with epichlorohydrin
丙三醇和表氯醇的反应
Garton42 investigated the cure behaviour of epoxy resin in the presence of an aramid surface by infrared spectroscopy. He found no evidence that the aramid functionality interacted chemically with the epoxy resin. According to Iyengar37, adhesion is obtained between polyester fibres and the epoxy predip by a diffusive interaction, and in the case of aramid fibres by both diffusion and hydrogen bonding. De Lange43, 44 has investigated the epoxy-aramid interaction for the application of adhesion activated aramid. The epoxy functionality is present in the spin finish, replacing the predip. According to de Lange, the adhesion can be explained by multiple-point hydrogen bond formation between polymerised epoxy and the aramid surface.
Garton利用远红外光谱仪研究了在芳纶表面的热处理特性，他认为名优证据可以证明芳纶与环氧树脂进行了化学的相互反应，根据Iyengar的观点，聚酯纤维和环氧树脂之间的粘合是由于扩散相互作用形成的。而芳纶则存在扩散和氢键粘合，De Lange为了预活化的芳纶纤维的应用，研究了环氧树脂芳纶的相互作用。环氧树脂可以添加在纺丝油剂中，替代与浸胶。根据de Lange解释，其粘合是由于缩合的环氧树脂和芳纶表面形成了多点的氢键结合。

2.3 ALTERNATIVES TO THE STANDARD TREATMENT 取代标准处理的替代方案。
2.3.1 Roughening the fibre surface 表面粗糙化
Until the 2nd World War, solely cotton was used for reinforcing tyres. The only adhesive treatment necessary was drying the fibre. Cotton fibres are not smooth; filaments are sticking out of the surface of the fibre. These filaments are anchored in the rubber matrix. The frictional forces that need to be overcome to pull or strip the fibre out of rubber result in a sufficient adhesion. Breznick45 and Roebroeks46 have tried to apply this principle to aramid fibres, by roughening the surface.
在二次大战前，轮胎就用棉纤维进行增强的。所谓的粘合力处理就是烘干纤维而已，由于棉纤维不是光滑的，微纤伸出纤维表面，这些微纤和橡胶形成锚接粘合。从橡胶中拉出或剥离纤维时，所需克服的摩擦力就可以形成足够的粘合力。
Breznick45 has further treated aramid with bromine to modify its surface. The bromine is adsorbed into the fibre surface and afterwards the fibre passes through an ammonia solution. The chemical reaction that takes place is shown in Scheme 2.4. Breznick 和 Roebroeks 试图应用这一原理，将芳纶纤维的表面毛糙化。

Scheme 2.4 Reaction of bromine with amine
示意图2.4 溴与胺的反应
The nitrogen gas that is produced penetrates from inside-out through the surface. In this way the fibre surface is chemically etched and roughened. The aramid should be exposed to the bromine for only a short period to prevent a strong reduction in the tensile properties of the fibre. For naked aramid, this treatment improved adhesion with 20%. The intrinsic fibre strength loss was 15%.
溴化产生的氮气从里到外，穿过表面，渗透出来，通过这一方法，纤维表面被侵蚀，从而毛糙化。芳纶只能短时间地暴露在溴中，防止造成纤维强度的过度下降。这一方法可以提高芳纶粘合性能20%，而强度将下降15%。
Roebroeks46 investigated the influence of fibrillation on the adhesive strength of aramid fibres to thermoplastic polyetherimide (PEI) resin. Aramid is easily split in the transverse direction, giving structures as illustrated in Figure 2.15. Controlled fibrillation was obtained by bringing the surface in contact with small oscillating particles. Only a small layer was affected and the rest of the fibre remained intact, to carry the tensile load. The author stated that an increase of more than 600% in adhesion was obtained without any loss in mechanical properties of the fibre. The increase in adhesion could be ascribed to an increase in mechanical anchoring of the fibrils comparable to cotton. However, this method has never been applied in rubber.
Roebroeks研究了芳纶纤维的纤化后与热塑性聚醚酰亚胺树脂的粘合影响，芳纶很容易横向分裂，形成如图2.15所示的结构，在纤维表面与有微小震动的粒子相接触，可以有控制进行纤化。作者强调，这样可以提高粘合强度600倍，而且不会对纤维有任何机械性能的损伤。粘合力的提高是增加了与棉纤维可以相提并论的锚和粘合强度。但这一方法，从来没有在橡胶中应用。

Figure 2.15 Schematic representation of the fibrillation of aramid filaments.

2.3.2  Adhesion promoting additives to rubber compounds 在橡胶中添加粘合促进组分
From the 1950¡¯s, adhesion activators were mixed into rubber compounds in order to enhance the adhesion to fabrics. Generally, three components are added extra to the rubber compound: resorcinol, a methylene donor and an active white filler: silica. Examples of methylene donors are hexamethoxymethylmelamine and hexamethylenetetramine. The role of the filler is not fully understood; it can improve the miscibility of the resorcinol and formaldehyde donor or it can act as a catalyst. In case of aramid fibres, isocyanate derivatives can be mixed into rubber to improve the adhesion.
从上世纪50年代开始，橡胶中就开始添加粘合促进剂：间苯二酚、亚甲基给体、白炭黑，比如作为亚甲基给体，白炭黑的作用目前未能完全理解，
Several adhesion promoting additives are found in patent literature.47-52 These additives can be used in combination with the RFL-treatment, for further enhancement. However, no additives have been found that completely eliminates the need for the RFL-treatment.
在一些专利文件中得知，有多种粘合促进剂，为了进一步加强粘合效果，这些粘合促进剂可以和RFL浸胶处理一同使用，但目前位置没有发现可以真正替代RFL浸胶处理的方法。
2.3.3 Impregnating fibres
The most common approach to find alternatives to the standard dip treatment is impregnating the fibres in some other way. Efforts have been made to combine the two-dip treatments for polyester and aramid fibres into a single dip treatment, by incorporating isocyanate in the RFL formulation.39, 53 Also a multiple-RFL-treatment has been patented.54 In order to achieve a resorcinol formaldehyde-free RFL-dip, Solomon55 patented an alternative for both aramid and polyester fibres. This dip was used in addition to the conventional epoxy predip step. The dip contained an acrylic resin dispersed in latex. In the example, styrene and methyl methacrylate, Figure 2.16A and 2.16B respectively, in combination with vinylpyridine-latex were tested. Compared to the conventional RFL-dip system, the H-pullout adhesion to a NR compound increased by 3.7%.
最接近于替代标准RFL浸胶的的方法是浸渍，就是将通过某些方法，浸渍纤维，其效果就是通过在RFL配方中添加异氰酸酯，将聚酯和芳纶的二浴浸胶合二为一，进行单浴浸胶处理。有一种多RFL处理方法申请了专利，为了得到无甲醛、间苯二酚的RFL浸胶液，Solomon 申请了一种专利方法，用于聚酯和芳纶的浸胶，浸胶液中的胶乳中分散有丙烯酸酯树脂。图2.16A和B，举例了苯乙烯、甲基丙烯酸甲酯与VP胶乳混合后的试验结果。与传统的RFL浸胶体系相比，其与天然橡胶的粘合力，H抽出力提高了3.7%。

Figure 2.16 Monomers used by Solomon55; styrene (A) and methyl methacrylate (B)
图2.16 Solomon所用的单体A 为苯乙烯，B为甲基丙烯酸甲酯
Van Gils56 patented the addition of trimethylolphenol, Figure 2.17, in the RFL recipe for better adhesion of a NR/SBR rubber to aramid. The methylol functionality can participate in the resorcinol formaldehyde reaction given in Scheme 2.1, as well as interact with the surface of the fibre.
图17为Van Gils申请的专利，在RFL配方中添加了trimethylolphenol，以提高芳纶和NR/SBR混炼胶的粘合力，如流程图2.1所示，羟甲基的功能是参与间苯二酚与甲醛的反应，以及与纤维表面的相互反应。

Figure 2.17. Structure of trimethylolphenol
图2.17  trimethylolphenol 的结构
Some of the attempts to replace the dip or predip treatment were based on entirely new approaches, rather than adjusting the existing RFL formulation. For example, Burlett57 treated aramid with an aramid-polydiene copolymer, as a replacement for the epoxy/RFL-dip. An example of the structural formula is shown in Figure 2.18. B and X in this structure are aromatic groups. This copolymer is placed on the fibre by using a solution as a dip, or by using it in the finish of the fibre. The copolymer has aramid functionalities for interaction with the aramid surface as well as allylic hydrogens that can participate in the rubber vulcanisation reaction. The adhesion properties are at maximum when used in a rubber that contains unsaturation, capable of sulphur vulcanisation. The adhesion increases by 10 to 15% in comparison with fibres without any treatment, but it does not come close to the adhesion reached with the standard two-dip treatment.
有人试图用全新的途径替代浸胶和预浸胶，而不是修正现有的RFL配方，比如，Burlet用芳族聚酰胺和聚二烯的共聚物，替代环氧树脂/RFL，图2.18B所示是其结构式，结构式中的X是芳香族基团。这种共聚物，用溶剂法浸胶，或者在纺丝时上油处理，共聚物中的芳香族具有与芳纶纤维表面进行相互反应的功能，而allylic hydrogens可以参与橡胶的硫化反应。当使用不饱和硫磺硫化的橡胶，粘合性能可以达到最大，与未经过处理的纤维相比，粘合力可以提高10-15%，但不能达到用标准的双浴浸胶处理粘合水平。

Figure 2.18 Example of an aramid-polydiene copolymer.
图2.18，芳族聚酰胺和聚二烯的共聚物

Li58 used a mixture of two silane compounds as adhesion promoters. One compound contained an amine functional group for interaction with the fibre, the other a radical functional group or unsaturated double bonds for reaction with the rubber. Examples are shown in Figure 2.19.
李采用了两种硅烷的混合物作为粘合促进剂，其中一个含有胺功能基团，可与纤维相互反应，其他的环状功能基团，或者不饱和双键可以与橡胶反应。如图2.19所示

Figure 2.19 Two examples of the structures patented by Li58
图2.19 LI专利的两种结构
A dispersion of the two silane components in water was added to the fibre; this fibre could be either polyester or aramid. Although one of the two types of silane components is not soluble, no surfactant could be used because that influenced the adhesion in a negative way. Using this treatment in combination with a RFL-treatment, an adhesion was measured close to that of a two-dip treatment.
在水中，这两种硅烷的分散，将粘附在纤维上，纤维可以是聚酯或芳纶，虽然这两种硅烷不溶于水，不能使用表面活性剂，因为活性剂对粘合力有负面影响，这种处理结合RFL处理，粘合力接近于双浴浸胶。

2.3.4 Plasma treatment 等离子处理
Plasma treatment is of interest since the late 1950¡¯s. A plasma state is a complex gaseous state containing free radicals, electrons, ions, etc. A fibre could be treated with plasma for several reasons. First, it can be used to clean or etch the surface of the fibre. Inert gases are then used in the plasma like argon, nitrogen, etc. Second, the use of more reactive gases introduces functional groups on the surface. Third, the use of monomers causes a thin polymer coating. Plasma treatment can therefore be used for all three approaches mentioned before: the mechanical interlocking of the fibres (etching), chemically changing the fibre surface (reactive gases) and adding an extra component (polymer coating). The advantage of plasma treatment is elimination of the need for hazardous solvents. A disadvantage is, that the nature of the plasma-modified surface is difficult to predict due to the complex plasma state.
在上世纪50年代后期，就对等离子处理感兴趣，等离子状态是一种复杂的气态，含有游离自由基，电子、离子等，纤维等离子处理基于下述原因。首先，其可以清洁纤维表面，等离子处理中使用氩气、氮气等惰性气体；其次，是使用活性更高的气体给纤维表面引入了活性基团；第三，单体的使用，能够产生很薄的聚合物涂层。等离子处理采用了上述所提的三种途径：纤维的机械锚接能力（侵蚀）、纤维表面的化学改性（活性的气体），添加附加组分（聚物涂敷）。等离子处理的最大优点是消除了有毒溶剂的使用。缺点是由于复杂的等离子状态，无法预估控制等离子处理后的表面状态，
Treating polyester fibres with inert plasma increased the adhesion to rubber, however not to the level of the two-dip treatment.59, 60 The inert plasma treatment was patented as a alternative for the predip step by Sharma.61 Also Morin62 patented a plasma treatment to replace the predip treatment, using a vinyl compound, for example vinylpyridine and acrylic acid. After this treatment, a standard RFL-dip was applied. Jasso63 reported the use of maleic acid as a monomer for plasma treatment to replace the RFL-dip itself. However, in this work the obtained adhesion values were not compared to values of the standard two-dip treatment.
采用惰性等离子处理后的聚酯纤维，提高了与橡胶的粘合力，但达不到二浴浸胶的效果。惰性等离子处理是Sharma替代预浸胶的专利，Morin同样申请了用乙烯基化合物进行等离子处理，取代预浸胶的专利，比如用乙烯基吡啶和丙烯酸，经过处理后，可以采用标准的RFL浸胶。Jasso的研究报告说采用马来酸作为单体进行等离子处理，可以替代RFL浸胶，但是，论文中的所获得的粘合力无法和标准的二浴浸胶处理相提并论。
Shuttleworth64 patented plasma treatment as an alternative for the predip as well as the RFL-dip. First, a cleaning step with for example tetrafluoromethane was applied. Second, a plasma treatment with carbon disulphide as monomer.
Shuttleworth的取代预浸胶以及RFL浸胶的专利技术是，第一步，清洁阶段，比如采用四氟化碳，第二步用二硫化碳作为单体进行等离子处理。
Van Ooij65 has investigated plasma polymerisation on cords. The types of monomers used were pyrrole and acetylene, Figure 2.20. The general idea behind these monomers was the availability of allylic hydrogens after polymerising on the surface of the fiber. The values for the adhesion were not compared to those of the standard RFL-treatment in his paper.
Van Ooij研究了帘线的等离子聚合，所用的单体是吡咯和乙炔，图2.20所示，使用这些单体的目的是为了这些单体在纤维表面聚合后，可以形成allylic氢键，其论文中所述的粘合力无法与标准的RFL处理相比较。

Figure 2.20 Structural formulas of A: pyrrole and B: acetylene
图2.20，结构式  A 吡咯 B 乙炔

2.4 SUMMARY AND CONCLUDING REMARKS
Untreated man-made fibres poorly adhere to rubber compounds, due to their smooth surface, high modulus and polar character. In order to reach an acceptable level of adhesion, Rayon and polyamide fibres are subjected to RFL-treatment, and polyester and aramid fibres to an epoxy or isocyanate treatment followed by a standard RFL-treatment.
未经处理的合成纤维，由于其表面光滑、缺乏极性、高模量，与橡胶的粘合力很低，要达到可以满足要求的粘合力，人造丝和锦纶纤维必须进行RFL处理，聚酯和芳纶进行环氧树脂或异氰酸酯处理，再进行标准的RFL处理。
The RFL-treatment is still widely used for almost all fibre/rubber composites. None of the alternatives that have been developed in the mean time seem to reach the same level, let alone a higher level, of adhesion. Despite the ¡°mature¡± age of the RFL-treatment invented in the late 1930¡¯s and the fact that no major improvements have been achieved since, the mechanism by which the adhesion is obtained when using the RFL treatment is still unclear. The RFL-dipping process is more an art than a science. For every fibre/rubber compound combination, the many parameters of the process have to be adjusted to optimise the adhesion.
RFL处理适用于绝大多数的纤维和橡胶复合体，目前没有可以开发出粘合力可以与其媲美的替代方法，更不用说粘合力比其高了。尽管RFL浸胶处理方法早在上世纪30年代后期就已经成熟，但随后并没有重大的改进，RFL处理后的粘合机理，到目前为止并不十分清晰，，RFL浸胶更像一个手工艺术，而不是一个科学手段。对于不同的纤维和不同的橡胶组成，必须调节浸胶过程的参数，使粘合力达到最优。
These parameters are:
- resorcinol/formaldehyde ratio
- resin/latex ratio
- latex type
- pH of the RFL-dip
- dip pickup.
- cure time of the dip
- cure temperature of the dip
这些参数包括：
- 间苯二酚/甲醛比
- 间甲树脂和胶乳比
- 胶乳的种类
- 浸胶液的PH值
- 附胶量
- 浸胶热处理时间
- 浸胶热处理温度

With new fibre materials introduced in recent years, in particular aramid fibres, it seems appropriate to revisit the fibre/rubber adhesion technology with modern analytical and engineering approaches, in order to achieve a required level of adhesion. Particularly for such high-safety articles like tyres it seems unacceptable, that otherwise optimal fibre materials like aramid cannot be applied fully by lack of appropriate, safe adhesive systems. The contents of this thesis is focussed on this issue.
近几年新型纤维的开发，特别是芳纶纤维，就有必要借助于现代的分析技术和工程手段，来回顾一下纤维和橡胶的粘合技术，提高粘合力。特别是像轮胎等有着更严格的安全性能要求规范，像类似于芳纶这样的高性能纤维，如果没有合适的、安全的粘合体系，是不能得到应用的。因此本论文研究重点就在于此。

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Chapter 3 Influence of the rubber curatives on rubber properties and adhesion to RFL-treated aramid cord
第三章橡胶组分对橡胶性能以及与RFL处理的芳纶帘线粘合力的影响

Although the RFL-treatment of tyre-cords was invented in 1938 and did not undergo any significant changes since then, the exact mechanism of RFL to rubber adhesion is still unclear. One of the proposed mechanisms of adhesion at the RFL-rubber interface is based on the co-vulcanisation of these two materials. In this chapter, the influence of the curatives of the rubber compounds on the adhesion is investigated. By using the method of Design of Experiments, the amounts of sulphur, MBTS and TBBS were varied in a statistical manner, and the influence of each curative on the adhesion was determined. Increasing the amount of MBTS and TBBS decreased the adhesion significantly. Increasing the amount of sulphur, leaving the two accelerators at their centre values, did not affect the adhesion marginally. The influence of the curatives on the mechanical properties of the rubber compounds was opposite to the influence on the adhesion measurements. Therefore, the important conclusion could be drawn that the adhesion measurements, H-pullout and SPAF at room and at high temperature, were indeed a measure for the adhesion rather than an indirect measurement for the mechanical properties. The only rubber bulk property that showed a correlation with the adhesion measurements, at a constant sulphur loading, was the t90 of the rubber compound. In other words, a slow curing rubber compound has a higher adhesion than a fast curing rubber compound.
虽然，1938年就开始用RFL浸胶处理芳纶帘线，但从此以后，没有得到任何明显的改进，RFL与橡胶的实际粘合机理依然不清。其中可能的机理是RFL和橡胶的界面处，两种物质进行了共硫化。本章，将讨论橡胶组分对粘合力的影响。采用正交试验法，从统计学的角度调整硫磺、MBTS、TBBS的用量，分析每种材料对粘合力的影响。增加MBTS和TBBS的用量，将造成粘合力的大幅度下降，保持促进剂的用量在平均水平，增加硫磺的用量，对粘合力没有大的影响；橡胶组分对橡胶的机械特性的影响与粘合力的影响正好相反。所以，可以得出这样的结论就是在室温和高温条件下进行粘合力的测试 -H抽出力以及剥离试验是考量粘合力的方法指标。而不是用非直接的测量机械性能方法来进行考量粘合力。
3.1 INTRODUCTION 引言
Cord reinforcement of rubber compounds plays a crucial role in high-pressure hoses, transmission belts, conveyor belts, tyres, etc. Good interfacial adhesion between the fibres and the rubber is essential to impart improved durability and product life. In order to bridge the large difference in polarity and stiffness between fibres and rubber, the fibres are commonly treated with a dip before being used in composites. The type of fibre of special interest in the present context is poly-p-phenylene-terephthalamide or p-aramid fibres. The selection of p-aramid is based on the fact that this fibre is extremely difficult to adhere to rubber compounds without application of complex dip treatments. The p-aramid fibres are treated with two dips: an epoxy pre-dip and a Resorcinol/Formaldehyde/Latex (RFL) dip to obtain proper adhesion. The RFL-structure consists of a continuous resin phase and dispersed latex particles as described in Chapter 2. The total adhesive system is complex and consists of many interfaces. The most frequent mode of failure of a composite during dynamic operation is at the interface between rubber matrix and RFL. The present study is therefore concentrated on the RFL-rubber interface.
帘子线增强的橡胶材料，在高压胶管、传动带、输送带、轮胎等里面担当一个十分关键的角色，在纤维和橡胶界面出的粘合力好坏，决定着产品的使用寿命，为了在纤维和橡胶的极性和刚性之间进行架桥，那么纤维通常进行进行浸胶处理。本文将对对位芳纶和锦纶纤维，选择对位芳纶是其因为其不经过非常复杂的浸胶，与橡胶的粘合十分困难。对位芳纶需2次浸胶才能有良好的粘合力，分别是浸胶环氧树脂和RFL。如第二章所述，RFL结构由连续的树脂形态和均匀分散的乳胶颗粒组成的。整个粘合体系十分复杂，由多个界面组成。最常见的橡胶复合体的破坏是动态工作下，橡胶与RFL界面的失效，因此本研究重点关心RFL和橡胶之间的界面情况。
Many RFL-variables, such as formaldehyde to resin ratio, resin to latex ratio, dip pickup, acidity of the dip, cure time and temperature of the dip and environmental aspects such as UV and ozone attack were investigated and their influence on the adhesion reported.1-11 However, a mechanistic insight into the process of adhesion was not provided by these authors. In studies carried out by Begnoche12 and Causa13 it was observed by using a Scanning Electrone Microscope coupled to an Energy Dispersive X-ray spectrometer (SEM-EDX), that sulphur and zinc migrate from the rubber into the RFL-layer. The type of rubber and compounding ingredients were however not mentioned in their publications.
有人分析了RFL的各种变化对粘合力的影响，比如甲醛和间苯二酚比，树脂和胶乳比，附胶量，浸胶液的PH值，浸胶热处理时间和热处理温度，紫外线臭氧攻击等等。但没有给出粘合过程中的详细机理，Begnoche 和Causa在多篇论文中，讨论了用电子扫描显微镜结合X射线衍射分光度计分析了硫和锌在橡胶和RFL浸胶层中的分布。但这些论文，没有提及橡胶的种类和橡胶组分。
The importance of the curative system of the rubber compound for the adhesion was discussed in several publications. Sexsmith14 observed an increase in pullout force when the amount of sulphur in a NR compound was increased. He explained this by the formation of a total chemical network between rubber and dip. Also Wootton15 ascribed the adhesion of RFL to rubber largely to direct crosslinking of the dip film to the rubber compound. The faster and more scorchy the cure system, the less time for migration of active species into the dip film. Darwish et al.16 have varied the sulphur content of a nitrile-rubber compound and measured the effect on the adhesion to a RFL-dipped polyamide cord. It was concluded that an optimum adhesion can be obtained at a sulphur content of 2 phr. The adhesion was low at lower sulphur content as well as at too high sulphur content. This was explained by lack of sulphur migration at low sulphur concentration and main chain modification by cyclic sulphur at high sulphur levels. Albrecht17 varied the amount of sulphur in a carcass compound and observed that the measured adhesion continuously increased with increasing sulphur content. An optimum was not observed. Albrecht also tested several types of sulphenamide accelerators and observed no difference in adhesion. All compounds containing sulphenamide accelerators exhibited a scorch time long enough to obtain complete wetting of the dipped cords by the rubber. By using tetramethylthiuram monosulphide (TMTM) in combination with N-cyclohexyl-2-benzothiazylsulphenamide (CBS), the scorch time was lowered to such an extent that the critical scorch time was not reached anymore and the adhesion was low. Erickson18 observed a correlation between the adhesion of dipped polyamide cords to a NR/SBR blend containing CBS as accelerator, and the cure rate of the rubber compound. This was explained by an increase in curative and polymer diffusion. Weening19 attempted to investigate the influence of several characteristics from the cure-rheogram independently: minimum and maximum torque level, scorch time and rate of vulcanisation. The scorch time was controlled by 2-mercaptobenzothiazole (MBT) or 2-mercaptobenzothiazyl disulphide (MBTS); a long scorch time resulted in high adhesion. The amount of sulphur determined the maximum torque level, and the rate of vulcanisation was controlled by adding accelerators such as diphenyl guanidine (DPG). These seemed to have a synergistic effect: increasing the rate of vulcanisation caused a low adhesion level, which was more pronounced at higher maximum torque levels. Hupj¨¦8 reported a correlation between the area above a rheometer curve and the adhesion. The area above the rheometer curve is shown in Figure 3.1. This area increases upon decrease of the minimum torque level (A), decrease of the cure rate (¦Á), increase of scorch time (B) and increase of the maximum torque level (C). According to the author, these four effects increase the level of adhesion. It was concluded that a rubber compound with a large area above the rheometer curve should result in a high adhesion and vice versa.
在一些论文中讨论了橡胶的硫化体系对粘合力的影响，Sexsmith观察到NR橡胶中，增加硫磺的用量可以增加抽出粘合力。他认为是由于橡胶和浸胶层之间形成了化学的网状结构所致。同样Wootton描述了RFL与橡胶的粘合是因为浸胶膜和橡胶之间进行了直接的交联。硫化体系的硫化速度过快，就会导致反应成分渗透到橡胶中去。Darwish et al.通过调整丁腈橡胶中的硫磺含量，分析了与RFL浸胶的锦纶帘线的粘合效果，结论是，当硫磺的含量是2份时，有最佳的粘合力。粘合力在硫含量很低与很高时，粘合力均不好。这个可以解释为：当硫磺含量较低时，硫的渗透就少，硫含量高时，主链就形成了硫环。Albrecht调整了骨架层橡胶的硫含量，发现随着硫磺的增加，粘合力同步上升，没有发现最佳点。Albrecht同样测试了不同的亚磺酰胺促进剂，没有发现粘合力的差异，所有含有亚磺酰胺促进剂橡胶可以有足够的焦烧时间，让橡胶湿润浸胶帘线的表面，采用TMTM结合CBS，焦烧时间就会下降到必要的焦烧时间以下，造成粘合力的下降。Erickson发现了浸胶锦纶帘线与混有CBS作为促进剂的NR/SBR橡胶以及橡胶的硫化速率之间的粘合力的相互关系，其用硫化剂的增加以及聚合体的分散进行了证实。Weening尝试用对最大、最小扭矩、焦烧时间和硫化速率等橡胶流变特性进行独立分析，焦烧时间用MBT和MBTS进行调节，发现焦烧时间长，粘合力好，硫磺的用量决定了最大力矩，硫化速率通过增加DPG等促进剂调节，发现其有着相互协调的作用，提高硫化速率，降低粘合力，最大力矩提高时有为明显。Hupj¨¦介绍了硫化曲线上方的面积与粘合力的相对关系，硫化曲线面积如图3.1所示，其面积随最小转矩降低、硫化速率降低、焦烧时间增加、最大转矩增加等变化而增加，上述四个因素，可增加粘合力。其结论是硫化曲线面积大的橡胶材料其粘合强度也高，反之亦然。

Figure 3.1 The area above the rheometer curve according to Hupj¨¦8
图3.1硫化曲线上方的面积
Overall, it can be concluded that, due to the often opposite observations described above, the influence of the vulcanisation system in the rubber compound on the adhesion between rubber and RFL-dipped cords remains unclear. In this chapter the co-vulcanisation behaviour of rubber to RFL is investigated by changing the amounts of sulphur, MBTS and TBBS in a carcass compound. A correlation will be made between the H-pullout force and strap peel adhesion force at room and at high temperature of the cord-rubber composites, with the cure characteristics and mechanical properties of the rubber compounds.
总之，结论为：由于上述的观察结果常常是相反的，在粘合方面，橡胶的硫化体系对RFL浸胶帘线与橡胶之间的粘合影响是不清的，在本章，将通过改变硫磺、MBTS和TBBS在骨架层橡胶中的用量，研究分析RFL与橡胶的共硫化特性。将列举在室温和高温下，帘线和橡胶复合体的H抽出力、剥离力与橡胶的硫化特性和机械特性的相互关系。

3.2 EXPERIMENTAL  实验
3.2.1 Materials 材料
All experimental work was performed on a model carcass masterbatch, as given in Table 3.1. For simplicity reasons, only NR was used instead of a NR/SBR blend. Polymeric sulphur (Crystex oil treated (OT) 20), 2-mercaptobenzothiazyl disulphide (MBTS), N-tertiary-butyl-benzothiazyl sulphenamide (TBBS) and N-cyclohexyl thiophthalimide (PVI) (ex. Flexsys Company) were used as curative package. The poly-p-phenylene terephthalamide fibres (Twaron.) were obtained from Teijin Twaron Company. The type of aramid used in this investigation was the Twaron 1008. The linear density was 1680 dtex (168 g per 1000 m) with a degree of twisting of 330/330 twists per meter. The aramid fibre had a water-based spin finish without adhesion activating additives. The type of latex used for preparing the RFL-dip was a styrene-butadiene-2-vinylpyridine terpolymer latex obtained from Eliokem (Pliocord 106s).
所有试验用一种结构的骨架层母胶，配方如表3.1所列，为了简单化，仅使用天然胶，替代NR/SBR混炼胶，使用聚合硫磺（用Crystex oil处理OT 20）、MBTS、TBBS、PVI等橡胶硫化助剂，使用帝人公司的芳纶纤维（TWARON），芳纶牌号为1008，细度为1680dtex，加捻330捻/米，芳纶用水基的纺丝油剂，没有活化组分，浸胶液所用的胶乳为Eliokem公司的VP胶乳，牌号为Pliocord 106s。
Table 3.1 Composition of the rubber masterbatch
橡胶母胶组分

3.2.2 Rubber compounds
A total of 180 kg of masterbatch was mixed in a Werner and Pfleiderer GK 270N tangential internal mixer. The curatives were added to the rubber compounds on a two-roll mill. The method of Design Of Experiments (DOE) was used to study the effect of curatives on properties. In the design, polymeric sulphur, MBTS, TBBS and PVI were used as curatives. Sulphur and the two accelerators were added according to the statistical ¡®Box Benhken¡¯ design; resulting in 15 compounds, as shown in Table 3.2. Two extra compounds were investigated to verify the validity of the model resulting from the design, they are called Ver 01 and Ver 02 in Table 3.2. Ver 01 corresponds to a model carcass compound as given in literature.20 MODDE 6.0 software from Umetrics was used to model the properties within the limits of the added amounts of curatives.
总共用了180公斤母胶，橡胶硫化助剂在双辊开练机上夹入，采用了正交实验法分析对性能的影响，设计中，聚合硫磺、MBTS、TBBS、PVI作为硫化体系，硫磺和促进剂按正交实验法的统计学规定添加，从而产生了15种配方，如表3.2所示，另外添加了两个配方，验证正交表试验的有效性。分别为VER 01和VER 02，VER 01是论文20所列的一种骨架层用胶参照数学模型。在添加橡胶硫化助剂的极限内， MODDE 6.0是来自Umetrics的软件，用作性能分析的参照数学模型
Table 3.2 Compositions of the Rubber Compounds
试验的橡胶组分配方

3.2.3 Compound characterisation 橡胶特性
The cure characteristics of the compounds were measured with an RPA 2000 dynamic mechanical curemeter of Alpha Technologies. The cure curves were recorded at 150oC, with a frequency of 0.833 Hz and 0.2 degrees strain. The responses used for the experimental design were the scorch time t2, the optimum cure time t90, the maximum Torque S¡¯max and the area above the rheometer curve, according to Hupj¨¦.8 The samples were cured in a moulding press at 100 bar pressure at 150¡ãC, for t90 plus 3 minutes. Mechanical properties of the compounds were measured with a Zwick BZ1.0/TH1S tensile tester, as set out in ISO 37 with type 2 tensile bars used. The measured responses were Young¡¯s modulus (E-mod), stress at 300 % strain (¦Ò300), tensile strength (TS) and elongation at break (e-a-b).
橡胶的硫化特性用Alpha Technologies生产的RPA 2000动态机械硫化仪测定，硫化温度为150度，频率为0.883HZ，应力角度为0.2度，实验设计的响应点是焦烧时间t2，正硫化时间t90最大力矩SMAX，以及硫化曲线上方面积。试样的硫化压力为100巴，温度为150℃，正硫化t90再加3分钟，橡胶的机械性能用Zwick BZ1.0/TH1S强力试验机试验，测试项目有杨氏模量(E-mod)、伸长300%的应力，强度和断裂强度。
3.2.4 Fibre treatment 纤维的处理
The p-aramid fibres were dipped twice: initially with an epoxy predip followed by a RFL-dip. The composition of the epoxy predip solution is depicted in Table 3.3; the solid content was 2 wt%. The preparation of the RFL-dip was carried out in two stages. First, a resorcinol formaldehyde resin solution was made and matured for 5 hours at 25¡ãC. Second, latex and more water were added to obtain a RFL-dip with a solid content of 17 wt%. The compositions of the resin solution and the total RFL-dip are shown in Table 3.3.
对位芳纶二次浸胶，最先进行环氧树脂的预浸胶，随后进行RFL浸胶。表3所列为环氧树脂组分，固含量为2%，RFL浸胶液份两步进行，起先，间苯二酚、甲醛树脂溶液在温度为25度，进行5小时的熟化，随后加入乳胶和水。使RFL浸胶也的固含量在17%左右，RF树脂溶液和RFL浸胶液的配方如表3.3。
The cord was pretreated by passing through the predip-container and through two ovens: the first with a temperature of 150¡ãC, the second 240¡ãC. Residence times were 120 and 90 seconds, respectively. Subsequently, the cord was passed through the RFL-dip container. The RFL-layer on the cord was cured in a third oven at 235¡ãC for 90 seconds. In every oven a tensile force of 8.5 N was applied to the cord. After dipping, the amount of dip on the cord was determined by dissolving the dip from the cords with a mixture of formic acid and hydrogen peroxide. The amount of dip present on the fibre is expressed as weight percentage, called the dip-pickup.
帘线现在与浸胶槽中通过，再经过2个烘箱进行与浸胶处理，第一组烘箱温度为150度，第二组为240度，停留时间分别为120秒和90秒，随后帘线进行RFL浸胶，帘线上的RFL浸胶层在第三组烘箱中进行处理，温度为235度，时间为90秒。每个烘箱，帘线的张力为8.5N，帘线的附胶量是通过用蚁酸和过氧化氢的混合液溶解浸胶层进行测定的。纤维上浸胶层的所占重量比，称做附胶量。
Table 3.3 Composition of the epoxy predip and the RFL-dip
表3.3 环氧树脂预浸胶和RFL浸胶液配方

3.2.5 Adhesion testing 粘合力试验
The adhesion between dipped cord and rubber compound after curing was measured by H-pullout measurements according to ASTM D 4776-98. The vulcanisation time for this experiment was adjusted to t90 plus 9 minutes. The maximum force recorded during the pullout test is referred to as pullout force. Each H-pullout value is the average of 40 measurements. Strap peel adhesion (SPAF) was measured according to ASTM D 4393-00. For the SPAF measurements the vulcanisation time was t90 plus 9 minutes just like the H-pullout measurements. The average force between the displacements of 40 and 140 mm is referred to as the Strap Peel Adhesion Force. Each value is an average of 6 measurements.
硫化后，浸胶帘线和橡胶之间的粘合力，根据ASTM D 4776-98标准进行H抽出力的测试分析的，本实验的硫化时间为正硫化时间t90加9分钟，在进行抽出试验时，所得到的最大力称做H抽出力，每个H抽出数据为40个试样的平均值。剥离力根据ASTM D 4393-00进行，剥离试验的硫化时间也为正硫化时间t90加9分钟。每个试样剥离量在40-140mm所获得的平均数称做剥离力。每个数据为6次试验的平均数。
3.3 RESULTS 结果
The cure data of the mixtures and the mechanical properties of the vulcanisates are summarised in Table 3.4. The data obtained from the adhesion measurements are shown in Table 3.5. These tables contain both data that are used as input for the models, compounds 1 to 15, and the verification models, Ver 01 and Ver 02. Drawing conclusions directly from these tables is not justified because a statistical setup is used. However, some compounds can be compared directly, for example compounds 9 and 11: the only difference is that compound 11 contains 1 phr of TBBS more than compound 9. As a result, compound 11 has higher mechanical properties than compound 9. For example the σ300 of compound 11 is 8.7 MPa versus 6.7 MPa for compound 9. On the other hand, the H-pullout force as well as the SPAF force at low and high temperature are much higher for compound 9 than for compound 11.
表3.4总结了硫化后的机械性能，表3.5为粘合试验的数据，这些表格中的数据是用于输入建立数学模型的，配方1-15，以及验证数学模型VER 01和VER02，从上表中直接得出结论是不正确的，因为使用了一种统计学方法，有些配方可以直接进行比较，比如配方9和配方11，其唯一差异是配方11的TBBS含量比配方9高了1份。其结果是配方11的机械性能高于配方9而已，比如配方11的300%伸长时的强度8.7 MPa，而配方9只有6.7 MPa，另一方面，配方9在低温和高温的H抽出力和剥离力则要比配方11高出许多。
The best way to look at the results is to model all responses as a function of sulphur, MBTS and TBBS contents (phr) and look at the behaviour of the models. The models of the cure characteristics and the mechanical properties are then compared to those of the H-pullout force and the SPAF at low and high temperature, to determine if there is a rubber bulk property dominating the adhesion behaviour.
查看试验结果的最好方法是将所有分析数据数学模型化，转化为硫磺、MBTS和TBBS含量的函数，再分析数学模型的特性。硫化特性和机械特性的数学模型才能和低温和高温下的H抽出力和剥离力数学模型相比较，确定是否有一种配方可以和粘合特性相匹配。

Table 3.4 Experimental results for the cure characteristics and the mechanical
表3.4试验的硫化特性和机械特性结果

Table 3.5 Experimental results for the adhesion measurements
粘合力试验结果
3.3.1 Evaluating the designs 试验设计的评估
To evaluate the results of the design, multiple linear regression (MLR) analysis is used. By the use the appropriate software, models are calculated relating the measured properties - the so called responses - to the variables, being the amounts of curatives added to the rubber compounds. In this way, the effect of each curative can be quantified independently. By interpolation, responses are calculated using these models and the properties (e.g. adhesion to dipped cord) can be predicted, as long as the input of these models stays within the limits of the design. Optimisation of the models can be achieved according to the principles of DOE, taking into account the goodness of fit, the robustness of the model and the reproducibility. For the optimum cure time t90, a logarithmic transformation was necessary in order to obtain an acceptable model; for the other responses no transformation was necessary. The calculated versus observed responses for all compounds are shown in Figures 3.2-3.7.
评估试验设计的结果，采用了多元线性回归分析，通过采用相关的软件，根据检测材料性能，也就是所谓的实际数据，进行数学模型计算出与变量，就是橡胶中的硫化助剂含量的关系，通过这种方法，可以将各种硫化助剂的影响进行量化，从而可以通过这些数学模型可以计算出理论的性能数据，只要这些数学模型的输入值在正交实验法的限制范围内，从而可以预测材料的性能（比如与浸胶帘线的粘合力）。考虑到匹配性，数学模型的可靠性和可重复性，可以根据正交实验法的原理对数学模型进行优化。对于正硫化时间t90，为了能够得到一个可接受的数学模型，有必要进行对数转换，对于其他数据，无需进行转换，各个配方的计算结果和实际结果见图3.2-3.7.
The responses on the horizontal axis are calculated according to the models that were obtained by the software. The data on the vertical axis are the measured values. The fully black squares indicate the compounds that participated in the design and the model that originated from the design. The white squares indicate the two verification compounds, Ver 01 and Ver 02. They were not included in the formation of the model. The straight line in the graphs passes the origin and has a slope of 1. In the Figures the values for R2, adjusted R2 and Q2 are given. These values are provided by the software used for the data analysis. R2 gives an indication of the goodness of fit: it has a value of 1 or lower: the closer to 1, the better the fit. R2adj is corrected for the amount of variables used to obtain the model, it reflects the balance between a good fit and the simplicity of the model. The value of R2adj is always lower than, but in the ideal case very close to, R2. The third parameter given in the figures is Q2; this is an estimation of the predictive power of the model. Like R2 and R2adj, the highest value it can reach is 1, but the lowest value is minus infinity. The predictive power is good when Q2 is higher than 0.5, and it is excellent when Q2 is higher than 0.9. The two verification compounds provide another indication of the predictive power of the model. The closer the white squares are to the straight line, the better the model predicted their values. The verification experiments were not taken into account when R2, R2adj and Q2 were calculated, since they were not part of the model set.
水平轴上的结果是根据软件得出的数学模型进行计算出来的，在垂直轴线上的数据是实际数值，黑色方块表示正交实验法生成的配方和数学模型，白色方块是验证配方，VER 01 和VER 02，他们不是在数学模型中，图中的直线穿过原点，斜率为1；在图中数值R2、调节后的R2 adj 以及Q2是给定的，这些数值是有软件计算出来的，用于数值分析。R2用于验证吻合度，数值为1或小于1，越是接近1，说明吻合度越好。R2adj用于修正建立数学模型的变量值，其反映了吻合度与数学模型简化之间的平衡，R2adj一般总是比R2低，但越接近越好，图中给出的第三个参数是Q2，这是用于评估数学模型的预测能力的，和R2、R2 adj一样，其数值最大为1，最小为负无穷大，如果Q2大于0.5，表示预测能力很强，最佳的是Q2大于0.9。两个验证配方，是用于验证数学模型的预测能力，白色方块越是靠近直线，数学模型的预测能力越强。由于验证试验不是数学模型设定的一部分，在R2、R2 adj、Q2计算后，验证试验是不作考虑的。
Taken the parameters from Figure 3.2 into account, the models for the t2, the t90 and the area above the rheometer curve resulted in good models. The model for the maximum torque level is excellent: R2 and R2adj are very similar and close to 1, and Q2 is higher than 0.9. Furthermore, the two verification compounds are exactly on the straight line. For the same reasons, the stress at 300% strain resulted in an excellent model: Figure 3.3. The models of the other responses in Figure 3.3 are good, as judged by the Q2 being between 0.5 and 0.9. The models for the hardness, Figure 3.4, and the H-pullout force, Figure 3.5, resulted in excellent models. Both the measured force and the rubber coverage of the SPAF measurements at room temperature, Figure 3.6, resulted in clearly poorer models compared to the previous ones. However, the Q2 is higher than 0.5 in both cases and therefore the models can be regarded as good. However, for the SPAF measurements at 120¡ãC, Figure 3.7, this is not the case. The model for the SPAF force itself is good, but for the SPAF rubber coverage a Q2 of -0.757 is obtained, which signifies a poor predictive model.
从图3.2中的数据看，t2, t90以及硫化曲线上部的面积的数学模型比较好，最大转矩数学模型非常好，因为其R2 和 R2adj接近于1，而Q2大于0.9，此外，两组验证配方，正好在直线上。同样，伸长为300%时的应力数学模型也非常好，图3.3中的其他试验数据的数学模型也比较好，它们的Q2均在0.5-0.9之间，图3.4，硬度以及H抽出力的数学模型非常好，但如图3.6所示，室温下的剥离力和剥离后橡胶覆盖率的数学模型不是太理想，但其Q2在0.5以上，数学模型也可以被认可，可是在120度下的剥离试验，情况有所不同，剥离力的数学模型是理想的，而剥离后橡胶覆盖率的Q2为-0.757，是一个预测能力很差的数学模型。
The reason that SPAF measurements are difficult to model lies in their complexity. When a layer of cords is separated from rubber, the observed force is a combination of both the adhesive failure between dip and rubber and the tear of the rubber bulk. On top of the complex nature of the test, the judgement of rubber coverage is not absolute. A value of 0% (red cords) and 100% (complete rubber tear) is straightforward, but the values in between are subjective. Even though the Q2 of the model for the rubber coverage at 120¡ãC is low, the two verification compounds are close to the straight line. Furthermore, the goal of this model is not to predict absolute values between 0% and 100%, but to indicate the regions of low and high coverage in the experimental space of the design. For this purpose, this model will be used despite of its poor predictive power.
无法建立剥离后橡胶覆盖率的数学模型的原因是其背后十分复杂，当帘线与橡胶剥离时，剥离力是浸胶层与橡胶之间的粘合破坏以及橡胶的剪切破坏的合成，除了试验的复杂性外，橡胶覆盖率的判定也不是绝对的，从露出红色浸胶线的0%到橡胶撕裂的100%，其余数值是由人的主观判定的。即使120度橡胶覆盖率数学模型的Q2很低，但两个验证配方还是接近直线的，此外建立数学模型的目的不是用于预测一个绝对正确的数值，而是用于表明实验的覆盖率高低的区间，即使其预测能力不高，但还是可以使用该数学模型的。
The models can now be used to calculate the influence of a single curative, for example MBTS, on one of the responses. The other two curatives, in this case sulphur and TBBS, will be kept at their centre points. When the levels of the two curatives that are fixed in the calculations turn out to have a significant influence, this will be shown by using additional graphs.
这些数学模型可以用来计算单一硫化助剂的影响，比如MBTS，另外的硫化助剂硫磺和TBBS，保持其中间值。在计算中两种硫化助剂固定了用量高低变得有很大的影响，这将在另外的图标中说明。

Figure 3.2 Observed versus calculated responses of the cure characteristics: compounds that are part of the model (¡ö) and verification compounds (¡õ); A: t2; B: t90; C: S¡¯max and D: area above rheometer curve, according to Hupj¨¦
图3.2 硫化特性的实际实验数据和计算理论数据对比数学模型的设计配方（■），验证配方（□），A: t2; B: t90; C: S’max , D: 硫化曲线上方面积

Figure 3.3 Observed versus calculated responses of the tensile tests: compounds that are part of the model (¡ö) and verification compounds (¡õ); A: E-modulus; B: M300; C: tensile strength; D: elongation at break
图3.3 实际与计算强度试验结果：A: E-模量; B: M300; C:强度; D: 断裂伸长


Figure 3.4 Observed versus calculated responses of the hardness measurements: compounds that are part of the model (¡ö) and verification compounds (¡õ)
图3.4 硬度的试验结果与计算结果

Figure 3.5 Observed versus calculated responses of the H-pullout tests: compounds that are part of the model (¡ö) and verification compounds (¡õ)
图3.5 H抽出力的试验结果与计算结果

Figure 3.6 Observed versus calculated responses of the SPAF tests at room temperature: compounds that are part of the model (¡ö) and verification compounds (¡õ)
图3.6 室温下剥离试验的实际数据和计算数据对比

Figure 3.7 Observed versus calculated responses of the SPAF tests at 120¡ãC: compounds that are part of the model (¡ö) and verification compounds (¡õ)
图3.7 120度剥离试验的实际数据和计算数据的对比

3.3.2 Cure characteristics 硫化特性
In Figure 3.8, the influence of the curatives on the t2 and the t90 is shown as derived from the DOE models. Taking the 95% confidence interval into account, sulphur does not have a significant influence on the t2. MBTS has a negative and TBBS has a positive influence on the t2. The latter is because, unlike MBTS, TBBS is an accelerator of the scorch-delay type. Increasing amounts of all three curatives cause a decrease of the t90 due to the higher concentration of reactants and, as a result, a higher speed of cure. An increase of reactants, or curatives, causes an increase of the amount of crosslinks formed and therefore an increase in the optimum torque level is observed in Figure 3.9A. The effect of the curative content of the rubber compound on the area above the rheometer curve, according to Hupj¨¦, is shown in Figure 3.9B. Increasing the MBTS content of the rubber decreases the area above the rheometer curve, whilst for TBBS and sulphur this area increases.
图3.8所示为根据正交实验法衍生出来的，硫化助剂对t2和t90的影响，置信度为95%，硫磺用量对t2的影响不明显，MBTS对t2有负影响而TBBS有正影响，后者与MBTS不同，是一种焦烧延迟型的促进剂，增加3种硫化助剂的用量，由于反应物的浓度增加，导致t90缩短，造成硫化速度的提高。增加反应物，即硫化助剂的用量，提高了交联程度，也就提高了最佳力矩，如图3.9A所示。橡胶中硫化助剂的份数对硫化曲线上方面积的影响，如图3.9B所示，增加MBTS的用量，会降低硫化曲线上方面积，而增加硫磺和TBBS则增加面积。

Figure 3.8 Influence of the amounts of curatives on A: t2; and B: t90
图3.8 硫化助剂用量的影响A: t2;  B: t90

Figure 3.9 Influence of the amount of curatives on A: the maximum torque level; and B: the area above the rheometer curve according to Hupj¨¦8
图3.9 硫化助剂用量的影响A:最大转矩;  B: 硫化曲线上方面积

3.3.3 Mechanical tests  机械特性试验
In Figure 3.10, the behaviour of the models obtained for the tensile properties is shown. The E-modulus, Figure 3.10A, the stress at 300% strain, Figure 3.10B, and the tensile strength, Figure 3.10C, all show the same trend as observed for the maximum torque level in Figure 3.9A. The same conclusion can be drawn for the results of the hardness measurements: Figure 3.11. The explanation for the behaviour of all these responses is the same as for the maximum torque level and is related to the fact that more curatives lead to the formation of more crosslinks. The elongation at break does not depend significantly on the MBTS content, but decreases when the amount of sulphur and TBBS increases, Figure 3.10D. Overall, it can be concluded that the models originated from the design of experiments software describe the dependency of both the mechanical and the cure properties on the curatives accurately.
图3.10 数学模型的强度特性，图3.10A为E模量，图3.10B为300%伸长的应力，图3.10C为强度，与图3.9A所示的最大力矩有着同样的趋势，图3.11所示为硬度，有着相同的结果，对上述所有数据的结果的原因解释与最大转矩提高是相同的，就是硫化助剂的增加，导致交联度的提高。断裂伸长与MBTS没有太大的联系，但随着硫磺和TBBS用量的增加，断裂伸长会降低，如图3.10D所示。总之，依据正交实验法设计的配方可以精确地独立地分析机械特性和硫化特性。

Figure 3.10 Influence of the amounts of curatives on A: E-modulus; B: stress at 300% strain; C: tensile strength; D: elongation at break
图3.10 硫化助剂用量的影响 A 初始模量，B 300%伸长时的应力，C 强度，D 断裂伸长

Figure 3.11 Influence of the amounts of curatives on hardness
图3.11 硫化助剂用量对硬度的影响

3.3.4 Adhesion tests 粘合力试验
Compound 5 from Table 3.2 turned out to be too weak for all the adhesion measurements. Instead of interfacial failure, complete tear of the rubber bulk material was observed. Because the resulting force that is measured is not a value for the interfacial strength between the dip and the rubber, the adhesion results for compound 5 was not taken into account for the models that describe the H-pullout force, the SPAF force at 20¡ãC and the SPAF force at 120¡ãC.
表3.2中的配方5，所体现的粘合力是最低的，不是界面破坏，而是橡胶被撕裂，由于其剥离力不是浸胶层和橡胶界面处的受力，不能作为数学模型的数据，来描述H抽出力、以及20度和120度时的剥离力。
The dependency of H-pullout force on the curatives content of the rubber matrix is shown in Figure 3.12. An increase in the amount of the two accelerators, MBTS and TBBS, decreases the H-pullout force significantly. Sulphur does not influence the H-pullout adhesion at all, when MBTS and TBBS are kept at their centre levels. Figure 3.13A shows the dependency of the H-pullout adhesion on the sulphur content at low and high MBTS content; TBBS is kept here at the centre level. Figure 3.13B shows the same at low and high TBBS levels, keeping MBTS at the centre. From Figure 3.13A and B, it can be concluded that at low levels of MBTS and TBBS, sulphur has a positive influence on the H-pullout force. At high levels, this influence is negative. However, in all cases the influence of sulphur, both negative and positive, is less than the influence of the amount of the two accelerators mixed in the rubber matrix.
图3.12 分别给出了橡胶中硫化助剂含量对H抽出力的影响，增加两种促进剂的用量MBTS和TBBS，H抽出力会急剧降低，在MBTS和TBBS保持中间值时，硫磺则对H抽出力没有影响。图3.13A所示为结果是MBTS含量分别在高低水平、TBBS保持中间值时，硫磺对H抽出力的独立影响。图3.13是MBTS保持中间值，TBBS分别在高低水平。从图3.13A、B可见，MBTS和TBBS在低水平时，硫磺份数增加，有利于提高H抽出力。在MBTS和TBBS为高水平时，硫磺的增加是不利的。不管如何，硫磺的影响是否有利，其影响比两种促进剂的影响小。

Figure 3.12 Influence of the amounts of curatives on H-pullout force
图3.12 硫化助剂对H抽出力的影响

Figure 3.13 Influence of the amount of sulphur on H-pullout force at low and high values of MBTS (A) and TBBS (B)
图3.13 MBTS(A) 和TBBS(B) 在高低水平时，硫磺对H抽出力的影响
The influence of the amounts of curatives on the SPAF force and the rubber coverage are shown in Figure 3.14A and B, respectively. The SPAF force behaves in a similar manner to the H-pullout force: the accelerators have a significantly negative influence on the SPAF force; sulphur shows a more moderate negative influence. The error bars, that represent the 95% confidence interval, are larger for the SPAF force than for the H-pullout force. This shows that the model for the H-pullout force is better than that for the SPAF force, as indicated before by the values of R2, R2adj and Q2 for these models. The rubber coverage, Figure 3.14B, also decreases with increasing amounts of curatives. There are two cooperating mechanisms that explain this decrease. The first mechanism is the decrease in adhesion, making the dip-rubber interface weak and most likely to fail. The second mechanism is the increase in mechanical properties of the rubber matrix, making it more difficult for a crack to propagate through the rubber and diverting it to the dip-rubber interface. These two mechanisms combined explain the large drop in coverage for especially the TBBS variation in Figure 3.14B.
图3.14A和B分别是硫化助剂对剥离力和橡胶覆盖量影响，剥离力和H抽出力有着一样特性，促进剂对剥离力有着很大的负面影响，硫磺的负面影响要轻一些。表示95%的置信度，剥离力的误差区间比H抽出力的大，这表明H抽出力的数学模型比剥离力的数学模型要好，如以前R2, R2adj和Q2数值所表达的一样。橡胶覆盖率如图3.14B所述，也将随着硫化助剂含量的提高而降低。这一现象可以用两种相关的机理进行解释。第一中机理是因为粘合力的下降，造成粘合界面薄弱，几乎失效；第二机理是橡胶的机械性能提高，使得其无法穿过橡胶，渗透到RFL浸胶层中，这两个机理合起来就可以很好地解释为何橡胶覆盖率下降的原因，特别是图3.14B所示的TBBS用量变化说造成的结果。

Figure 3.14 Influence of the curatives on A: SPAF force; and B: rubber coverage
图3.14 硫化助剂用量对剥离力A和橡胶覆盖率的的影响，

Figure 3.15 Influence of the amount of sulphur on SPAF at low and high values of MBTS (A) and TBBS (B)
图3.15 在MBTS (A)和TBBS (B) 用量高低水平时硫磺用量对剥离的影响

In Figure 3.15A and B, the dependency of the SPAF force on the sulphur content is shown at low and high accelerator level. Unlike for the H-pullout force, increasing sulphur content does not increase the SPAF force, but lowers it. Figure 3.15A and B shows a level difference between low and high accelerator level, but the slope of the graphs is similar in both cases. The SPAF force and the rubber coverage at 120¡ãC as a function of the amount of curatives are shown in Figure 3.16A and B. The SPAF force at 120¡ãC shows basically the same behaviour as the SPAF at room temperature and the H-pullout force: the accelerators have a negative influence and sulphur hardly or no influence. As judged earlier from the values for R2, R2adj and Q2, the rubber coverage at 120¡ãC resulted in a poor predictive model. This is the reason that the error bars in Figure 3.16B, corresponding to the 95% confidence interval, are large. Despite the poor model, the rubber coverage at 120¡ãC shows a similar dependency on the curative content as the rubber coverage at room temperature, but at a lower level.
图3.15A和B所示为在高低水平时，硫含量对剥离力的影响。与H抽出力不同，增加硫的含量，不会提高剥离力，反而降低剥离力。图3.15A和B所示，促进剂的高低水平不同，但两种情况的斜率是相似的。图3.16A和B所示是在120度下的剥离力和橡胶覆盖率与硫化助剂含量的关系，120度时的剥离力与室温下的剥离力特性与H抽出力特性基本相同：促进剂有着负面的影响，而硫磺几乎无影响。如先前R2, R2adj 和Q2值所判定的那样，120度下的橡胶覆盖率是弱预示性的数学模型。这就是置信度为95%的置信区间大的原因。尽管这是一个弱预示性的数学模型，但在低水平下，硫化助剂含量对120度时的橡胶剥离覆盖率的影响与室温下的橡胶覆盖率影响是相似的，
The effect of sulphur on the SPAF force at 120¡ãC is different at low and at high MBTS levels, Figure 3.17A. At low MBTS level, increasing the sulphur content of the rubber compound increases the SPAF force. However, at high MBTS level, the SPAF force at 120¡ãC decreases. For low and high TBBS levels, keeping MBTS at the centre point, changing the amount of sulphur does not influence the SPAF force: Figure 3.17B.
在MBTS含量水平高低不同时，硫磺对120度下的粘合力影响也是不同的，图3.17A所示，在MBTS是低水平时，增加硫磺用量，可以身价剥离力，但在MBTS是高水平时，在120度的剥离力是下降的。如果MBTS为中间值，TBBS为高、低水平时，改变硫磺用量并不改变粘合力，如图3.17所示。

Figure 3.16 Influence of the curatives on A: SPAF force at 120¡ãC; and B: rubber coverage at 120¡ãC
图3.16 硫化助剂对A120度下的剥离力 B 120度的橡胶覆盖率

Figure 3.17 Influence of the amount of sulphur on SPAF at 120¡ãC at low and high values of MBTS (A) and TBBS (B)
图3.16 在MBTS (A)和TBBS (B)的高、低水平时，硫用量对120度下剥离力的影响

3.4 DISCUSSION
3.4.1 Correlation between mechanical properties and adhesion models
机械特性与粘合数学模型之间的关系
Adhesion measurements, both H-pullout and peel, record a force that depends on both the mechanical properties of the rubber compound and on the adhesion between fibre and rubber. The adhesion measurement therefore only gives an approximation of the “real” adhesion. Erickson18 reported that the degree of influence of the mechanical properties of the rubber in H-pullout measurements is lower than for peel measurements. This effect is the cause that the models for the SPAF force, at both 20¡ãC and 120¡ãC, are not as good as that of the H-pullout force. Despite the difference in quality, all three models show a comparable behaviour of the cord-rubber composite, judging from Figures 3.12, 3.14 and 3.16. However, these models show a different influence of the amount of sulphur at low and high accelerator levels. For low and high levels of TBBS and high levels of MBTS, Figures 3.13, 3.15 and 3.17, this difference is hardly significant, taking the error bars into account. However, at low levels of MBTS, increasing the amount of sulphur increases both the H-pullout force and the SPAF at 120¡ãC, but decreases the SPAF at room temperature.
H抽出力和剥离力的粘合力测试，其力的大小取决于橡胶的机械特性和纤维和橡胶之间的粘合。所以粘合力测试结果仅仅表示大致的“真实”粘合力。Erickson研究表明橡胶机械性能对H抽出力的影响比对剥离力的影响小。这就造成在20度以及120度时的剥离力数学模型没有H抽出力的数学模型好。尽管有数学模型特性的差异，但根据图3.12，3.14，3.16，所有三种数学模型均有能够可以进行帘线橡胶复合体的特性比较。然而，在促进剂含量的高低不同水平时，这些数学模型说明了硫磺用量的影响，在MBTS为高水平，TBBS的用量水平高低不同时，如图3.13，3.15，3.17所示，几乎没有重大的变化。但在MBTS为低水平，增加硫磺用量可以提高120度时的H抽出力和剥离力，但造成室温下剥离力的下降。
Comparing the graphs of the H-pullout force and both SPAF forces with those of the mechanical properties, Figure 3.10, it turns out that they show inverse relationships. Low concentrations of accelerators provide high rubber-cord adhesion, but low mechanical properties. Therefore, it turns out that the H-pullout and peel tests are not dominated by the rubber properties, but rather by adhesion phenomena between rubber and RFL-dip.
用机械特性比较H抽出力和剥离力，如图3.10，可以发现它们由反比关系，低的促进剂浓度，可以获得高的橡胶与帘线之间的粘合力，但机械特性差，因此H抽出或剥离试验不是有橡胶的机械特性控制的，而是有橡胶与RFL浸胶层的粘合现象决定的。
3.4.2 Correlation cure properties and adhesion models 硫化特性与粘合数学模型之间的关心
The scorch time increases with increasing amount of TBBS, as shown in Figure 3.8A. However, the adhesion decreases with increasing amounts of TBBS, as shown in Figure 3.12, 3.14 and 3.16. Therefore, the scorch time is also not the dominating rubber property that determines the adhesion, unlike what was proposed by Wootton15 and Albrecht.17
TBBS用量的增加，延长了焦烧时间，如图3.8A所示，但粘合力随TBBS用量增加而下降，如图3.12，3.14，3.16，因此焦烧时间同样不是橡胶的决定粘合的特性，并不像Wootton15 and Albrecht.17所建议的那样。
The area above the rheometer curve was determined for all the compounds of this design, resulting in a good model. Figure 3.9B shows how the area varies upon variation of the amount of curatives in the rubber compound. Increasing the MBTS content decreases the area, whilst increasing the amount of TBBS and sulphur causes an increase. Figure 3.9B does not correspond to the H-pullout and SPAF measurements shown in Figure 3.12, 3.14 and 3.16. Increasing the amount of TBBS increases the area but decreases the adhesion; and increasing the amount of sulphur increases the area significantly, but there is hardly a change in adhesion. According to these results, the area above the rheometer curve is again not the dominating rubber property that determined the rubber-cord adhesion.
根据正交实验法设计的所有配方的硫化曲线上方面积，建立了一个良好的数学模型，图3.9B所示，面积随硫化自己的用量改变而改变，增加MBTS的用量，将减小面积，而增加TBBS和硫磺的用量，则增加了面积。图3.9B与图3.12, 3.14 和3.16所显示的H抽出和剥离力测试不一致，增加TBBS用量，面积增加，但粘合力下降，增加硫磺的用量，面积达到大幅度提高，但粘合力不花不大，根据这些结果，硫化曲线上方的面积也并不是橡胶的决定粘合力的特性
The model for the t90, on the other hand, shows a close correlation to that of the H-pullout force. To illustrate this, two three-dimensional graphs for both the t90 and the H-pullout force are shown in Figure 3.18. In this figure, the sulphur level is kept at its centre value of 2.5 phr. From this figure, it can be concluded that, at a constant sulphur level, a rubber compound with a slow cure has a high H-pullout force and a rubber compound with a fast cure has a low H-pullout force. This agrees well with the study of Erickson.18 The t90 is the only rubber property that shows a good correlation with the adhesion results.
另一方面，T90的数学模型，则体现出与H抽出力相接近的关系，在图3.18中的T90和H抽出力的三维图对此进行解释，在图中，硫磺的用量为中间值：2.5份。通过该图，得出一个结论：硫磺用量固定，硫化速度慢，H抽出力大，硫化速度快，H抽出力小。这和Erickson的研究结果相同。t90是决定粘合力好坏的橡胶特性。

Figure 3.18 Three-dimensional graphs as a function of accelerator content of the rubber matrix, keeping a constant sulphur level of 2.5 phr; A: t90; and B: H-pullout force
图3.18 硫用量为2.5份时，促进剂含量影响的三维图， A t90 ,  B  H抽出力

3.5 CONCLUSIONS 结论
An important conclusion of the experiments described in this chapter is that the mechanical properties of the NR rubber compound show behaviours opposite to those of the adhesion measurements, confirming that the H-pullout and SPAF values primarily depend on adhesion phenomena rather than on the rubber mechanical properties.
本文的一个重要结论是，NR橡胶的机械特性的表现与粘合力测试结果正好相反，H抽出力和剥离力的大小主要取决于粘合而不是橡胶特性
The amounts of curatives that are mixed into the rubber compound, play an important role in the fibre-rubber adhesion mechanism. Especially the accelerators affect the adhesion significantly. Increasing the amounts of MBTS and TBBS decreases the adhesion measured by H-pullout force, SPAF at 20¡ãC and SPAF at 120¡ãC. When the accelerators are kept at their centre levels, the sulphur level hardly influences the adhesion.
橡胶中硫化助剂用量在纤维和橡胶的粘合机理中起到一个重要作用，特别是促进剂对粘合有着很大的影响。增加MBTS和TBBS的用量，H抽出力，20度和120度时的剥离力等粘合力下降，当促进剂用量为中间值，硫磺的用量，对粘合力几乎没有影响。
When comparing the models that originated from the cure curves to those of the adhesion measurements, it turned out that the scorch time of the rubber compound also is not a dominating factor that determined the level of adhesion. Also the area above the rheometer curve did not correlate with the adhesion, as was proposed by Hupj¨¦.8
当比较源自硫化曲线的数学模型与粘合力试验结果的关系，焦烧时间不是决定粘合力水平的决定因素，硫化曲线上方面积大小同样与粘合力无关，不像Hupj¨¦.所建议的那样。
The only model of a rubber bulk property that showed an excellent correlation with the adhesion models is that of the t90. When varying the amounts of MBTS and TBBS in the rubber compounds, at a constant sulphur level, the t90 behaves similarly to the H-pullout force and the SPAF force at low and high temperatures. In other words, within this experimental framework a slow curing rubber compound results in a high adhesion and a fast curing rubber compound results in a low adhesion.
发现与粘合力有着很好的正相关的橡胶特性是t90，当改变橡胶中MBTS和TBBS用量，硫磺用量保持不变，t90与H抽出力和高低温时的剥离力正相关，在本试验架构中，硫化速度慢的橡胶粘合力高，硫化速度快，着粘合力低。
3.6 REFERENCES 参考文献
1. W. Hupj¨¦, "Hechting van Textiel aan Rubber", in De Nederlandse Rubber Industrie. 1970.
2. N.K. Porter, J. Coat. Fabrics, 21, 230-239 (1992).
3. R.V. Uzina, I.L. Schmurak, M.S. Dostyan, and A.A. Kalinia, Sovjet Rubber Technology, 20, 18-22 (1961).
4. T. Takeyama and J. Matsui, Rubber Chem. Technol., 42, 159-257 (1969).
5. N.K. Porter, J. Coat. Fabrics, 23, 34-45 (1993).
6. A.L. Miller and S.B. Robison, Rubber World, 137, 397 (1957).
7. M.I. Dietrick, Rubber World, 136, 847-851 (1957).
8. W.H. Hupj¨¦, De Tex, 29, 267-271 (1970).
9. R.T. Murphy, L.M. Baker, and R. Reinhardt, Ind. Eng. Chem., 40, 2292-2295 (1948).
10. T.S. Solomon, Rubber Chem. Technol., 58, 561-577 (1985).
11. H.M. Wenghoefer, Rubber Chem. Technol., 47, 1066-1073 (1974).
12. B.C. Begnoche and R.L. Keefe, Rubber Chem. Technol., 60, 689 (1987).
13. A.G. Causa, Tire Reinforcement and Tire Performance, ASTM STP 694, 200- 238 (1979).
14. F.H. Sexsmith and E.L. Polaski, "Elastomer to textile bonding", in Polymer science and technology, L.H. Lee, Editor. 1975, Plenum Press, New York.
15. D.B. Wootton, "The Application of Textiles in Rubber". 2001, Shawbury: Rapra technology LTD.
16. N.A. Darwish, A.B. Shehata, S.N. Lawandy, and A.I. Abou-Kandil, Journal of Applied Polymer Science, 74, 762- 771 (1999).
17. K.D. Albrecht, Rubber Chemistry and Technology, 46, 981- 998 (1973).
18. D.E. Erickson, Rubber Chemistry and Technology, 47, 213- 230 (1974).
19. W. Weening and W.H. Hupje, Kautsch. Gummi Kunstst., 25, 321-324 (1972).
20. R.N. Datta, "Rubber Curing Systems". Rapra Review Reports. Vol. 12. 2002. p. 48.

Chapter 4 Curative migration from rubber into the RFL-dip film
硫化助剂从橡胶中渗透到RFL浸胶层
The RFL-rubber interface was investigated by three analytical tools: scanning electron microscopy coupled to energy dispersive x-ray spectrometry, Raman spectroscopy and nano-indentation. The Raman measurements failed due to a high absorbance of the laser light by the resin phase and fluorescence of the latex phase of the RFL-dip. By using SEM-EDX, a high level of atomic sulphur and zinc was observed in the RFL near the RFL-rubber interface. With the nano-indentation technique it was verified that this led to a high modulus, linked to a high local crosslink density. By using SEM-EDX on all compounds of the statistical design of Chapter 3, it was concluded that the RFL has a high affinity to especially the accelerator molecules that are mixed in the rubber compound. Since the adhesion also largely depends on the amount of the same accelerator molecules, it is proposed that the high local crosslink density of the RFL near the RFL-rubber interface influences the adhesion in a negative way, for example by causing a brittle layer.
RFL浸胶界面采用了三种分析工具进行分析，带有能量衍射的X射线分光机的电子扫描显微镜、拉曼光谱学，纳米压痕技术。由于RFL浸胶层中的树脂相有很高的吸收激光以及胶乳相有荧光特性，所以拉曼测定结果是无效的，利用SEM-EDX分析，发现在靠近RFL/橡胶界面处的RFL中有高含量的原子态硫。采用纳米压痕技术，验证确认由此造成了模量的提高，这与高的交联密度相关。使用SEM-EDX对第三章所述的用正交实验法设计的配方橡胶进行了分析，其结论是RFL对橡胶中的促进剂分子有着强烈吸引，由于粘合力很大程度上取决于同样的促进剂分子的数量，这可能就是靠近RFL与橡胶界面处的RFL有着较高的交联密度，从而对粘合造成负面影响，比如造成脆性的浸胶层。

过木 · 发表于 2010-3-18 20:44:34

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dasher · 发表于 2010-3-18 21:23:27

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lhx0309 · 发表于 2010-3-18 21:59:53

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leiz_2000 · 发表于 2010-3-19 08:20:55

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chh31wxm · 发表于 2010-3-19 10:27:47

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chengcheng · 发表于 2010-3-19 19:59:58

呵，这么多内容，真是辛苦了。

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