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ULTRASONIC CAVITATIONS AND PRECISION CLEANING
The rapid advancements in various current technologies and the constant trend in miniaturizing of components have created a need for higher cleanliness levels. Precision or critical cleaning is currently in great demand and is expected to increase in the future. The rapid advancements in various current technologies and the constant trend in miniaturizing of components have created a need for higher cleanliness levels. Contamination in the level of mono-layers can drastically alter surface properties such as wet-ability, adhesion, optical or electrical characteristics. Particles in the range of few microns down to submicron levels, trace contaminants such as non-volatile residues (NVR) in the range of micrograms/cm2 and pictogram/cm2, ionics in the same range or traces of corrosion have become part of the daily concerns of the manufacturing engineers in major industries such as semiconductors, automotive, disk drive, optics, ophthalmic, glass, medical, aerospace, pharmaceuticals and tool coatings, among others. The specifications on trace contaminants and particle sizes are being tightened periodically to reflect the new technology trends. Every industry has its own set of cleanliness specifications and the focus differs. For example, while NVR has not been an automotive industry issue until now, it has been crucial for the semiconductor and the disk drive industries for years. Trace contaminants are not acceptable in the carbide, optics and ophthalmic industries, as they may cause adhesion failures in a multi-coating process that follows cleaning. For obvious reasons, absolutely clean surfaces are an extremely critical requirement in cleaning medical devices. Concern about particles has become a common denominator among all industries. Precision Cleaning For example, if the cleaning of organic and ionic contaminants is achieved by an aqueous process, it is important to have high quality water and the proper parameters in the rinsing stages. Otherwise, residual detergent and/or ionics from the rinsing water will be the new contaminants. If drying is slow, de-ionized rinse water may react with some metallic surfaces at high temperatures and create undesirable stains or marks. Re-contamination of cleaned parts with out-gassed residues produced from packaging or storing materials is another big concern. To select an effective cleaning method, the three essential factors directly influencing cleaning results are the cleaning chemistry, the scrubbing method and the process parameters. The subject of examining various combinations of available cleaning methods and their effectiveness, or lack thereof, is massive and well-explained in the current literature. The focus in this article will be on ultrasonic cavitations and the ultrasonic cleaning mechanism. Ultrasonic technology is proven to be a versatile method for cleaning various organic, inorganic and particle contaminants from various metallic and nonmetallic surfaces.
The removal of contaminants is consistent and uniform, regardless of the complexity and the geometry of the substrates. Ultrasonic waves are mechanical pressure waves formed by actuating the ultrasonic transducers with high frequency, high voltage current generated by electronic oscillators (power generators) (Figure 1). A typical industrial high power generator produces ultrasonic frequencies ranging from 20-120 kHz. Typical PZT transducers are normally mounted on the bottom and/or the sides of the cleaning tanks or immersed in the liquid. The generated ultrasonic waves propagate perpendicularly to the resonating surface. The waves interact with liquid media to generate cavitation implosions. High intensity ultrasonic waves create micro vapor/vacuum bubbles in the liquid medium, which grow to maximum sizes proportional to the applied ultrasonic frequency and then implode, releasing their energies. The higher the frequency, the smaller the cavitation size. The high intensity ultrasonics can also grow cavities to a maximum in the course of a single cycle. At 20 kHz the bubble size is roughly 170 microns in diameter (Figure 2). At a higher frequency of 68 kHz, the total time from nucleation to implosion is estimated to be about one third of that at 25 kHz. At different frequencies, the minimum amount of energy required to produce ultrasonic cavities must be above the cavitation threshold. In other words, the ultrasonic waves must have enough pressure amplitude to overcome the natural molecular bonding forces and the natural elasticity of the liquid medium in order to grow the cavities. For water, at ambient, the minimum amount of energy needed to be above the threshold was found to be about 0.3 and 0.5 watts/cm2 per the transducer radiating surface for 20 kHz and 40 kHz, respectively. The energy released from an implosion in close vicinity to the surface collides with and fragments or disintegrates the contaminants, allowing the detergent or the cleaning solvent to displace it at a very fast rate. The implosion also produces dynamic pressure waves which carry the fragments away from the surface. The implosion is also accompanied by high speed micro streaming currents of the liquid molecules.
Cavitation Generation and Abundance
Cavitations are generated in the order of microseconds. At the 20 kHz frequency, it is estimated that the pressure is about 35-70 K Pascal and the transient localized temperatures are about 5000ºC, with the velocity of micro streaming around 400 Km/hr (Figure 2). Several factors have great influence on the cavitation's intensity and abundance in a given medium. Among these factors are the ultrasonic wave form, its frequency and the power amplitude. Other determining factors are the colligative properties of the liquid medium, including viscosity, surface tension, density and vapor pressure; the medium temperature and the liquid flow, whether static or dynamic or laminar; and dissolved gases. In general, at low frequencies (20-30 kHz), a relatively smaller number of cavitations with larger sizes and more energy are generated. At higher frequencies, much denser cavitations with moderate or lower energies are formed. Low frequencies are more appropriate for cleaning heavy and large-size components, while high frequency (60-80 kHz) ultrasonics is recommended for cleaning delicate surfaces and for the rinsing step. For example, at 68 kHz, the cavitation abundance is high enough and mild enough to remove detergent films and remove submicron particles in the rinsing steps without inflicting damage on surfaces. The 35-45 kHz frequency range was found to be appropriate for a wide range of industrial components and materials.
Therefore, one would expect that at the higher frequency, at a given energy level, the scrubbing intensity would be milder, particularly on soft and thin or delicate surfaces, and more penetration and surface coverage into the recessed areas and small blind holes would be expected. Ultrasonic Frequency and Particle Removal
Aqueous and Semi-Aqueous Ultrasonic Cleaning
For example, we have found that ultrasonic cavitations enhanced the removal efficiency of hydrophobic solvent cleaning films by about 30 to 40 percent versus using a spray rinse technique, when coated metallic and non-metallic surfaces were treated with aqueous displacement solutions (ADS). The ADS material is chemically designed to be compatible with the substrate and to rapidly displace hydrophobes. All tested surfaces were rendered solvent-free and hydrophilic. Particles, in general, are not spherical and have irregular shapes. Some of the adhesive forces that influence detachment of a particle are van der Waals, electrical double layer, capillary and electrostatic. One would expect that small particles are easier to remove. The fact is that the smaller the particles, the more difficult they are to remove. The weight of the particle is another factor greatly influencing a particle detachment. Kaiser has recently reported that although the force between a particle and an adjacent surface decreases with particle size, it becomes more difficult to remove a solid particle from a solid surface because of the value of the ratio, Fa/W, where Fa is the force of attraction and W is the weight of the particle. The value of Fa/W increases rapidly as the diameter of a particle decreases. Ultrasonic Systems
Mechanism of Cleaning Three general classes of common contaminants are organic, inorganic and particulate matter. Particles do not necessarily belong to a certain class and can be from either class or a mixture. Contaminants of any class could be water soluble or water insoluble. Organic contaminants in most cases will be hydrophobic in nature, such as oils, greases, waxes, polymers, paints, print, adhesives or coatings. Most inorganic materials are insoluble in solvents that are water-immiscible. Water is the best universal solvent for ionic materials, organics or inorganics. However, water insoluble inorganics, such as polishing compounds made of oxides of aluminum, cerium or zirconium, require a more complex cleaning system.
Organic contaminants are removed by two main mechanisms. The first is by solubilization in an organic solvent. Degree of solubilization in various solvents is directly related to their molecular structure. The second mechanism is by displacement with a surfactant film followed by encapsulation and dispersion. In aqueous cleaning, the detergent contains surfactants as essential ingredients. Surfactants are long chain organic molecules with polar and non-polar sections in their chains. Surfactants can be ionic or non-ionic in nature, based on the type of functional groups attached to or part of their chains. When diluted with water, surfactants form aggregates called micelles (Figure 4) at a level above their critical micelle concentration (CMC). The mechanism of removal of organic contaminants by detergent involves wetting of the contaminant as well as the substrate. According to YoungÕs equation, this will result in increasing the contact angle between the contaminant and the surface, thus decreasing the surface area wetted with the hydophobe, reducing the scrubbing energy for removal (Figure 5). The ultrasonic cavitations play an important role in initiating and finishing the removal of such hydrophobic contaminants. The shock wave (the micro streaming currents) greatly speed up the breaking of the hanging contaminants, enhancing displacement with the detergent film. The removed contaminants are then encapsulated in the micellic aggregates, thus preventing their re-deposition. The net result is that ultrasonic cavitations accelerate the displacement of contaminants form the surface of the substrate and also facilitate their dispersion throughout the cleaning system.
However, the smaller particles are always more difficult to detach. This is mainly due to the lodging effect. Smaller particles tend to get trapped in the valleys of a rough surface. The mechanism of particle removal involves shifting the free energy of detachment to be near or smaller than zero, according to Gibbs adsorption equation (Figure 6). Surfactants play a very important role in decreasing by adsorption at particle and substrate interfaces and with the bath. The wet-ability of the surface plays an important role in achieving this step. The ultrasonic cavitation's role is to provide the necessary agitation energy for the detachment (i.e., the removal force). At high frequency (60-70 kHz) ultrasonics, the detachment or the removal efficiency of one micron particles, measured in deionized water, was found to be 95 percent , equaling the efficiency obtained by using the megasonics at about 850 kHz, versus 88 percent at 40 kHz. This is expected in light of the fact that cavitation size is smaller at higher frequencies and can reach deeper into the surface valleys. One would then anticipate that by using a combination of the high frequency ultrasonics at 65-68 kHz and the appropriate chemistry, the removal efficiency of various particles can be further optimized. Re-deposition of Contaminants
Therefore, allowing the increase in the soil load in a cleaning solution to reach saturation point, without good filtration, will result in a significant decrease in the detergent cleaning efficiency, at which point the cleaning action may cease. To ensure steady cleaning efficiency, the dispersed contaminants must be removed by means of continuous filtration or separation of contaminants, along with maintaining the recommended concentration of the cleaning chemical. References
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