Cohesive silicon

Because of their low intermolecular cohesion, silicone polymers generally have low mechanical strength. At the same time, the low intermolecular cohesion is associated with excellent gas permeability and low surface energy (Kyokaishi, 1993). 

To increase cohesion, silicone elastomers can easily be cross-linked via radicals generated by thermal decomposition of peroxides or by electron beam radiation. 

This chapter first reviews the general structures and properties of silicone polymers. It goes on to describe the crosslinking chemistry and the properties of the crosslinked networks. The promotion of both adhesive and cohesive strength is then discussed. The build up of adhesion and the loss of adhesive strength are explained in the light of the fundamental theories of adhesion. The final section of the chapter illustrates the use of silicones in various adhesion applications and leads to the design of specific adhesive and sealant products. 

Pure PDMS networks are mechanically weak and do not satisfy the adhesive and cohesive requirements needed for most applications in which the silicone adhesive joint is subjected to various stresses. For crosslinked silicones to become high performing adhesives, they need to be strengthened. 

The performance of a product where adhesion plays a role is determined both by its adhesive and cohesive properties. In the case of silicones, the promotion of adhesion and cohesion follows different mechanisms [37]. In this context, adhesion promotion deals with the bonding of a silicone phase to the substrate and reinforcement of the interphase region formed at the silicone-substrate interphase. The thickness and clear definition of this interphase is not well known, and in fact depends on many parameters including the surface physico-chemistry of... 

Since the locus of failure can clearly distinguish between adhesive and cohesive failures, the following discussion separates loss of adherence into loss of adhesion and loss of cohesion. In the loss of cohesion it is the polysiloxane network that degrades, which can be dealt with independently of the substrate. The loss of adhesion, however, is dependent on the cure chemistry of the silicone, the chemical and physical properties of the substrates, and the specific mechanisms of adhesion involved. 

Weak boundary layer. WBL theory proposes that a cohesively weak region is present at the adhesive-substrate interface, which leads to poor adhesion. This layer can prevent the formation of adhesive bonds, or the adhesive can preferentially form bonds with the boundary layer rather that the surface it was intended for. Typically, the locus of failure is interfacial or in close proximity to the silicone-substrate interface. One of the most common causes of a WBL being formed is the presence of contaminants on the surface of the substrate. The formation of a WBL can also result from migration of additives from the bulk of the substrate, to the silicone-substrate interface. Alternatively, molecular... 

Silicone networks that form the matrix of the adhesives are not susceptible to degrade or to depolymerize when exposed to a wide range of conditions of temperature and relative humidity. Therefore, the cohesive strength will not change, as... 

We have attempted to relate the basics of silicone chemistry to applications where adhesion is an important property. These applications cover a vast industrial arena that does not make a review of this sort easy. Instead, we focused on the fundamental aspects of silicone physics and chemistry and related them to adhesion and adherence properties. We have attempted to use a logical structure to help the reader understand silicone adhesion. Adhesion and cohesion have been considered as they both determine the ultimate performance of an adhesive joint. 

The design of a silicone adhesive naturally considers both the creation of adhesive and cohesive strengths to provide the performance needed. 

Molecular dynamics simulation (MDS) is a powerful tool for the processing mechanism study of silicon surface fabrication. When a particle impacts with a solid surface, what will happen Depending on the interaction between cluster and surface, behaviors of the cluster fall into several categories including implantation [20,21], deposition [22,23], repulsion [24], and emission [25]. Owing to limitations of computer time, the cluster that can be simulated has a diameter of only a few nanometres with a small cohesive energy, which induces the cluster to fragment after collision. 

The interaction between particle and surface and the interaction among atoms in the particle are modeled by the Leimard-Jones potential [26]. The parameters of the Leimard-Jones potential are set as follows pp = 0.86 eV, o-pp =2.27 A, eps = 0.43 eV, o-ps=3.0 A. The Tersoff potential [27], a classical model capable of describing a wide range of silicon structure, is employed for the interaction between silicon atoms of the surface. The particle prepared by annealing simulation from 5,000 K to 50 K, is composed of 864 atoms with cohesive energy of 5.77 eV/atom and diameter of 24 A. The silicon surface consists of 45,760 silicon atoms. The crystal orientations of [ 100], [010], [001 ] are set asx,y,z coordinate axes, respectively. So there are 40 atom layers in the z direction with a thickness of 54.3 A. Before collision, the whole system undergoes a relaxation of 5,000 fsat300 K. 

An absorbent may also be necessary when the formulation contains a hygroscopic ingredient, especially when absorption of moisture produces a cohesive powder that will not feed properly to the tablet press. In such instances, silicon dioxide has been found to be of particular value. 

An aqueous base is the least expensive vehicle and poses no toxicity problems. A solution of the drug in water or water and cosolvent is made. Glycerin, glycols, natural and synthetic gums, and/or polymers are used to increase viscosity, cohesiveness, and plasticity. To overcome syneresis, or water separation in the gel, a common problem with aqueous bases, one can use absorbing materials such as microcrystalline cellulose, kaolin, colloidal silicon dioxide, starch, etc. 

---