Adhesive Bonding of Clean and Oil-Contaminated Electrogalvanized Steel Substrates

The performance of two-part, amidoamine-cured epoxy adhesives on clean and oil-contaminated electrogalvanized steel (EGS) was studied using screening and lap shear tests. On exposure to boiling water, the cured epoxy adhesives with amidoamines having higher amine value delaminated from the clean and oil-contaminated EGS surfaces before those cured with amidoamines having low amine value. The results of X-ray photoelectron spectroscopy (XPS) showed that the adhesives cured with amidoamines having high amine value were unable to displace the oil from the EGS substrate. However, the durability and the strength of the adhesive bonds on the oiled EGS could be improved by adding proper amounts of silane or wetting agent to the adhesive. The preferential adsorption of amino curing agents occurred on the clean EGS surface, confirmed by XPS and reflection absorption infrared spectroscopy, and this decreased the durability of the bonds in boiling water. In addition, from XPS analyses of various specimens, different amounts of cured resins were detected in the adhesive/EGS interfacial regions which affecting the durability of the adhesive bonds. In addition, the amidoamine curing agents may form complexes on the EGS surface.     

固化剂对低温固化环氧建筑胶性能的影响

研究了6种不同固化体系在-12～0℃温度下的固化情况,探讨了不同固化剂对胶粘剂固化反应速度、压缩强度及钢一钢拉伸剪切强度的影响。试验结果表明,MS-0021固化剂各项性能优于其他固化剂,其压缩强度值为62．56MPa,钢－钢拉伸剪切强度值为1523MPa,可满足胶粘剂的冬季施工要求。     

水下环氧树脂胶粘剂用水下固化剂的性能研究

目前可用于水下粘接的EP(环氧树脂)胶粘剂用水下固化剂种类不多,主要是一些憎水类改性胺固化剂(如810和301P等)。以不同种类的水下固化剂作为试验对象,着重探讨了水下固化剂的本体黏度、相应水下EP胶粘剂的某些性能(如水下凝胶时间、水下拉伸剪切强度及水下压缩强度等)。研究结果表明:水下EP胶粘剂的适宜凝胶时间为1h左右;水膜隔离胶粘剂/被粘物的界面问题只影响拉伸剪切强度,而不影响压缩剪切强度,故水下固化剂的憎水性良好时,相应EP胶粘剂的压缩强度相对较高,但其钢/钢拉伸剪切强度会受到一定的影响;810和301P具有一定的憎水性,并且相应EP胶粘剂的水下凝胶时间均为1h左右,故不同黏度的810和301P复配可制得综合性能更好的水下EP胶粘剂。     

Fracture mechanism and oil absorption of an oil-accommodating adhesive

We have studied the fracture mechanism and oil absorption in an oil-accommodating adhesive. Shear and T-peel tests were carried out for test pieces prepared from two steel plates bonded with the adhesive, which is mainly composed of epoxy resin, modified NBR, and inorganic powders. When the modified NBR content was varied from 3 to 25 wt%, both the shear and the T-peel strengths increased with the modified NBR content and levelled off at around 10 wt% modified NBR content. This behavior was coincident with that in the tear test by the samples prepared from cured adhesive. Therefore, fracture in the shear and T-peel tests is attributed to the tearing of cured adhesive. The oil absorbed in the non-cured adhesive bleeds out during curing. However, this oil can be stored in the grooves of steel plates.     

提高RTV732硅酮胶剥离强度的试验研究

以RTV732单组分硅酮胶作为硅橡胶/铝合金粘接用胶粘剂,探讨了不同的固化条件对胶接件粘接性能的影响。结果表明:RTV732硅酮胶在不同固化条件下的剥离强度虽有所差异,但硅橡胶/铝合金胶接件经常温固化24 h、130℃固化2 h后的剥离强度明显优于常温固化24 h后的剥离强度。     

适用于低温固化的低黏度高强度环氧树脂结构胶

以碳酸丙烯酯(PC)为活性稀释剂、自制增韧型421固化剂/快固型DETA(二乙烯三胺)固化剂作为复合固化剂,制备环氧树脂(EP)结构胶。研究结果表明:当m(EP)∶m(PC)∶m(421)∶m(DETA)=100∶20∶24∶6.0时,EP结构胶的初始黏度(60 mPa.s)相对较低,其强度和韧性俱佳(拉伸强度为45 MPa、压缩强度为70 MPa和钢/钢剪切强度为12.0 MPa);该EP结构胶可低温固化(5℃或常温固化7 d后的拉伸强度基本一致),也是一款适用于冬季施工的低黏度高强度EP结构胶。     

Molecular Structure of Polymer/Metal Interphases

The molecular structure of interphases in aluminum/epoxy and steel/epoxy adhesive joints was characterized using infrared spectroscopy. In one series of experiments, adhesive joints were prepared by curing beams of epoxy against aluminum or steel substrates. When the joints were cooled to room temperature, the residual stresses were sufficient for crack propagation along the interface. The adhesive and substrate failure surfaces were then analyzed with reflection-absorption infrared spectroscopy (RAIR), attenuated total reflection infrared spectroscopy (ATR) and X-ray photo-electron spectroscopy (XPS). When an epoxy/anhydride adhesive was cured against aluminum substrates primed with an aminosilane coupling agent, amide and imide groups were formed in the interphase. Chemical reaction between the primary amine of the primer and the anhydride of the curing agent precluded chemical bridge formation between the primer and adhesive. Metal cations from the 2024 aluminum substrate reacted with the anhydride to form carboxylate salts on the surface. When an epoxy/tertiary amine adhesive was cured against steel substrates, evidence of oxidation of the primary amine to imine was observed in the interphase.     

Molecular Structure of Polymer/Metal Interphases

The molecular structure of interphases in aluminum/epoxy and steel/epoxy adhesive joints was characterized using infrared spectroscopy. In one series of experiments, adhesive joints were prepared by curing beams of epoxy against aluminum or steel substrates. When the joints were cooled to room temperature, the residual stresses were sufficient for crack propagation along the interface. The adhesive and substrate failure surfaces were then analyzed with reflection-absorption infrared spectroscopy (RAIR), attenuated total reflection infrared spectroscopy (ATR) and X-ray photo-electron spectroscopy (XPS). When an epoxy/anhydride adhesive was cured against aluminum substrates primed with an aminosilane coupling agent, amide and imide groups were formed in the interphase. Chemical reaction between the primary amine of the primer and the anhydride of the curing agent precluded chemical bridge formation between the primer and adhesive. Metal cations from the 2024 aluminum substrate reacted with the anhydride to form carboxylate salts on the surface. When an epoxy/tertiary amine adhesive was cured against steel substrates, evidence of oxidation of the primary amine to imine was observed in the interphase.     

有机硅烷偶联剂对丙烯酸酯胶粘剂粘接作用的研究

利用剪切粘接强度、SEM等方法 ,考察了有机硅烷偶联剂的种类和处理方法对丙烯酸酯类胶粘剂 ,粘接强度的影响。结果表明 :将偶联剂KH - 570预处理物体表面及掺入乳液、适当高的固化温度都能显著地提高粘接强度。     

新型可见光固化口腔正畸粘合剂研制

介绍了一种新型可见光固化正畸粘合剂的组成、性能及正畸粘接的工艺。此粘合剂由一种单组分液体底胶和单组分糊剂组成。与化学固化粘合剂相比,其操作使用方便,固化时间短。这种新型粘合剂的粘接强度完全满足了正畸粘合剂的要求。     

Selected aspects of epoxy adhesive compositions curing process

The paper focuses on selected parameters of curing process – temperature and time. The tests aimed at evaluating the impact of short-term thermal recuring on 1050A and 2017A aluminium alloy sheet adhesive joints strength. Joints were formed with two different adhesives, the main component of which was in both cases epoxy resin Epidian 53 and two different cure agents – poliamineamide C (PAC) and triethylenetetraamine (PF) curing agents. Curing conditions – first curing time, recuring time and recuring temperature – were modified for each of the four tests conducted. For the sake of comparative analysis, adhesive joints were subjected to a single-stage cure cycle at ambient temperature. A two-stage cure cycle of both Epidian 53 compositions at 80?°C for 1 and 2?h produces a material of different mechanical properties than the same material which submits a single-stage cure cycle at ambient temperature, as well as at 60?°C for 30?min. Simultaneously, Epidian 53/PF/100:50 composition proves to produce higher joint strength after recuring than Epidian 53/PAC/100:80; the strength of a joint formed with the former composition increases up to 50% when compared with joints subjected to a single-stage cure cycle. Moreover, tests show that recuring of the adhesive joint formed with both compositions at 60?°C for 30?min does not have a considerable influence on either 1050A or 2017A aluminium adhesive joint strength.     

新型有机硅多元胺环氧树脂固化剂结构与性能

评价了3种有机硅多元胺APS、SFA和PSPA分别固化环氧树脂E51(DGEBA)时,固化物的力学性能和粘接强度,并与常见脂肪胺类固化剂[乙二胺、己二胺、聚醚胺(D-230)]作了对比。固化物基体力学和热性能测试表明,有机硅多元胺环氧固化物表现出较佳的冲击强度、弯曲强度和热稳定性。有机硅多元胺/环氧树脂胶粘剂的铁片粘接强度以及耐水性明显高于脂肪胺/环氧胶粘剂体系,其中含苯基有机硅多元胺作为固化剂时粘接强度最高,达到14.8 MPa。()     

塑纤编织袋用胶粘剂的研制

采用聚氨酯为主要原料,加入固化剂、增粘剂等辅助材料,研制成功了一种聚乙烯、聚丙烯塑纤编织袋用胶粘剂,讨论了其配方组成和操作条件对胶粘剂性能的影响。该胶粘剂初粘力强,胶膜附着牢固,耐冲击性好,适用于编织袋生产中袋口的粘接自动化。     

金属工件的表面处理及胶接工艺对胶接剪切强度的影响

采用环氧树脂-DDS固化体系作为胶接剂,探讨了各种金属表面处理方法、胶接时对胶接面施加的压力、胶层厚度等因素对胶接剪切强度的影响.结果表明,对不锈钢工件采用盐酸氧化法及草酸-硫酸氧化法进行表面处理,得到的胶接剪切强度最好;对铝合金工件采用硅酸磷酸钠法进行表面处理,得到的胶接剪切强度最高.胶接时对胶接面施加0.1～0.4Mpa的压力、胶层厚度在0.10～0.23 mm范围内时胶接效果最好.由于处理液对金属表面产生适度的化学腐蚀,改变了金属表面的物理化学性质,表现出更好的可浸润性和更强的表面吸附力,可以有效地提高胶接剪切强度.     

固化温度对缓凝黏合剂固化时间和强度的影响

为研究固化温度对缓凝黏合剂固化时间和强度的影响,将缓凝黏合剂在固化温度分别为25、45、65、85 ℃的条件下养护。通过邵氏硬度试验研究了3种缓凝黏合剂在不同固化温度条件下的固化速率,测试了缓凝黏合剂在不同固化温度条件下的拉伸剪切强度、抗折强度和抗压强度。结果表明,固化温度越高,缓凝黏合剂固化时间越短,以25 ℃为基准,45 ℃条件下的固化时间缩短约50 %,45 ℃以上,温度每升高20 ℃,固化时间缩短约10 %;以25 ℃条件下的强度为基准,缓凝黏合剂在不同固化温度条件下拉伸剪切强度的变化率在6 %内,抗折强度的增加率在6 %~45 %,抗压强度的增加率在9 %~50 %。     

The effect of curing temperature on thermal,physical and mechanical characteristics of two types of adhesives for aerospace structures

The effects of cure temperatures on the thermal, physical and mechanical characteristics of two types of thermosetting structural epoxy film adhesives were determined in detail. The aim of this paper is to assess the effect of cure temperatures (82–121 °C) on the degree of cure of the two adhesives and the relevant void formations that need to be addressed in bonded part production and repair. Two thermal parameters were used to characterize the advancement of the reaction, such as degree of cure and glass transition temperature. The joint properties with respect to the cure temperatures were characterized by void content and bond-line thickness measurements and lap shear strength tests. Experimental results presented that all lap shear strengths were well within minimum shear strength (29 MPa) required by the specification of the film-type adhesive. However, the lap shear strength testing after aging at 82 °C and 95%R.H for 1000 h showed that the improved durability when the adhesive is cured at 121 °C did not occur for the 82 °C cure. Low curing conversion (75–77% degree of cure) combined with high voids (over 2 areal%) has a catastrophic effect on the bonding qualities at the metal-adhesive interface and due to lack of cohesion in the adhesive. The changes in the interface caused by the low temperature curing may contribute to an increased susceptibility of the bonded joint to moisture and consequent bond-line degradation.     

A Method of Predicting the Stresses in Adhesive Joints after Cyclic Moisture Conditioning

The durability of adhesive joints is of special concern in structural applications and moisture has been identified as one of the major factors affecting joint durability. This is especially important in applications where joints are exposed to varying environmental conditions throughout their life. This paper presents a methodology to predict the stresses in adhesive joints under cyclic moisture conditioning. The single lap joints were manufactured from aluminium alloy 2024 T3 and the FM73®-BR127® adhesive-primer system. Experimental determination of the mechanical properties of the adhesive was carried out to measure the effect of moisture uptake on the strength of the adhesive. The experimental results revealed that the tensile strength of the adhesive decreased with increasing moisture content. The failure strength of the single lap joints also progressively degraded with time when conditioned at 50°C, immersed in water; however, most of the joint strength recovered after drying the joints. A novel finite element based methodology, which incorporated moisture history effects, was adopted to determine the stresses in the single lap joints after curing, conditioning, and tensile testing. A significant amount of thermal residual stress was present in the adhesive layer after curing the joints; however, hygroscopic expansion after the absorption of moisture provided some relief from the curing stresses. The finite element model used moisture history dependent mechanical properties to predict the stresses after application of tensile load on the joints. The maximum stresses were observed in the fillet areas in both the conditioned and the dried joints. Study of the stresses revealed that degradation in the strength of the adhesive was the major contributor in the strength loss of the adhesive joints and adhesive strength recovery also resulted in recovered joint strength. The presented methodology is generic in nature and may be used for various joint configurations as well as for other polymers and polymer matrix composites.     

环境友好型底胶的研究进展

在航空工业中的胶接领域,为了降低底胶中含有的大量挥发性有机溶剂（VOC）和铬酸盐,促进了环保型底胶的研发。对于水基底胶、无机底胶以及不合铬酸盐的底胶的胶接耐久性试验表明,一些新型的环保型底胶的性能与传统的溶剂型底胶处于同一水平甚至更好。新型底胶也同样能够提高复合材料的胶接强度和耐久性能,但应该寻找更环保、更简便的方法来获得耐久性的胶接。磷酸阳极化作为铝合金胶接中最好的表面处理方法本身具有很好的耐久性,使用耐久性较好胶粘剂获得耐久胶接是较好的方案之一。     

碳基复合材料用耐高温胶黏剂的研制

采用耐热酚醛树脂杂化了磷酸盐胶黏剂,以纳米氧化铝、氧化锆和氧化锌为固化剂,制备了一种对C/C和C/SiC复合材料具有良好粘接性能的胶黏剂。通过不同测试温度下的剪切强度,差示扫描量热仪（DSC）,热失重（TG）以及扫描电子显微镜（SEM）探究了杂化胶黏剂的力学性能、固化行为、耐热性能以及高温下胶黏剂结构的变化。结果表明：酚醛树脂的加入,保持了耐热性能,降低了体系固化的固化温度,有效地提高了磷酸盐胶黏剂对C/C、C/SiC两种复合材料力学性能,室温下剪切强度均高于10MPa。     

预聚物对UV固化胶黏剂性能的研究

预聚物作为胶黏剂的主要成膜物质,它的性能基本决定了固化后胶黏剂的主要性能.采用不同类型的丙烯酸酯共混聚合的方法研究了预聚物对紫外光固化胶黏剂性能的影响.主要讨论了预聚物的种类、含量及复配对胶黏剂的固化速率、黏附力及粘接强度的影响.实验发现预聚物的种类和含量是胶黏剂的主要影响因素,脂肪族聚氨酯丙烯酸酯6148J和改性脂肪族聚氨酯丙烯酸酯6079性能较好,且二者比列为3:7,含量为50%时胶黏剂综合性能较好.