Epoxy resin, CTBN-toughened

Recently it has also been shown that modified spherical nanosilica particles can be used to toughen epoxy resins without the loss of other properties, such as glass transition temperature or modulus.28 When such surface modified nanoparticles are added to CTBN toughened epoxy resins, the performance of both one- and two-component epoxy adhesives was greatly improved. 

Figure 2. Electron micrograph of a bisphenol A modified CTBN-toughened epoxy resin (X8000)...

An electron micrograph of a fracture surface of a CTBN-toughened epoxy resin is shown in Figure 5. This CTBN is particular in that the in situ formed particles are less than 0.5 /zm in diameter. A tensile bar of this system also shows shear deformation which indicate that the small particles have not interfered with the shear deformation characteristic of the unmodified resin. The deformation bands are nearly parallel to the planes of maximum shear stress—i.e., roughly at 45° to the principal... 

Fig. 1. Chemical Reactions During the Cure of CTBN-Toughened Epoxy Resin...

Adhesive KH-225 is a paste structural adhesive based on CTBN-toughened epoxy resin. It can be cured with EMI at a temperature such as 60 to 80 C under contact pressure. 

Epoxy-nitrile adhesives have also been developed for the purpose of toughening conventional epoxy adhesives. These early adhesives were made from homogeneous blends of nitrile elastomer and epoxy resin. They are not similar to the modern-day CTBN toughened epoxy adhesive where the nitrile phase consists of discrete particles. An advantage of the... 

Siebert and Riew (4) described the chemistry of the in situ particle formation. They proposed that the composition of the particle is a mixture of linear CTBN-epoxy copolymers and crosslinked epoxy resin. The polymer morphology of the CTBN toughened epoxy systems was investigated by Rowe (5) using transmission electron microscopy by carbon replication of fracture surfaces. Riew and Smith (6) supported the... 

The solubility of CTBN in epoxy resin increases directly with the acrylonitrile content (3). Systems toughened with CTB and CTBS have the least improvement in fracture energy. This probably arises from the poor solubility of the polymers in epoxy resin however the solubility of CTA is very good. Although the particle sizes from acrylate polymers are rather small, the improvement in fracture energy is very good. 

Pearson and Lee (1991) examined the effects of particle-size and particle-distribution effects on rubber-toughened epoxy resins. They examined a variety of CTBN liquid rubbers and a methacrylated butadiene styrene core-shell particle in a DGEBA-piperidine system. They found that the toughening mechanism for small particles was internal cavitation of the... 

Section 19.S.1.2), and reported increases in toughness comparable to those achieved with CTBN. A further, but inconclusive, study compared pre-formed poly(n-butyl aciylate)-based particles made by emulsion and by suspension polymerization [97]. Dispersion polymerization in an epoxy resin has been used to give directly dispersions of acrylic rubber particles in the epoxy for subsequent use in toughening epoxy resins [98]. Core-shell toughening particles comprising 70 wt% of CFOSslinked polybutadiene cores, with a grafted functionalized shell have been claimed [99] to improve the fracture toughness of a methylene dianiline cured epoxy resin by a factor of 10. 

Fig. 35. Dependence of fracture energy on the modifier composition (CTBN 1300 X 9 = carboxyl-tenninated acrylonitrile, acrylic acid and butadiene rubber with 18% acrylonitrile and 2% acrylic acid contents CTBN 1300x 13 = carboxyl-terminated acrylonitrile, butadiene rubber with 26% acrylonitrile content) (Reprinted from Journal of Materials Science, 27, T.K. Chen, Y.H. Jan, Fracture mechanism of toughened epoxy resin with bimodal rubber-particle size distribution, 111-121, Copyright (1992), with kind permission from Chapman Hall, London, UK)...

An intense interest, currently without abatement, in the characterization of rubber-toughened thermosets in general, and rubber-toughened epoxy resins in particular, has surfaced over the last several years. Riew (18) summarized work leading to the optimization of toughness in an epoxy/CTBN/piperidine model. Concurrently, Kaelble (19) reported on such systems from a block copolymer orientation and examined properties related to adhesive... 

CTBN and ATBN are the most commonly used in structural epoxy adhesive formulations. CTBN (Fig. 8.6) is generally the elastomer of choice because of its miscibility in many epoxy resins. These tougheners were originally developed by BF Goodrich (now Noveon, Inc.) under the tradename Fly car. 

Carboxy-terminated curative, such as CTBN, provides excellent toughening in part due to its miscibility in many epoxy resins. Phase separation during cure is required to obtain toughening, and generally the phase separation requires an elevated-temperature cure. However, by prereacting the CTBN with a portion of the epoxy to obtain an adduct, a room temperature curing toughened epoxy is possible. Adduction reduces the likelihood of early phase separation and maintains the solubility of the elastomer in the uncured resin system. 

The use of rubbers (particularly epoxy-terminated butadiene nitrile, ETBN, rubber or carboxy-termi-nated butadiene acrylonitrile, CTBN, rubber) to toughen thermoset polymers is perhaps the most widely explored method and has been applied with some measure of success in epoxy resins. Phase separation of the second rubbery phase occurs during cure and its incorporation in the epoxy matrix can significantly enhance the fracture toughness of the thermoset. Although the rubber has a low shear modulus, its bulk modulus is comparable to the value measured for the epoxy, ensuring that the rubber inclusions introduced... 

Figure 1.34. Change in the phase boundary (UCST) during the cure reaction for a system of a rubber (e.g. CTBN) dissolved in an epoxy resin. Toughening requires that phase separation be achieved during the cure cycle. After Pascualt et al. (2002).

In a fundamental study of the factors affecting the growth of the rubber domains in a CTBN-toughened DGEBA epoxy resin cured by piperidine (Manzione and GilUiam, 1981) the kinetics of phase separation were linked to the diffusivity, Uab, of the rabber (A) dissolved in the epoxy resin (B). The relevant dependence on the molar volume of the rubber (proportional to the radius of the rubber molecules when dissolved in the epoxy resin) at the viscosity for the temperature T of reaction is given by the Stokes-Einstein equation ... 

It was noted in the previous section that the carboxyl end groups on the CTBN elastomer affected the final performance of the material as a toughener since these groups would co-react with the epoxy resin and facilitate stress transfer from the brittle matrix to the phase-separated elastomer. Without this adhesion the particles could debond prematurely, which would lead to poor dissipation of the energy of the growing crack. It has also been noted that excessive adhesion between an epoxy resin and a thermoplastic could be deleterious to the performance (Williams et al, 1997). The process of toughening of a thermoset... 

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