Void formation

Aluminum, the most common material used for contacts, is easy to use, has low resistivity, and reduces surface Si02 to form interfacial metal-oxide bonds that promote adhesion to the substrate. However, as designs reach submicrometer dimensions, aluminum, Al, has been found to be a poor choice for metallization of contacts and via holes. Al has relatively poor step coverage, which is nonuniform layer thickness when deposited over right-angled geometric features. This leads to keyhole void formation when spaces between features are smaller than 0.7 p.m. New collimated sputtering techniques can extend the lower limit of Al use to 0.5-p.m appHcations. 

Orientation sometimes leads to lower permeabiHty values (better barrier properties). Orientation can iacrease packing density, which lowers the diffusion coefficient D it can also iacrease the difficulty of hopping or diffusiag ia a direction perpendicular to the film. In the latter case, movement ia general may be fast, but movement through the film is limited. However, mere stretching does not always lead to orientation of the molecular chains. In fact, stretching can lead to void formation, which iacreases permeabiHty. 

In the initial stage of carbonization, it is critical to control the off-gases that evolve from the fiber as it is heated. Excessive heating rates result in void formation, stmctural dismption, and lower carbon fiber properties. 

Figure 8.35. 1100-0 aluminum Taylor impact specimen (12.5 mm diameter) sectioned and polished illustrating void formation near impact interface. 

Probably the most comprehensive measurements of the effect of voids on rates are those of Cohen "" and his school. They have published data on the oxidation of pure irons for a wide temperature range and for oxygen pressures ranging from 1-3 x 10 "N/m to lOOkN/m. The interactions between void formation and oxygen uptake are complex but only at pressures below 1 3 X 10 N/m do voids have no effect. Some of their results are summarised in Fig. 1.85 over the pressure range 1-3 x 10 N/m to... 

At temperatures above or near the eutectic temperature of the polymer phase, CSEi values are typically in the range of 0.1-2 pFcm-2 [5], However, for stiff CPEs or below this temperature, CSEI can be as low as 0.001 pFcm 2 (Fig. 16). When a CPE is cooled from 100 °C to 50 °C, the CSE1 falls by a factor of 2-3, and on reheating to 100 °C it returns to its previous value. This is an indication of void formation at the Li/CPE interface. As a result, the apparent energy of activation for ionic conduction in the SEI cannot be calculated from Arrhenius plots of 1// sei but rather from Arrhenius plots of 7SE)... 

Uniform wall thickness Wall requirements are usually governed by the load, the support needs for other components, attachment bosses, and other protruding sections. Designing a product to meet all these requirements while still producing a reasonably uniform wall will greatly benefit its durability. A uniform wall thickness will minimize stresses, differences in shrinkage, possible void formation, and sinks on the surface it also usually contributes to material saving and economy in production. 

Curing of Polyimlde Resin. Thermoset processing involves a large number of simultaneous and interacting phenomena, notably transient and coupled heat and mass transfer. This makes an empirical approach to process optimization difficult. For instance, it is often difficult to ascertain the time at which pressure should be applied to consolidate the laminate. If the pressure is applied too early, the low resin viscosity will lead to excessive bleed and flash. But if the pressure is applied too late, the diluent vapor pressure will be too high or the resin molecular mobility too low to prevent void formation. This example will outline the utility of our finite element code in providing an analytical model for these cure processes. 

The basic mechanism of toughening is one of void formation and shear band formation (cavitation) when stress is applied. 

Kirkendall void formation can, however, be prevented from occurring by choosing the right metal species. For example, whereas platinum coating on copper is subject to the Kirkendall void creation process, the same coating on electrodeposited nickel is free of it even if heated to as high as 600°C for many hours (more than 10 hours ). 

Other than in polymer matrix composites, the chemical reaction between elements of constituents takes place in different ways. Reaction occurs to form a new compound(s) at the interface region in MMCs, particularly those manufactured by a molten metal infiltration process. Reaction involves transfer of atoms from one or both of the constituents to the reaction site near the interface and these transfer processes are diffusion controlled. Depending on the composite constituents, the atoms of the fiber surface diffuse through the reaction site, (for example, in the boron fiber-titanium matrix system, this causes a significant volume contraction due to void formation in the center of the fiber or at the fiber-compound interface (Blackburn et al., 1966)), or the matrix atoms diffuse through the reaction product. Continued reaction to form a new compound at the interface region is generally harmful to the mechanical properties of composites. 

Three triple bonds react to give the aromatic cyanurate ring without any hy-products. This is especially enticing for fiber matrices where void formation will he reduced. 

The outer side cools and solidifies first the inner part remains fluid the longest its shrinkage in the final stage of solidification is constrained. Its density will, therefore, be lower than at the outer side and tensile stresses are being built up, even with the risk of void formation. 

The occurrence of voids has been thoroughly documented in thick laminates [2], In almost all cases, they are apparently associated with the prepreg surface. The exact mechanism of void formation depends on the system, but in the most general case it can include mechanical entrapment as well as nucleation of stable voids in the resin phase. 

The model framework for describing the void problem is schematically shown in Figure 6.3. It is, of course, a part of the complete description of the entire processing sequence and, as such, depends on the same material properties and process parameters. It is therefore intimately tied to both kinetics and viscosity models, of which there are many [3]. It is convenient to consider three phases of the void model void formation and stability at equilibrium, void growth or dissolution via diffusion, and void transport. 

Figure 6.10 Void stability map for pure water void formation in epoxy matrixes. Note the significant effect of initial relative humidity exposure of the resin...

The second ramp portion of this cure cycle is critical from a void nucleation and growth standpoint. During this ramp, the temperature is high, the resin pressure can be near its minimum, and the volatile vapor pressure is high and rising with temperature. These are the ideal conditions for void formation and growth. 

Several viscosity and kinetic models, and experimental procedures for developing these models, are available for a number of commercially available resin systems [1-5]. These models allow insight into autoclave process decisions based on changes in resin viscosity and kinetic behavior and can be used to determine hold temperatures and durations that allow sufficient resin flow and cross-linking to avoid over bleeding, exotherms, and void formation. 

High pressures are commonly used during autoclave processing to provide ply compaction and suppress void formation. Autoclave gas pressure is transferred to the laminate due to the pressure differential between the autoclave environment and the vacuum bag interior. Translation of the autoclave pressure to the resin depends on several factors, including the fiber content, laminate configuration, and the amount of bleeder used. 

An appreciation of the importance of hydrostatic resin pressure must be developed to understand void growth fully. Because of the load-carrying capability of the fiber bed in a composite layup, the hydrostatic resin pressure needed to suppress void formation and growth is typically only a fraction of the applied autoclave pressure. The hydrostatic resin pressure is critical because it is the pressure that helps to keep volatiles dissolved in solution. If the resin pressure drops below the volatile vapor pressure, then the volatiles will come out of solution and form voids. 

In the early stages of the cure cycle, the hydrostatic resin pressure should be equal to the applied autoclave pressure. As resin flow occurs, the resin pressure drops. If a laminate is severely overbled, then the resin pressure could drop low enough to allow void formation. Thus, the hydrostatic resin pressure is directly dependent on the amount of resin bleeding that occurs. As the amount of bleeding increases, the fiber volume increases, resulting in an increase in the load carrying capability of the fiber bed. 

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