WO2012012349A2 - Novel methods for improving surface characteristics - Google Patents

Abstract

A cleaning solution is provided that includes an inert particle in a liquid medium, wherein the medium allows propagation of ultrasonic waves through the medium. A method is also provide that cleans a surface to remove foreign materials, in which a cleaning solution is provided that includes an inert particle in a liquid medium and a cleaning apparatus that emits ultrasonic energy.

Description

NOVEL METHODS FOR IMPROVING SURFACE CHARACTERISTICS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of provisional application serial no. 61 ,399,749, filed on July 17, 2010, the contents of which are incorporated herein by reference in their entirety.

FIELD

[0002] The present disclosure relates to a cleaning solution and method of using the solution for removing foreign materials from surfaces, such as metal, food, plastic and printed circuit boards.

BACKGROUND

[0003] The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.

[0004] An ultrasonic cleaner is a cleaning device that uses ultrasound typically in frequencies ranging from 15-400 kHz. The ultrasonic cleaner requires the use of a liquid referred to as an ultrasonic bath. Ultrasonic waves are generated by transducers affixed to the vessel. The transducers produce ultrasonic waves that are conducted through the bath liquid producing millions of microscopic voids or partial vacuum bubbles known as cavitations. The collapse of the bubbles exerts tremendous pressure on the surface resulting in cleaning minute features, including blind holes, recesses and cracks, and substantially completely removes tightly adhering materials from solid surfaces.

[0005] The collapse of the microbubbles generated by ultrasonic transducers in combination with cleaners is well known in the art. Further, since ultrasonic cleaning action is based on the cavitation effect caused by high frequency wave vibration through a fluid medium, the result of the waves striking an object in the bath is the formation of microbubbles, which implode violently.

SUMMARY

[0006] The present disclosure employs micro and nano particles to interact with the ultrasonic energy and especially with the bubbles formed by in ultrasonic cleaners. The present disclosure uses not only the ultrasonic wave to accelerate the particles, but also uses the energy release reaction of the bubble implosion to breaking up the particles into finer particles.

[0007] The instant invention is directed to nanoscrubbing via inert particles such as silicone dioxide and the like.

[0008] Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.

DRAWINGS

[0009] In order that the disclosure may be well understood, there will now be described various forms thereof, given by way of example, reference being made to the accompanying drawings, in which:

[0010] Figure 1 : is an SEM image of typical corrosion and adhesive found on stainless steel instruments that had received currently acceptable processes for sterile decontamination;

[0011] Figure 2: is a SEM/EDX spectra illustrating analysis of spots #1 -3; and

[0012] Figure 3: is a SEM/EDX spectra illustrating analysis of spots #1 -3 after cleaning.

[0013] The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.

DETAILED DESCRIPTION

[0014] The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses.

[0015] The present disclosure is directed to a novel cleaning solution and method of nanoscrubbing.

[0016] The present disclosure is advantageous for cleaning of medical devices and well as any food processing including meat and produce at the supplier/processer, wholesaler, retail, food processing, or in-home use. In one form, the food articles are cleaned at the point of harvest, and in another form, the food articles are cleaned at the point of use, or could be cleaned anywhere in between.

[0017] Delivery of the cleaners with the nanoscrubbing inert particles would be accomplished in conventional plastic dispensing jugs, pumps or vacuum delivery. [0018] In one form, the delivery of the cleaner and nanoscrubbing particles would be via a sealed chemical pack (so called pillow pack) encased in a water soluble solution.

[0019] The action and/or the nano could either be liquid and/or powder.

[0020] Food borne pathogens continue to extract huge resources from the global economy, but more importantly the exposure of pathogen may result in death and untold human suffering. The American expectation for our system of food distribution to delivery substantially pathogen free foodstuffs is broken, as evidenced by recalls that continue to greet us in the headlines, supermarkets, and restaurants.

[0021] In one embodiment, the invention of a method of producing substantially pathogen-free foods stuff. The present invention follows the path established by the quality community using six-sigma problem-solving to arrive at the "root-cause" of the problem and to then present an effective and long-lasting solution.

[0022] Substantially pathogen-free food stuff can be accomplished by deploying ultrasonic cleaning of food with novel products followed by ultrasonic rinsing. The products may include, but are not limited to citric-based or citris-contaning components; the result of exposure serves to kill any live undesirable materials from the food. The rinsing, which is preferably ultrasonic, but may also be immersion, spray, triple-flow, or other acceptable forms of engineering rinsing results in removing all remaining foreign material, including but not limited to the dead pathogens remaining after decontamination

[0023] All tools, hardware, tables, culinary items used in food processing may also be cleaned in a like manner, but also may be coated with silicon dioxide to provide a soresistant surface, less susceptible to pathogen or foreign material attachment.

[0024] The combination of clean surfaces, tools, and the like with clean food stuff will result in substantially pathogen-free™food stuffs.

Novel Methods and Formulations for Improved Cleanliness of Stainless Steel [0025] Effective cleaning and inspection of stainless steels used in human and animal health care, drug, food, dairy, and blood processing for total removal of all foreign materials, including corrosion, has been problematic. The current cleaning methods in the above mentioned industries have been observed as ineffective for prevention of the transmission of certain biomaterials. Corrosion, accumulated residue, and biomaterial that is remaining after processing with the ineffective methods serve as attachment points for additional biomaterial that may include infectious materials, including bacteria, proteins, or prions, or mixtures thereof. Infectious materials, including prions, have been identified as a threat to human and animal life and are not removed and/or destroyed with the current practices. The need exists for formulations, processes and procedures to remove all biomaterial, and corrosion products from stainless steels used in the subject industries. A method is disclosed to lift and remove the passive oxide film upon which all foreign material is attached thereby rendering the surface substantially void of all contaminants and foreign materials. After cleaning and passivation, silicon-containing compounds may be deposited to coat or seal the surface and fill pores while rendering the surface hydrophobic thereby less susceptible to adhesion of infectious materials including but not limited to prions, soils, bacteria, biomatter or mixtures thereof. This process may be accomplished in a laboratory setting or in hospital decontamination facilities using a stand-alone closed automatic machine and/or a novel cleaning formulation used in existing decontamination machinery. Incineration or separation by filtration methods is also disclosed to provide a resolution for isolation and treatment/disposal of process materials.

[0026] U.S. Patent Nos. 61 ,931 (Fleury, Feb 12,1867); 3,565,675 (Sams, Feb 23, 1971 ); 3,940,511 (Deal, et al., Feb 24,1976); 7,252,720 (Foster et al., AU9 7, 2007); 7,217,685 (McDannel et al., May 15, 2007); 7,118,852 (Purdum, October 10,2006); 7,011 ,873 (McDonnell et al., February 21 ,2006); 6,613,505 (Shih, September 2,2003) are incorporated by reference in their entirety.

[0027] The invention further relates to a process and materials for cleaning and coating metals for use in human health care, animal health care, dental, and also food, drug, dairy, and blood processing.

[0028] Cleaning is defined as removing all foreign material, which may include inorganic and organic materials. In one embodiment, this invention also relates to passivating of metals. In another embodiment of the invention, it relates to overcoating or treating with novel silicon materials.

[0029] The passivation may occur on metals that have been cleaned using the instant invention. The silicon may be applied to parts that have been cleaned using the instant invention, or may be applied to parts that have been passivated using the instant invention. The silicon-containing materials may also be applied in some embodiments to parts that have been cleaned using the instant invention, and also passivated using the instant invention.

Stainless Steels

[0030] Corrosion resistant steel was first developed in the last century, based on alloys containing iron, nickel, and chromium as its primary elements. Chrome concentration can vary between 11-24%. Stainless steel is notorious for rapid, if not catastrophic wear of cutting tools. Sulfides of sulfur and or magnesium are added to create free-machining grades of stainless steel as these steels are resistant to cutting, machining and forming.

[0031] Most metals form naturally occurring passive oxide films upon exposure to the earth's atmosphere. The oxide films typically are thin, ranging in thickness from 5-50 Angstroms. The oxides render an active metal surface to a passive state, passive to the atmosphere and/or its environments. Some oxides also contain air borne compounds that may dominate a particular geographic region in coastal areas, in rural areas and in industrial areas.

[0032] Oxides of zinc in coastal areas will contain chloride as zinc chloride, zinc sulfide in industrial areas, and zinc carbonate in rural areas. Some oxides are more stable than other with different variation in solubility depending upon exposure. As in the previous example, zinc carbonate is very stable where zinc chloride is unstable and soluble. Similarly, oxides of iron may be stable or soluble.

[0033] Of particular interest in this endeavor is the passive film found on stainless steels used in surgical instruments, blood separation, chemical synthesis, food or dairy processing, and culinary uses. The basic resistance of stainless steel occurs because of its ability to form a passive film or protective coating which resists further oxidation or rusting. Nature typically provides a passive, chromium oxide surface from exposure to oxygen or oxygen bearing compounds. This oxide film is conformal, tightly adhering, and covers the entire surface.

[0034] Passivation is a post-machining method to maximize the inherent corrosion resistance of stainless steel. Tools and hardware machined from stainless steels must be properly passivated to ensure the "stainless" characteristics of these alloys. By the term "passivating", it is meant processes and materials to alter the surface from active to the environment to passive to the environment.

[0035] When secondary operations are performed such as grinding, forming, machining and polishing, contaminants such as soils, dirt or iron-containing particles may be transferred to the stainless steel surface. The foreign material is embedded in the surface and disrupts the passive oxide film rendering local areas active and a response to the environment ensues typically in the form of corrosion. To insure full passivation of the surfaces on stainless steel, the standard practice is to immerse, thoroughly alkali-cleaned hardware in a nitric acid (20% by volume) bath. If the hardware is a free machining grade containing sulfides, an alkaline-clean, nitric acid, alkali cleaning process is followed to ensure removal/neutralization of acid from the microscopic discontinuities in the surface of the hardware. Recent developments in stainless steel passivation include the use of citric acid in lieu of mineral acids such as nitric acid for which operator safety issues and noxious fumes handling issues are well known.

[0036] Electropolishing of stainless steel is an electrochemical process developed to provide the bright luster typical of stainless steel used in the before mentioned applications. The electropolishing process etches the least noble phase, namely iron, removing microscopic quantities from the surface. The process provides a very smooth, hygienic, mirror finish required on surgical tools. Various acids including nitric, phosphoric and sulfuric are deployed in a bath. The electropolishing is then accomplished when the work piece is the anode (reverse current) or cathode (direct current) with a conformal anode or cathode. Under DC current, the iron is slowly dissolved from the surface, rendering a bright luster. The new microfinish can reduce adhesion and contamination buildup on surfaces.

[0037] As stated earlier, stainless steel is an alloy of iron, nickel, and chromium. The passive oxide film found on stainless steels is predominately chrome oxide which is a very durable and stable oxide. In order to enhance the stainless steel for long use, particularly threaded items, electropolishing or a thin dense layer of electroplated chromium is used to enhance the surface finish. The goal in the process is to either reduce the iron content on the surface through selective etching electroplating or overcoating with chrome. In either case, the predominate oxide would be an oxide of chrome. [0038] However, the protective passive film of stainless steel can be comprised. In ultra pure water, iron from the substrate bulk is leached into the passive oxide film forming a dull orange/brown appearance termed "rouge" by corrosion engineers. The National Association of Corrosion Engineers define rouge as rust. Observed in pharmaceutical synthesis processes, rouge must be removed so as not to contaminate necessarily clean processes in pharmaceutical manufacturing. Standard pharmaceutical engineering procedures for removal include pumping hot nitric acid through the tanks and vessels to remove rouge. Personal protection for use of hot mineral acids may include full body suits and selfcontained breathing apparatus or ventilation or combinations thereof. These techniques are not feasible for hospitals or field sites, including but not limited to hospitals, food processing centers and blood processing centers and the like. Rouge has been observed to form with repeated exposure to steam sterilization.

INSPECTION

[0039] Inspection of instruments is also problematic in many safety-aware industries, such as health, food processing, dairy and such. In many cases, the level of inspection that is achievable is highly dependent upon the level of cleanliness that is achievable through the adopted cleaning process. This is especially true of rouge on surgical instruments, as the mottled and discolored surface can camouflage and hide pits, cracks, nicks, or flaws in the metal. In the case of accumulated biomaterial or adhesives foreign material may fill any flaws in inserts or metal continuity after several decontamination cycles. The only way to be sure of the integrity of the instrument is to inspect a clean article, free of corrosion, including rouge, free of adhesives and accumulated biomaterial.

Cleaning Methods & Decontamination

[0040] The science for cleaning is found in physics. The process of cleaning deals with forces and energy. In the case of the instant invention, foreign and undesirable materials, including adhesives, biomatter or mixture thereof are held to the surface to be cleaned by forces and it takes energy to overcome those forces and to separate the soil and foreign material from the article. Both intramolecular and inter molecular forces must be addressed (Physics of Cleaning by Ed Kanegsberg, BFK Solutions LLC). By definition, foreign material includes all material not inherently a part of the metal article, and may include biomass which is defined as tissue or bone or fluid or mixtures thereof, and may include adhesives or fluids, including but not limited to oils, used in the procedures or mixtures thereof, or may include tape used for identification of instruments, or may include infectious materials which is defined as including but not limited to bacteria, protein, prions, or mixtures thereof of any type that may cause infectious or undesirable outcome as a result of the exposure. Metal articles, including but not limited to instruments and hardware deployed in many industries, go through a rigid decontamination process which includes hand cleaning with scrubbing, enzymatic sprays, immersion soaking, chemical sterilization, and high temperature autoclaving. These industries may include, but not be limited to surgical centers and blood processing. Other industries, such as food processing and dairy facilities, may only use chemical sterilization and hot-water (180F) wash-down.

[0041] Emulsion cleaning is effective for removing mineral oils by breaking the intermolecular bonds adhering the foreign material to the article. These cleaners depend on the physical action of emulsification in which discrete particles of contaminant are suspended in the cleaning medium. Alkaline cleaning solutions contain combinations of ingredients such as surfactants, sequestering agents, saponifiers, emulsifiers, and chelators. These types of cleaners are deployed in many industrial cleaning processes.

[0042] Cleaning by scrubbing with soap and detergents, some containing enzymes, is reported to accomplish removal of visible soil, as long as the foreign material is identified and scrubbed away during the cleaning procedure.

[0043] Steam cleaning uses steam's expansion to accelerate water droplets at the boiling point to a high velocity. At 320F, water in a steam cleaning system expands 1 ,500 its volume. The tremendous expansion is the key to the steam cleaning. Adding cleaning chemistries and detergents to the process allows for rapid cleaning of metals, even blind holes.

[0044] Solvent is effective for precleaning to remove heavy oils in mechanical scrubbers, spray systems and ultrasonic devices. In addition to the well established uses of petroleum-based organic solvents, there is a group of materials known as natural solvents. Economic and environmental issues have driven naturally derived solvents to the forefront with several advantageous characteristics. For example, methyl soyate from soybeans provides solvent cleaning without the flammability issues while also being biodegradable. Likewise a citricbased product, d-limonene is available and derived from several biomolecules including, but not limited to grapefruit, lemons, limes, and oranges and provides substantial solvency to cleaning applications. Another commercial source for citric acid is a bacteria-based production route. Natural solvents is defined as materials derived from biomass such as corn, soybeans, algae, sugar cane, native grasses, or grasses, among other or mixtures thereof which provide a renewable source for fuel and cleaning solvents. These materials are considered environmentally preferred to petroleum-based materials.

[0045] Plasma cleaning is deployed as a method to clean metals and plastic, and is typically performed in a vacuum chamber. Room air, oxygen, or argon have been used as the process gas. An oxygen or room air plasma generates chemically reactive oxygen species that react with the organic contaminants on the surface of the sample, creating CO, and H₂0 byproducts to be pumped out of the plasma chamber. Thus the oxygen/room air plasma is more of a chemical cleaning process. With an argon plasma, cleaning occurs mainly through ion bombardment and physical removal of contaminants on the sample surface. However, as the applied power in plasma cleaners is relatively low (10-30W), plasma is designed mainly to remove monolayers (not microns) of contaminants at a time and to remove weakly bound organic layers on the surface. The etch rate of plasma equipment is I Onm/rnln. The process time can certainly be extended to remove thicker adhesive layers. However, the etch time required may not be cost effective for very thick layers, if the removal is technically possible.

[0046] Regarding the removal of rust, plasma cleaning would not be a cost effective method to remove rust. Use of an oxygen plasma would most likely promote further oxidation. As described above, an argon plasma can be used for cleaning by ablation and physical removal of the contaminant. Researchers have reported the use of high powered pulsed lasers to remove rust and have applied power densities on the order of MW/cm2. (Private Communication, Connie Lew)

[0047] Corrosion and residue adhesives, however, are not removed in the standard decontamination procedures. Several specialty chemical products are available for removing corrosion ranging from low pH to high pH. Recent lab tests indicate these are not effective. Another common technique to corrosion is aggressive brushing and buffing which may obliterate the identifying numbers and may affect the surface finish, creating sites for biomass adhesion. Also, it has been reported that after buffing the instruments the surface may redevelop rust very quickly, likely due to mechanically activating the surface with no deliberate procedures to passivate which leaves the surface in an active and therefore corrosion-susceptible state.

ULTRASONICS

[0048] It is well known to those skilled in the art of metal finishing and cleaning that both acid and mixtures thereof, and alkaline compounds each can clean certain foreign substances from surfaces of metals. However, the addition an energy source, an intermolecular force, from collapse of microbubbles generated by an ultrasonic transducers in combination with strong acids or alkalis or solvents, are capable of improving the cleaning of the surface. Ultrasonic cleaning action is based on the cavitation effect caused by high frequency ultrasonic wave vibration signal in fluid. Microscopic bubbles are formed and these bubbles implode violently, creating the cavitation effect on the surface, providing an intense scrubbing action. The addition of heat further enhances the cleaning action.

DECONTAMINATION

[0049] The currently recommended process, if followed correctly, removes most, but not all, microorganisms. Sterilization is used as the primary defense in sterile environments to deactivate the remainder through thermal exposure in the form of dry heat or moist heat, a chemical in a liquid or gaseous state or radiation. It is well-known to those skilled in the art of sterile processing that the ability to make an instrument or article completely without risk of spreading infection is to first clean all foreign materials, and then sterilize using established practices. The Association of Operating Room Nurses (AORN) establishes the industry standard for sterile processing, and has established general processes which are hereby incorporated by reference and include the following general process.

[0050] 1. enzyme clean 2. ultrasonic clean 3. lubricate 4. sterilize

[0051] Saturated steam has been shown to be the most effective sterilant, destroying all forms of microbes. It is an extremely effective carrier of thermal energy and steam is used typically around 270F-285F in autoclaves which destroy all life forms. The conditions required for effective steam sterilization are adequate contact, sufficient elevated temperature, and adequate time at temperature and adequate moisture.

[0052] These engineering processes and procedures are embodied in guidelines found in decontamination units in use today. Although steam sterilization is an integral component of an overall infection control program its performance on the surface of an article cannot be fully verified by inspection or testing after completion of the process. Biological and chemical indicators in conjunction with physical monitoring of the process (charts, gauges, readouts) are the typical quality criteria.

PRIONS

[0053] A prion - short for proteinaceous infectious particle - is a poorly-understood hypothetical infectious agent - that according to the "protein only" hypothesis is composed only of proteins. ^[2] Prions are thought to cause a number of diseases in a variety of mammals, including bovine spongiform encephalopathy (BSE aka "mad cow disease") in cattle and the Creutzfeldt-Jakob disease (CJD) in humans. All thus- far hypothesized prion diseases affect the structure of the brain or other neural tissue, and all are currently unbeatable and thought to be fatal. .^[3] In general usage, prion can refer to both the theoretical unit of infection or the specific protein (e.g. PrP) that is thought to be the infective agent, whether or not it is in an infective state.

[0054] Prions are mutated proteins that pose a threat to life, and are known to transmit Mad-Cow disease in cattle, wasting disease in deer and elk, scrappie in sheep, CJD in humans and are suspected in contributing to Alzheimer's and Dementia. These mutated proteins are extremely resistant to decontamination. Other mutated unidentified prions may be responsible for a host of aging diseases as suggested by the National Institute of Health.

[0055] Conventional decontamination and sterilization procedures for surgical instruments, blood handling, and food processing equipment and the like that have come in contact with prion infected tissue have been demonstrated as ineffective as the prion is capable of regeneration after the sterilization process. A plethora of proposed methods ranging from thermal! enzymatic treatment to oxidation with acids have been proposed including sterilization in concentrated caustic which created unacceptable danger from burns and caustic fumes to decontamination personnel. [0056] The National Institute of Neurological disorder and stokes (NINOS) has identified prions as responsible for different neurodegenerative diseases which involves modification of the normal cellular prion protein to a mutated form. Prion diseases are highly contagious and may be manifest as infections, genetic and sporadic disorder all resulting from the accumulation of mutant prion in the brain and in lymphoid tissues. (National Institute of Health, Department of Health and Human Services, Mechanism of Transmission and Dissemination of Prions, 2007).

[0057] Prion infection of cattle, sheep, mule deer and elk, are well documented. Research work has identified how the prion are incubated in soils and passed up to the food chain. An article in Science News, Vol 172, pg 36, July 21 , 2007 from research by Judel Aiken of University of Wisconsin- Madison "Prions enter the environment from the remains of infected animals, and, to some degree, from body fluids such as urine and saliva. Prions linger in soil for at least 3 years by binding tightly to clay and other minerals. The binding of infectious agents in soil actually greatly enhances the infection, thereby making a route of transmission from wild to domestic grazing animals, such as cattle, sheep, or other food livestock.

[0058] Awareness of the prion transmission to humans came with the mad cow disease in the United Kingdom. Prions can be transmitted from animals to humans. The challenge is prion decontamination. Gerald McDannel writing in Clinical Infection Diseases (C/D) 2003,; 36:1 1 52-4 indicated prions can be transmitted to humans via surgical instruments He states further "Prions are regarded as being highly resistant to the routine methods of decontamination and sterilization that are currently accepted for medical device reprocessing. No single method has been shown to be 100% effective against prion. Enzymatic cleaners do enhance the physical removal of soil from a device and are currently deployed in medical decontamination units.

[0059] Furthermore, C. Weissman from the Institute of Molecular Biology stated that prions, the transmissible agent of Creutzfeldt- Jakob disease (CJD) is not readily destroyed by conventional sterilization and transmission by surgical instruments have been reported.

[0060] Residual organic and inorganic materials may remain on cutlery, surgical, organic synthesis tools following current cleaning procedures. These residual include blood, bone, tissue, adhesives and soap containing enzymes.

[0061] Ian Lipscomb completed an extensive survey of Sterile Service Departments in the United Kingdom hospitals, finding that over 60 percent of the instruments showed a high degree of protein soiling (0.4 to 4.2 mg protein/mm (2)). Some instruments appeared soiled with crystalline deposits that may consist of a potentially hazardous material contributing to inflammation and/or surgical shock.

[0062] Also, the use of local PVC applied by overmolding or plastisol dipping and colored identification tapes are noted by the author as problematic as these create not only crevices but also leave residual adhesive for biomass adhesion.

[0063] NIH has reported the current decontamination methods as ineffective in cleaning surgical tools for the reduction of prion transmission.

[0064] In an exhaustive paper by Ian Lipsocomb, currently at the University of South Hampton, published in the Journal of Clinical MicrobiologV(44,(1 0) 3728- 3733a). In this paper, hereby incorporated by reference, Lipscomb clearly states that "the ineffective cleaning of surgical instrument may be the vector for the transmission of hospital acquired infection. He concludes that protein contamination remains (after sterilization).

[0065] Another author, C. Weissman from the UK (now at Scripts, FL) affirms the problem and also calls for assessment of sterilization procedures.

[0066] German researchers from the Robert Kock Institutes writing in the Journal of General virology (2004) Vol 85, 3805-3816 are quoted, "However, there finds of some efficacy with Sodium Hydroxide is process problematic in surgical centers to health exposure and respiratory problem with handling hot caustic. Therefore a better solution in needed."

Silicon Coating_^

[0067] Silicon is used in a variety of solvent, water borne solutions, or vapor deposition to impart or deposit coatings, thin films, or seals from polymeric organosilicone compounds. These compounds are known as silica which may be linear, cyclic, or cross-linked. Organosiloxanes are remarkably stable towards heat and chemical reagents and are not wetted by water. Objects may be coated with organisilocones by spray or immersion or exposed to vapors of silane containing compounds such as trimethylchlorosilane and the like.

[0068] Silicates have been used in sealing metal for a variety of purposes. Sodium, potassium and lithium silicate are found in many formulations for metal finishing seals being applied to retain the bright luster of electroplated hardware. Additionally, the application of silicon dioxide coating deposits from vapor in CVD or PVD are well known in the art of coatings for microelectronics.

[0069] The most desirable protective coating would be amorphous in structure. The reason for this is that the absence of grain boundaries, inevitable in crystalline substance, eliminates known failure modes of crystallinity. The grain boundaries of crystalline coatings are usually anodic to intergranular material. Secondly, grain boundaries render coatings prone to mechanical deterioration such as stress corrosion cracking. The optimum coating for metals would be amorphous (private Communication, Joe Mazia, Jan, 1997).

[0070] Corrosion is caused by environmental conditions, most notably for the instant invention, repeated exposure to high purity steam as in the steam sterilization units (aka autoclave). Continuous decontaminations has been observed to create pits. Compounding the issue, surgical stainless steels are electropolished as the last process prior to assembly to chemically remove all asperities from forging/machining. Although bright and polished to the human eye, in reality the surface presents a karst surface topography full of microscopic pits, crevices, and the like. Additionally, sulfides are added to the stainless alloy to improve machinability, and these sulfides have been identified as critical to the pitting corrosion process in stainless steel. A paper in Nature 415, 770 (2002) by M. Ryan addresses the corrosion sequence leading to pitting corrosion in stainless which compromises the passive oxide film. All of these inherent surface anomalies serve as potential attachment for biomaterial, including foreign and undesirable materials to attach.

[0071] The goal in all cleaning endeavors whether it be for surgical instruments, blood processing, dental, tattoo, dialysis, food processing, or dairy is to remove soil, biomaterial and then sterilize. The literature in this area make well known the fact that the current decontamination methods are not sufficiently hygienic or effective at removal of potentially hazard containing biomaterial. It is well known by those skilled in the art that the current procedures found in the before mentioned industries apply neither sufficient force nor adequate energy to remove all surface contamination. Of great concern is that the current decontamination and sterilization procedures are not effective against the unconventional nature of the prion as it is capable of regenerating after sterilization. [0072] In summary, the corrosion products resulting from repeated autoclaving, as well as the micropits inherent to many stainless steel allow allow angstrom-sized particles, as well as adhesive use in surgical drapes, to lodge with great tenacity. This foreign, sometimes infectious materials, undermines the overall safety of the procedure and exposes patients and consumers to a unreasonable risk of exposure to undesirable materials. A stop-gap solution implemented in the United Kingdon uses strong caustic at high temperature and combustible materials in decontamination facility creating a significant health exposure hazard to workers. This challenge is a global problem with no apparent solutions at hand. Therefore, a need exists in these industries for a more effective process and products for cleaning and sealing.

[0073] Historically, the medical, cosmetic, tattoo, as well as blood, dairy, and food processing industries relied on alkali based cleaning and steam sterilization to provide clean and sterile tools and equipment. The use of ultra pure water in the autoclave creates a corrosion phenomenon known as "rouge", an iron dominated oxide manifesting a dull orange/brown hue on stainless steels, upon which rests and attaches all sorts of contamination, including infectious materials, including but not limited to bacteria and/or prions.

[0074] The medical industry has used cleaners specifically for removal of foreign material, including biomaterial, and relied upon sterilization for deactivating any remaining biomatter. Rust, in the form of rouge and even to the point of red rust, is tolerated in the current medical and surgery decontamination units. Although some detergents are sold as rust removers, no in-hospital processes exist for the removal of rouge. Experiments using commercially available cleaners, obtained from ISI and Steris, among others, for removing rust and rust stains were conducted according to label instructions. None of the products tested removed "rouge" in the decontamination equipment.

[0075] Conversely, the centerpiece for the metal finishing industry is cleaning for removal of soils, oils, metals, oxides, organic and inorganic foreign material. The instant invention solves the problem of inadequate decontamination by deploying energy forces (intramolecular and intermolecular) to remove the oxide layer and the surface contamination resting upon the oxide in new and novel method and processes, using new and novel materials and formulations. [0076] In one embodiment, the instant invention improves the stainless steal making it more easily cleaned by applying a novel seal to fill surface anomalies and substantially decrease the number of sites available or foreign and undesirable materials to attach. In another embodiment of the invention, the novel processes and formulations are made available for use in a machine to clean soiled articles.

[0077] The loss to society due to corrosion and contamination in terms of human life and resources is staggering. Estimates range from the hundreds of millions to billions of dollars annually. Losses, due to corrosion, are compounded in the medical, blood processing, and culinary markets with the report of infectious materials, including but not limited to bacteria or prions, among others, attached to the corroded and/or stained or clean stainless steels used in these industries making the instruments unsafe and increasing the risk for infectious disease transmission. The outbreak of Mad Cow Disease only highlights an already known condition with no viable solutions. Prions are infectious proteins and are suspect in other diseases. Additionally, the on-going recalls of food products ranging from ground beef to tomatoes indicates problems in decontamination across many food processing disciplines..

[0078] The Association of Operating groom Nurses (AORN) has published recommended practices for care of surgical instruments and the like. Similarly, guidelines and cleanliness standards are provided by the US Food and Drug Administration and the National Institute of Health, and others, and the like for all food, drug, blood, and dairy process with the goal of preventing the spread of infections to animals and humans.

[0079] The instant invention addresses cleaning problems across all the above mentioned disciplines through the following novel methods which are effective methods for cleaning the subject article to restore the item to its original luster, and substantially removes all foreign or undesirable materials from the surface of the article. In another embodiment of the invention, the invention is used to seal the subject article to reduce the locations to which foreign or undesirable materials may attach, and thereby allow the article to be maintained in a clean state with less energy. In another embodiment of the invention, the invention is used to maintain the cleanliness of the articles that have been cleaned and/or sealed with the instant invention. [0080] In one form of the disclosure, disclosed is a novel method for a "deep clean" to substantially remove all surface contamination by virtue of removing the oxide film that exists on the surface of the article. By removing the underlying oxide, the novel process is successful in removing all foreign or undesirable material that is on and/or in the oxide. This method may be accomplished in open tanks with batches of articles that are hand moved between substeps. The method may also be accomplished in an automated machine as well as a closed machine wherein either the articles to be cleaned or the cleaning materials are shuttled to or through the cleaning station. The inventive method is effective when using novel cleaning process fluids that are exposed to the articles in immersion, immersion with ultrasonic energy, heated or room temperature, or delivered through spray systems, or high energy impingement spray systems. The instant inventive formulations may be mixed as concentrates and diluted at the final point of use, as in a hospital decontamination facility, among other facilities.

[0081] In another form of the disclosure, disclosed is a novel application method and novel formulation for the application of coatings that substantially seal the surface and fill a substantial portion of the micropits and surface anomalies, making the surface less susceptible for adhesion of foreign and/or undesirable materials. In one embodiment of the invention, the seal may be accomplished with novel formulation that results in a silica-based coating, among other novel formulations. The seal may be applied in immersion or spray or brushed on, at high temperatures or room temperature.

[0082] In yet another embodiment of the invention, disclosed is a novel application method and novel formulation for the continued cleaning and maintenance of luster for articles that have experienced the novel "deep clean" cleaning techniques of the instant invention. The maintenance of the clean surface may be accomplished through the use of novel formulations that may be contacted to the article through immersion, hot immersion, spray, heated or room temperature or delivered through high energy impingement spray systems.

[0083] The instant invention therefore provides a new and novel method of removal of biomass, but also strips off the passive film upon which all foreign material resides, repassivates and in some embodiment of the invention, seals the microsurface defects with a thin film of silicon dioxide based lithium, potassium, or sodium silicate, and/or amorphous colloidal silica. [0084] The instant invention is an effective cleaning method to restore the metal to its original luster, free from foreign material while presenting a dry product for further processing and sterilization using acceptable techniques. The instant invention is preferably accomplished with a combination of d-Limonene-based and citrus-based mixtures in conjunction with not only ultrasonic cleaning, but also ultrasonic rinsing, with conventional counter flow or static rinsing, citric acid clean, ultrasonic rinse, alkali rinse, to neutralize any residual acid. The article may then preferably be exposed to heated or room temperature repassivating in D.I./R.O. water or in hot humid air. Certain embodiments of the invention are preferred formulations for novel cleaners that can be used in each daily decontamination event as a cleaner in both ultrasonic and washer sterilizer units (that use impingement energy), as an environmentally and process preferred alternative to current state of the art.

[0085] The instant invention includes several steps and formulations including, but not requiring all of the following, nor limited to the following steps: (NOTE: Steps 1 -6 are typically used for non-stainless steel items whereas steps 1 -12 are typically used for stainless steel items. However, suitable formulations are anticipated for both stainless and non-stainless items.)

[0086] 1 ) Inspection - visual viewing at both low and high magnification to identify worn or flawed components;

[0087] 2) Sort - metal articles, including instruments or hardware, are sorted by materials of construction so as not to mix different metal ions in the subsequent cleaning processes;

[0088] 3) First clean solution (ultrasonic) - The initial cleaning operation is designed to loosen and substantially remove soils and adhesives with ultrasonic and optionally heat energy.

[0089] 4) Rinse (ultrasonic) - dislocates residue cleaner and foreign material from blind holes, crevices, pores, and tubular items with ultrasonic and optionally heat energy.

[0090] 5) Rinse - counter flow or static - Presents a clean surface substantially free of foreign material, ready for further processing and sterilization using acceptable techniques.

[0091] 6) Acid clean (untrasonic) - substantially removes any residual from step 1 -6 while removing the oxide film, and thereby removing all deposits, metals ions, foreign materials, infectious materials or mixtures thereof, that were attached to and/or integrated in the metal surface

[0092] 7) Rinse - (ultrasonic) -- dislocates residue cleaner and foreign material from blind holes, crevices, pores, and tubular items.

[0093] 8) Rinse and passivate - counter flow or static - Presents a clean surface free from foreign material, upon which is restored the original passive film conforming to ASTM A380-88 (specification for stainless steel passivation) and luster, ready for further processing and sterilization using acceptable techniques.

[0094] 9) Alkali rinse - buffers any residual acid retained on the part

[0095] 10) Dry - optional

[0096] 11 ) Seal with Si-containing material - Used in conjunction with step 10 (dry) to apply a thin film of silica-containing material

[0097] 12) Dry (optional) - for use with step 1 1 only

[0098] 13) Rinse - used after step 12 to remove any soluble species or residual process fluid from the coated articles.

[0099] 14) Inspect - Visual inspection at both low and high magnification to verify process and detect any flaws that may not have been visible on the stained, or uncleaned article.

[00100] 15) Package.

DETAILS for STEPS 1-15

[00101] 1 ) Inspection - Close attention is paid to surface flaws, cracks in hinged items, flawed inserts, or types of corrosion, or mixtures thereof, identified using visual inspection methods.

[00102] 2) Sort - Material types are sorted into separate groups and identified for processing.

[00103] 3) First cleaning bath (ultrasonic) - In one embodiment of the invention, an alkali bath is used to substantially remove biomass including but not limited to adhesives, proteins, prions, bone, and blood residues. The cleaning bath may contain a mix of alkali and or an acid and may include at least one naturally occurring solvent, or may include scrubbing additives, including but not limited to colloidal silica. The concentration of alkali ranges from 0.1 % to 10%. The naturally occurring solvent may be a solvent derived from plant or microbial cultures, including but not limited to materials obtained from soybean, corn, rice, sugar cane, grass or algae among others. The concentration of naturally occurring solvent ranges from .1 % to 10% using natural citrus solvent. In some embodiments of this invention, a material is added to act as a scrubbing agent, and give physical scrubbing in the energy enhanced process exposures, such as ultrasonic or impingement spray. The materials used for this scrubbing action include but are not limited to colloidal silica, crystalline silica, among others, or any particle not soluable in water. The concentration of scrubbing agent ranges from 0.01 % to 10% . Other additives to the bath may included, but not limited to caustic soda, sodium, potassium, or lithium hydroxide or mixtures thereof or carbonates, sodium potassium, sodium hydrogen carbonate, sodium decahydrate or the like in a mixture of a natural solvent such as d-lemonine, methyl soyate, or any natural solvent derived from biomass. The concentration of additives will range from 0.01 % to 5%. The addition of gycols, esters, or mixtures thereof, or other suitable solvents, may be included in some embodiments to enable aggressive removal of baked on adhesives. The water used for this novel formulation may be preferably RO/DI, but not limited to plain tap water. The pH would be adjusted to a range of 8-14, preferably 11 for aggressive removal of biomass and adhesive. In another embodiment of the invention, the addition of ammoniated citric acid to buffer, added dropwise, to a neutral pH acts to remove rust stains which are tramp deposits of corrosion products not originating from the instrument. The above cleaning mixture may be contacted with the soiled article in immersion, with or without ultrasonic energy, at temperatures ranging from 60F to 140F, with a preferred embodiment of 7SF to 120F. The duration of contact ranges from 1 to 30 minutes, with a preferred embodiment of 3-1 5 minutes. The cleaning mixture may be contacted with the soiled article in a spray application in another embodiment of the invention. The spray may be manual or automated, or may be high energy impingement spray as are existing in many cleaning and decontamination units. The use of this inventive formulation in an existing machine, on preferably articles previously process with the inventive "deep clean" represents a highly effective path to maintenance of clean articles for the subject industries. The above mentioned embodiment may be used in a daily decontamination area as a cleaner in either ultrasonic and washer sterilizer units that use impingement energy. Without wishing to be bound to any theory or explanation, the use of this daily regimen of novel cleaner will make instruments used in sterile procedures safer, and lead to an increased health of the patients.

[00104] 4) Ultrasonic Rinse - Ultrasonic energy is utilized in some embodiments of the invention to dislocate residual cleaner, foreign, infectious, or undesireable materials from the soiled article after contact with the inventive cleaning solution. When combined with the varied embodiments and deliveries of the first cleaning bath, the use of ultrasonic is a novel and effective method to insure full removal of the soils and/or cleaning bath. Di/RO water is preferred, but tap water may also be deployed at temperatures between 80F - 150F. The process time for ultrasonic rinse ranges from 1 to 20 minutes, with the most effective rinsing observed at 5-15 minutes.

[00105] 5) Static Rinse - In some embodiments of the invention, a static or counter-flow rinse of DI/RO or tap water is used to ensure a clean surface. The temperature of this rinse ranges from 65F - 1 OOF with a preferred embodiment at 80F. The process time for rinse ranges from 1 to 20 minutes, with the most effective rinsing observed at 5-15 minutes.

[00106] 6) Acid Clean - Ultrasonic - In some embodiments of the invention, an acid cleaning bath would be used to substantially removes contamination and undesirable materials and also substantially removes the passive oxide film containing iron species typically termed rouge as well as the iron oxide (rust) from pits and pores. Without wishing to be bound to any theory or explanation, the embodiment of the invention is effective to substantially removes any remaining adhesive residue and residual biomass potentially containing infectious materials, which may include bacteria, prions, among others, as well as the naturally occurring passive oxide containing iron oxides in the form of rouge from metals deployed in medical and dental, food, dairy, or blood processing industries, among others. In one embodiment of the invention, citric acid combined with ammonia or phosphoric acid and with sometimes an addition of chelates The process time for solution contact ranges from 1 to 20 minutes, with the most effective cleaning observed at 5-15 minutes.

[00107] In one embodiment of the invention, the novel formulation would contain mixture acids including mineral acids, and/or naturally derived acids such as citric acid and the like as well as ro-/di water, surfactants and chelators such as Dow Corp, Visiene. In one embodiment of the invention, citric acid is combined with one or a mixture of two or more suitable water dilutable acids, including but not limited to the following, ammonia, sulfamic, or phosphoric acid with sulfamic acid preferred. The concentration of acid is in the range of 0.05 to 50%, with a preferred embodiment of 5-40%. In this form of the disclosure, additives are including but not limited to surfactants, chelaters, or enzymes among others, to be used at a concentration range of 0.001 % to 20%.

[00108] In one embodiment of the invention, the instant invention is used as a concentration, and diluted for final use with preferable DI/RO water (tap water may be used). The instant formulation is heated to a range of 80F-1 50F with 130F preferred with cycles ranging from 5-20 minutes with 15 minutes preferred or until all foreign material and chrome oxide is substantially removed with typical ultrasonic power in 20-100 Hz. Circulating the bath is preferred. Additionally, sodium citrate can be added can be added as a buffering agent and/or a sequestering agent. Components with similar functions include sodium carbonate, sodium EDTA, pentasodium petetate and tetrasodium etidroate.

[00109] Without wishing to be bound to any theory or explanation, the cleaning of instruments with the "deep clean' achieved by this novel cleaner formulation will make instruments used in sterile procedures safer, and lead to an increased health of the patients.

[00110] 7) Ultrasonic Rinse - Ultrasonic energy is utilized in some embodiments of the invention to dislocate residual cleaner, foreign, infectious, or undesireable materials from the soiled article after contact with the inventive cleaning solution. When combined with the varied embodiments and deliveries of the first cleaning bath, the use of ultrasonic is a novel and effective method to insure full removal of the soils. Di/RO water is preferred, but tap water may also be deployed at temperatures between 80F - 1 50F, with the most effective rinsing observed at 75 F. The process time for ultrasonic rinse ranges from 1 to 20 minutes, with the most effective rinsing observed at 5-1 5 minutes.

[00111] 8) Static Rinse - In some embodiments of the invention, a static or counter-flow rinse of DI/RO or tap water is used to ensure a clean surface and to passivate. The temperature of this rinse ranges from 65F - 100F with a preferred embodiment at 75 F. [00112] 9) Alkali Rinse - An alkali rinse is prepared from any suitable alkali source combined with preferabably DI/RO water, but tap water may be used. The process bath temperature may be between 50-150F with 75F preferred.

[00113] 10) Dry - A drying step is deployed in some embodiments of the invention to expedite the process. Oven or spin drying are acceptable processing methods with or without additional heat.

[00114] 11 ) Seal Application - In another embodiment of the invention, the articles are exposed to an inventive process/formulation to deposit a thin film of silicate (sodium, potassium, or lithium, among others) seal with or without colloidal fillers. In a preferred embodiment of the invention, the seal is in a final rinse after a high temperature dry cycle, which may be followed by a rinse to remove excess starting materials. Without wishing to be bound to any theory or explanation, the inventive seal fills voids, pores, draw lines, machine grinding lines, and electropolish etching, among other surface anamolies. Without wishing to be bound to any theory of explanation, the resultant article has the characteristics of hot-water resistant, more cleanable, or soil-resistant, or self- cleaning, surface which in turn is less prone to adhesion of foreign material such as infectious materials, including proteins, bacteria, and prions, among others.

[00115] 12) Seal Drying- A drying step is deployed in some embodiments of the invention to expedite the process. Oven or spin drying are acceptable processing methods with or without additional heat.

[00116] 13) Rinse - In one embodiment of the invention process, a warm water rinse may be used to substantially remove residual silica deposition bath from the instant article. DI/RO water or tap water at 70-1 20F is preferred.

[00117] 14) Inspection - The final inspection is used in another embodiment of the invention which allows the opportunity to detect flaws which were hidden by adhesive, foreign materials, stains, soils, biomass, rouge, or corrosion, among others.

[00118] 15) Package - Any customer approved method is recommended to complete the process.

[00119] In the one form, the instant disclosure therefore provides a new and novel method of one of many beneficial characteristics, and may include all, including, removal of biomass, but also strips off the passive film upon which all foreign material resides, repassivates and seals the microsurface defects with a thin film of silicon dioxide based lithium, potassium, sodium silicate, with or without amorphous colloidal silica.

[00120] In yet another form of the disclosure, the novel formulations and processes may be used to clean and/or remove the oxide from metal that is not in the form of an instrument, device or article, but may be larger areas of metal including but not limited to tanks, pipes, vessels, reaction vessels, pressure vessels, autoclaves, food processing equipment, animal cages, containers, among others. In this embodiment, the inventive processes and formulations would be used to clean metal that would not fit or is not required to be sterilized with steam, as in an autoclave, and would thereby be an environmental preferable process to the chemical sterilization presently used.

PROCESS EQUIPMENT

[00121] In yet another form of the disclosure, a system to sequentially move the components individually or grouped in baskets or the like through individual process station and/or tanks ranging from alkali to acid with interim rinses a manual or robotic system is employed to move baskets from station to station. In another embodiment of the invention, a system of a singular cleaning station or tank wherein the liquid cleaning/rinsing and sealing liquids are dispensed from isolated tanks that may be heated, and moved through the tank thereby saving critical space in decontamination areas. A lift system would be deployed in the tank in one embodiment to receive the items to be cleaned and lowered into the solution. Also a data acquisition system to monitor and record each process event is included. In some embodiments, the liquid would be filtered prior discharge from the processing tank. The above delineated process can be performed in a bench-top arrangement where each station is separate or stand alone, manual or robotic. In another embodiment of the invention, each process or partial process could be contained in an automated closed system module.

[00122] In another form of the disclosure, large processing equipment such a reservoir tanks, pressure vessels, sterilization autoclaves and the like can be cleaned by passing the inventive chemistry through devices with or without inline sonicators. In another embodiment of the invention, the novel formulations chemistry can be gelled with conventional gelling agents such as fumed silica, carbopol, or the like, among others. The gelled embodiment of the invention may be applied via spray, sponge, or hand application on the interior surfaces, such as an autoclave, or tank, among others, and then sonicated with a hand-held sonicator.

[00123] In yet another form of the disclosure, the entire cleaning line would be packaged in a mobile vehicle or other suitable transportation, such as a trailer or other mode of transporting the processing line, and the before mentioned embodiments of the invention for cleaning or passivating or sealing the metal articles will occur at the location of use.

[00124] In another embodiment of the invention, the processing order may be altered to accomplish the appropriate cleaning, such as the bath described in previously described embodiments may be switched, or replaced with one another, or two of the same bath may be used in a process flow, or other inclusions, and reductions of the multiple steps that were described.

DISPOSAL METHODS

[00125] In yet another form of the disclosure, the cleaners, alkali or acidic would be filtered through suitable membranes or cartridge filters before return to storage vessel or accumulation vessel. Likewise, the rinse water, preferably ro/di, would be filtered prior to return to the storage vessel or accumulation vessel or the like. Final disposal of the fluids can be through ultra filtration, combusted via pressure injection in a fuel system sufficient to reduce the prion, adhesive and biomaterial to carbon.

[00126] The process employs the use of proteins, natural or synthetic, or a mix of the as the pretreatment, predisposing silica deposition in the form of SiOz. The process uses proteins to effect the deposition of material to form nano-scale coatings. The process can be applied to most, preferably clean, surfaces by immersion, roll, spray, electrolytic, or brush in a batch or continuous process. The protein interacts with silica, metal or other mixtures containing elements or compounds to effect the deposition of said materials. Without wishing to be bound to any theory or explanation, the combination of the protein results in flocculation, charge reversal, and subsequent deposition of silica on conductive or nonconductive metals.

[00127] The inventive pretreatment can be applied to either nonconductive or conductive surfaces and applied either to the surface to be coated or in the silica- containing material to be applied as coating. Since the pretreatment is polymeric in nature, the conductivity of a surface which has been pretreated is altered towards nonconductive. The novel pretreatment process employs the use of a protein, peptides, dipeptides natural or synthetic or a mix of the same. Subsequent to the pretreatment, a silica containing coating is deposited to most surfaces, preferably cleaned per industry standard, by immersion, roll, spray, or brush in a batch or continuous process. The protein interacts with silica/metal compounds resulting in the deposition of silica on the surface thereby forming a coating. Without wishing to being bound to any theory or explanation, in certain formulations, the protein type materials can be mixed into one solution thereby pretreatment occurs upon a silica- containing medium prior to application onto a surface and deposited on conductive on non-conductive surfaces.

[00128] In one form of the disclosure, additives can be used in the silica-containing medium to alter surface texturing with benefits of paint adhesion by mechanical attachment.

[00129] There have been numerous reports of extraordinary corrosion performance afforded by silicates applied to steel, zinc, magnesium, and aluminum. (James Vail, Soluble Silicates, Reinhold, 1952). However, the reliability of such systems is questionable due to the lack of presence in the marketplace. The literature on silica abounds with the writings of many, with Vail and Her among the most notable. Coatings derived from silica were initially derived from aqueous systems. For instance, U.S. Patent 2, .978,349, J.S. Walsh et al described aqueous coatings formed from colloidal silica, a wetting agent and water applied to 120F surfaces and dried at 250F. Also, U.S. Patent 3,177,085, N.M. Adams, describes aqueous colloidal silica sols with wetting agents. U.S. Patent 3,796,608, M.B. Pearlman, protected metals from corrosion by depositing an adsorbed layer of silica from a slightly acidic colloidal aqueous dispersion of silica-containing sugars. U.S. Patent 3,133,829, M.E. Cupery et al disclosed the use of fumed silica but required curing temperature ranging from 400-1900F. U.S. Patent 3,455, 709, G.W. Sears, et al, disclosed the use of aqueous lithium silicate and again colloidal silica as well as zinc powders to form self curing paints for protecting metals. A follow-on U.S. Patent 3,549,395 also by G.W. Sears et al disclosed the use of organosilicates in lithium polysilicate with colloidal silica and carbopol, a thickening agent along with a variety of metallic filler and additives. The above described water-borne coatings were thin coatings and graduated to paint systems containing metals and clay fillers.

[00130] The advent of tetraethyl orthosilicate and tetramethyl orthosilicate by early pioneers such as Carl Munger brought zinc rich paints and primers to the market place and are still in use today as the primer of choice in the oil field, pipe line and bilge primer for US Navy due to the galvanic protection provided by zinc rich systems. The sol-gel based systems spelled the end of aqueous systems with improved stability, shelflife, and corrosion performance. Early sol-gels in low pH aqueous systems such as in US Patents 2,574,902 and 3,013,898 were the fore runners of organic solvent-borne sol gels. The development of sol gel in organic solvents methods over 50 years ago and deposition methods of spin coating and the like along with chemical vapor deposition (CVD) pressure vapor deposition (PVD) as well as others now provide the building blocks for the burgeoning microelectronics industry.

[00131] Water-borne thin silica films, however, are still used as seals over electroplated zinc hardware with chromate based passivate. Sodium and potassium silicates are generally used to seal chromate passivates. The seals improve corrosion performance for both the hexavalent and the trivalent based passivates. As a matter of fact, the trivalent passivates must have a topcoat or seal to provide corrosion protection. Chromate seals are also used on phosphate-based coatings to improve corrosion performance.

[00132] Silicate patents for protecting surfaces include US Patent 4,225,350 and 4,225,351 which discloses a method of preventing corrosion of zinc-plated surfaces by treatment with a solution containing silicates, and phosphorous compounds. U.S. Patent 5,068,134 also discloses protection of zinc metals with silica compounds as well as U.S. Patent 5,672,390 discloses silicate-containing solutions for forming coatings. These silicates coating claim performance as in 6,077,605. As the marketplace becomes more global, so do standards for corrosion performance. The standards now exclude certain silicate-based coatings in many industries due to the unacceptable "grey veil" (carbonate and silicate compounds) which occurs as residual soluble species of sodium silicate in the coating are slowly dissolved during the accelerated corrosion test. None of the above delineated patents have found success in the marketplace. [00133] A Canadian Patent 488,765 disclosed electrodeposited silicates. Also US Patent 3,630,869, C. Y. Man, discloses an anodic deposition of silicate. Both systems required continuous replenishment of the bath and have subsequently lost out to phosphating in the marketplace.

[00134] One use of silica and/or silicate as a passivate rather than a coating or seal is found in the Elisha processes disclosed in U.S. Patents 6,599,643; 6,592,738; 6,149,794; 6,153,080; 6,258,243; and 6,322,687, Heimann, et al, wherein the use of an electrolytic process is disclosed while 6,7661 ,934; 6,753,039 are electroless systems while 6,572,756, Heimann, et al, disclosed a sodium silicate aqueous bath medium. Under this inventor's previous patented work, a process is described under electrolytic conditions, the work piece is the cathode; hydrogen is evolved at the surface with a corresponding increase in pH. In a similar manner, the electroless method of the Elisha process deploys borohydride to raise the pH.

[00135] Both methods favor formation of colloid products of increasing quantity and/or size which capture silica and deplete the bath of feedstock.

[00136] While the electrolytic method of the Elisha process had some commercial success, the electroless never made it to market as there was an underlying flaw in the technology, namely high material cost for the reducing agent, high energy costs and pores along with the every present grey veil. Subsequent to the electrolytic patents referenced above, a paper, "Novel Nonchrome Processes for the Protection of Metal Substrates", by Branko Popov of University of South Carolina, School of Chemical Engineering, in 2002 discloses an electroless process and also infers a catalyzed precipitation, but this also has not found commercial favor.

[00137] The mentioned patents and references are incorporated by reference in their entirety.

[00138] Metal finishing, in particular electroplating process uses a variety of zinc baths including alkaline zinc baths. These baths leave a residual film known by those skilled in the art as a cathodic film. These films at times are largely comprised of epichlorohydrin and zinc metal ions in the form of zinc sulphates and the like along with other polymeric materials. Many commercial operations use a fast rinse in dilute nitric acid, called a "sour dip" to remove the cathodic film prior to passivating as this leaves the workpiece as a bright zinc, acceptable in the marketplace. Epichlorohydrin was researched and found to be highly toxic. [00139] It was recently discovered the removal of the cathodic film totally annulled not only the electrolytic but also the electroless process. Of importance is that further investigation revealed the cathodic film is not completely dissolved during the electrolytic process indicating the claimed coatings are not only the result of dissolution but also are deposited on top of the residual polymeric film. A review of the literature indicates the dissolved polymeric film is capable of flocculating colloids and reversing the charge and thus allowing the electrodeposition on the cathode. However once the colloids enter the Helmholtz zone, the dual zone found in all electrochemical process such as in the Elisha process, where the surface pH is greater than 1 1 at the cathode, the colloids are dissolved and monomeric silica in the form of hydrated gel is deposited on the residual polymeric film.

[00140] Without wishing to bound to any theory or explanation, it is believed in the Elisha process that elemental zinc is reacted in the outer zone portion of the Helmholtz with monomeric and dimeric species of silicate thereby forming zinc silicate species particles which do not provide corrosion protection, only patent novelty. In addition to all of the above, the hydrogen evolution at the cathode continues to create a porous structure from gas bubble evolution due to decomposition of water which happens concurrent to coating deposition. These pores result in early corrosion failures.

[00141] All the while, in the Elisha process, colloid production in the bath continues unabated covering anodes and plugging filters producing an ever-changing unstable bath. This is an undesirable characteristic in metal finishing.

[00142] In one form, the present disclosure solves problems associated with sodium and potassium silicate coatings applied in electrolytic or electro less processes both as a passivates or as a thin sealer. The invention also addresses the replacement of phosphoric acid based coatings and novel liquid metal corrosion problems. The process employs a medium comprising silica in the form of colloids dispersed in water having a controlled and predetermined concentration.

[00143] The medium may be produced as a gel for storage and transport and subsequently diluted with deionized or distilled water prior to application. The surface to be treated, conductive or non-conductive can be pretreated or the pretreatment incorporated in the medium. As a result, the medium interacts with the pretreatment or incorporated pretreatment to form a new and novel surface coating having one or more improved properties. The coating surface itself can be modified to improve subsequent paint adhesion.

[00144] The inventive process can form a thin film or seal comprised of amorphous silica, i.e. colloidal silica on conductive or nonconductive surfaces. The surface that is treated, i.e. coated, by the inventive process can possess resistance to soiling, improved corrosion resistance, increased electrical resistance, resistance to heat both long term and short term, flexibility, resistance to oxidation, improved adhesion of paints, sealers and topcoats among other sealant properties. Since the coating is amorphous, secondary forming operations such as upsetting tubular rivets, bending, stamping may be performed without compromising the silica coating.

[00145] The novel process is a marked improvement over conventional methods by obviating the need for solvents, solvent containing systems, passivates such as hexavalent or trivalent chromium, cobalt, cesium, phosphates, and cumbersome electrolytic/electroless process and the like. The inventive process thereby reduces worker exposure, waste disposal among other undesirable environmental impacts.

[00146] Additionally the inventive process can be used over passivates, phosphates, and the like to improve performance in a symbiotic manner. In another embodiment of the invention, the inventive process produces a stand alone sealer on stainless steel and other metals for medical, culinary, dental or food and blood processing devices.

[00147] The instant invention relates to a process for depositing or forming a beneficial surface upon a conductive or nonconductive surface. These surfaces are metallic or nonmetallic, oxides or glass-like surfaces wherever a silica film is beneficial. The process contacts at least a portion of the surface with silica containing medium having a controlled concentration, temperature and pH.

[00148] The process may be deployed as one step or a two-step process depending upon the application and or the desired results. The two step processes places a protein or polymeric thin film between the substrate and the silica coating whereas the one step process is applied direct to the surface being coated.

[00149] By metallic, it is meant to refer to sheets, shaped articles, weld aments, fibers, rods, billets, particles, continuous lengths, such as coil and wire, metalized surfaces. By nonmetals, it is meant, naturally occurring oxides, deposited oxides, polymer coatings, polymers, glass and the like. [00150] By surface, it is meant any surface. And may be nonconductive due to oxide or polymeric coatings or conductive which can be rendered nonconductive by the inventive process.

[00151] The inventive process can be applied by dip immersion coatings, spray, roller, and brush in a batch or continuous process. Contact time ranges from a few seconds to ten minutes, and normally about 1 to 5 minutes.

[00152] The inventive process can be operated on a batch or continuous basis. The type of process will depend upon the configuration of the surface being treated. \

[00153] The medium can be a fluid bath, gel or spray, among other methods for contacting the substrate with the medium. Examples of the medium comprise a mixture of silica in the form of colloidal silica with no monomeric species of silica to avoid any chemical reactions with the surface constituents. Additionally surfactants, thickeners, and the like can be added to enhance the film forming capabilities of the medium. Proteins and/or synthetic proteins can be used in aqueous dispersion to pretreat a surface thereby rendering it more resistant or non conductive and/or the proteins and/or synthetic proteins, peptides, derivatives and the like can be added to the medium, causing flocculation of the medium. Additionally, fully reacted lithium polysilicates that are fully polymerized with no monomeric species capable of chemical reacting within the medium or with the surface can be deployed with polycationic flocculants to further enhance the film performance. The medium can be modified with fillers, fumed silica, polymers, wear enhancers and the like. Alternatively, lithium hydroxide can be added to colloidal silica to enhance film forming.

[00154] By silica it is meant silicone dioxide.

[00155] By colloidal silica, it is meant a gelatinous substance made up of insoluble non diffusible particles larger than molecules but small enough they remain suspended in a fluid medium. Commercially available colloidal silica such as LUDOXTM, as well as other commercially available sources, are described as discrete uniform spheres of silica which have no internal surface area or detectable crystalinity. Most are dispersed in an alkaline medium which reacts with the silica surface to produce a negative charge. Due to the negative charge, the particles repel one another resulting in stable mediums.

[00156] By cationic polymer, it is meant a polymer stable at elevated pH and capable of flocculation of colloidal silica. A cationic polymer may be linear and/or branched and may include any or several from the following group of compounds including: HvAzirine, dihydro-, Aethylenimin, Aethyleminim (German), Aminoethylene, Azacyclopropoane, Aziran, Azirane, Aziridin, Aziridin (German), Aziridine, Aziridine homopolyer, Aziridine, Homopolyer, Dihydro-I HOazirine, Dihydroazirene, Dihydroazirine, Dimethyleneirnine, Dimethylenimine, Ethirydine, Ethoxiylated polyethylenimine, Ethyleenimine, Ethyleenimine (Dutch), Ethylene imine, Ethyleneimine, Ethyleneimine, homopolymer, Ethyleneimine, inhibited (UN 1 185) (Poison), Ethylenimine, Ethylenimine polymer, Ethylenimine resins, Ethylenimine, Homopoloymer, Ethylenimine, polymers, Ethylenimine, polyerms (8CI), Ethylinime, Etilenimina, Etilenimina (Italian), Poly (ethylenimine), Poly (ethylenimine), Polyaziridine, Polyethyleneimine, Polyethyleneimine (V AN) POL YETHYLEMININE, Polyethylenimine (10,000), Polyethylenimine. Epichlorohydrin is not included, as it is a highly toxic material and known carcinogen.

[00157] By emulsion aid it is meant surfactants that enable additions in water- borne mixtures to stay in suspension as well as improve the wetting of surfaces.

[00158] By flocculation, it is meant the adsorption of a cationic material simultaneously on the surfaces of two different silica particles, colloids in the invention at hand, thus linking them together. Complete flocculation occurs when there is enough adsorbed flocculants to create bridges to form a three dimensional network throughout the medium with an accompanying charge reverse to a positive charge.

[00159] The temperature of the medium at the time of application is usually between 15°C and 40°C with 38°C being preferred embodiment in order to insure a stable medium. The surface temperature of the product to be coated by the medium can be between freezing 0°C to under boiling of water 100°C with the preferred between 30°C and 75°C. After the medium is applied the products can be force dried at 1 15°C or air dried depending on the application. Rinsing after coating is optional, depending on the application, but not necessary to the formation of the films. The pH of the medium can be from 4.5 to 1 1 .0 depending if acid modified coatings are conducive to the application of low pH. High pH is limited to II as at that point the colloidal silica phase dissolves to diverse species of silica. The preferred pH of the medium is around 9-10.

[00160] The surface of the thin film or seal formed from the inventive medium disclosed herein can be modified by the addition of vagrant carbon nanospeheres, glass nanospheres, frets, flakes, PTFE and PVDF powders, spheres, chips and the like and pretreated with silicate or silane or other polymeric coatings to render them non adherent to the medium thereby leaving a textured surface when the coating is dried. By vagrant is meant a portion is not integral to the coating. In one embodiment of the invention, particles or spheres larger than the coating thickness are included and treated to be nonadherent to the coatings. These added particles or spheres are expelled or non adherent to the condensed silica film thereby leaving trace imprints of the shape there affording subsequent coating mechanical attachment points similar to sand or bead blasting.

[00161] By gel concentrate is it meant a medium formulated to produce a gel including all addition to facilitate shipping, handling with additional water added at the point of use or subsequent distribution.

[00162] Depending on the intended usage of the workpiece treated by the invention medium and/or metal of application, the workpiece can be rinsed and subsequently overcoated with secondary layer or layers. Example of such layers or coating comprise; additional layers of the inventive medium, paints containing polymers such as acrylics, epoxies, urethanes, silicones either solvent or water- borne, catalyzed, heat cured or air dried, powder paints, such as polyester epoxies and molten metals and the like. Combine with the overcoated modified surface described herein, it is meant the combination of the silica surface and overcoats are capable of passing ASTM D522 conical mandrel bent test, ASTM D2794 impact tests and ASTM D3359 cross hatch adhesion tests on various metallic substrates, such as steel, galvanized steel, phosphated steel, zinc, aluminum, copper, and mixtures/combination thereof.

[00163] The thickness of the inventive thin film or seal derived from the herein described medium can range from submicron to multiple microns in thickness. Thickness of coatings control many attributes ranging from abrasion resistance to water permeation multiple layers of the inventive coating. Thickness is controlled by colloid size, mixed colloid sizes and fillers, particles, and fillers and shrinkage rate of the three dimensional network of branched and flocculated silica particles.

[00164] The following delineates constituents in the inventive medium and process to coat nonconductive surfaces as well as methods to render surfaces nonconductive prior to or integral to the coating process. [00165] Aqueous sol-gels containing colloids may form a fragile non adherent deposition (ILER pg 379). The inventive coatings are based on inert colloidal silica in aqueous systems in to insure non reactivity with the coated surface. The inventive process uses a flocculent to bind normally nonadherent colloids to one another and to the underlying surface. The inventive layer may be tailored to have varying degrees of porosity, thickness, conductivity or resistance, adhesion to the surface, as well as formability and other coating characteristics.

[00166] The inventive process consists of contact of a surface with a medium in a one or two step process. In a one step process, the medium consists at a minimum of a mixture of colloidal silica, water, and a polycationic polymer. Other fillers and additives may also be included. The two step process involves the pretreatment of the surface to be coated with a protein, synthetic protein or other suitable flocculants in an aqueous solution. This coating is dried, and then the silica mixture is then applied. The two step process can leave a film of protein, or synthetic proteins or polymer flocculent on the surface, underlying the silica layer.

[00167] The content of the colloidal silica ranges from 5% to 50%. The colloid silica of various sizes from 3mm to 300 mm is and mixtures thereof. Without wishing to be bound to any theory or explanation, it is believed that in the inventive one-step process, the colloids are flocculated with simple proteins, synthetic proteins, or polyimine cationic water born polymers which provide coating adhesion to the coated surface and/or co adhesion within the colloids in solutions as well as in the coating. The content of the cationic polymer ranges from 0.01 % to 5%. The minimum concentration of cationic polymer concentration is that level that is adequate to enhance adhesion to substrates which also provides flocculation as taught by Glindqist, R Stratton wherein the Critical Flocculation Point (CFP) is discussed. The addition of cationic polymers beyond the CFP improves adhesion, flexibility and fills the voids between the colloids and fillers. Mixing in warm 40C-65C deionized water is preferred. The water phase comprises between 50-98% of the mixture.

[00168] In a two-step form of the disclosure, proteins, or polycationic polymers capable of flocculating the colloids can be deployed in aqueous solution at concentration of 0.01 % to 5% as pretreatment to reduce resistivity of the surface of the material, as well as initiate flocculation when the surface is contacted with a silica-containing medium. The first step to apply the flocculation material may be applied through immersion, dip, spray, or a variety of typical water-based solution application techniques. The first step mayor may not need to be dried before the silica medium is contacted to the surface, however drying between steps is also used in some applications. Without wishing to be bound to any theory or explanation, the two-step process results in a flocculation of the silica on the surface of the material to be coated rather than in-situ flocculation as in the one step embodiment of the invention.

[00169] In both the one-step or two-step embodiment of the disclosure, various fillers and additives may be used to enhance overall process or coating performance. Surfactants or emulsion aids are added for wetting in a range of 0.01 -2.0%. Zeolites may be added to produce a porous film. Various additives such as fumes silica as filler, carbopol as thickener and viscosity builder, also CAB-O-Sil as a thickener, gel former, inert fillers to provide bulk. Also silica-based flattening agents may be added to mitigate "picture framing" i.e. pull back of coating around edges of panels. Also for conductivity and surface modification additives such as carbon or PTFE, PVDF particles are added and designed to become vagrant materials. These may be coated to enhance the release from the silica get as it dries. These additions enhance adhesion of secondary coatings, paints or seals, alter the resultant surface in improved adhesion. Water miscible alcohols can be added to freeze proof the inventive mediums. These additives range in content from 1 -10%.

[00170] Surfaces studied in this endeavor include silicone dioxide wafers, steel, silicone steels, stainless steel, aluminum, copper, zinc, plated steel, phosphated steel, electregalvanized steel, glass, and surfaces of metal and glass having oxide and/or polymeric coatings. Preheating the surface to be coated to 40-94C provides improved condensation of a film.

[00171] After coating by various methods described herein, the coating can be left to air dry or drying at 100-120C for acceptable films. A rinse following the drying is optional depending on the final application of the film.

Inhibiting Bacterial and Protein Adherence to Stainless Steel Surfaces

[00172] The cleanliness of metal surfaces is paramount to safe conditions for animal health care and dairy production. Cleaning techniques and chemistry for cleaning solutions are well-established areas of study. However, these industries are necessarily changing to face the new realities and threats of emerging antibiotic- resistant pathogen strains, an increasing scope of health care for companion animals, as well as public concern and perception of food safety, food animal disease and human exposures via food routes. These new circumstances mandate that innovative technologies are developed to assist the growing challenge to veterinary medical, dairy, animal care, and food processing organizations.

[00173] Animal healthcare is a growth industry in the United States and especially in Missouri, particularly in the area of companion animal care and continued expansion of beef, chicken and pork markets. Health care-associated infections are a national concern affecting not only human patients, but also animal patients, and animal health care workers. It is well established by all animal health care, livestock, and dairy production procedures that cleanliness is the primary technique against animal infections or zoonotic (animal to human) transmission. Agricultural areas of concern for cleanliness of metal surfaces are primarily focused on dairy production and the prevention of mastitis. Antibiotic resistant strains are increasing the challenge to drug remedies and treatment of this condition. In the case of many surgical procedures, the rigor of autoclave sterilization is established to eliminate pathogen exposure. However, autoclave sterilization is not practical in many animal care or dairy applications, and thus is not a viable tool to combat the subject of this work. There are many areas of agriculture or animal health that are also challenged to maintain cleanliness of instruments and tools as a front-line means of infection control or foreign material (including toxin) exposure including meat processing and human health care, especially surgical procedures.

[00174] Stainless steels (SS) are preferred in countless animal health and agricultural applications for both their corrosion resistance (not corrosion proof) and the ability to produce products with a hygienic surface. However repeated exposure to ultra-pure water, autoclaving, and chlorides will initiate corrosion sites, and will develop a corrosion termed "rouge" or cause the development of micropits (1 ). The surface morphology changes caused by corrosion are thought to act as attachment points for potentially hazardous biomass, pathogens, proteins, and undesirable materials that can decrease the safety of these SS instruments and equipment (2, 3). Additionally, adhesives and other polymeric materials used in various activities, including medical procedures, are tenaciously attached to SS (Fig. 1 ) and also act as potential attachment points for pathogens, or other undesirable materials.

[00175] Foreign materials identified are proposed to be from three distinct sources, 1 ) corrosion (rouge, pitting, & exfoliation), 2) biomass that is remaining on instruments that have undergone accepted decontamination procedures, and 3) soap residue clinging to "clean' surgical instruments from the current cleaning procedures.

[00176] Processes and materials have been developed to clean SS surfaces of virtually all foreign materials. The first embodiment of the technology is a multi-step process using a novel citrus-based chemistry. The SEM image in Fig. 1 and spectra from the above mentioned study are of the same sample after cleaning with the processes and materials according to the present disclosure.

[00177] In order to reduce the likelihood for pathogens and other foreign materials to attach, a process results in a thin film coating of silicon dioxide to render the surfaces more soil resistant. The seal technology is based on emulating a natural phenomenon of thin film deposition. The diatom, photosysthetic algae, one of the workhorses of the carbon cycle, has the unusual capability of producing its skeleton entirely of glass from silicic acid found in natural waters. It has only been recently discovered that each diatom is equipped with silica precipitating proteins. The organic molecules meditate the formation of the inorganic silica nanospheres in a protein matrix.

[00178] A deep seal procedure uses an engineered process that mimics the biomineralization process found in simple diatoms through the use of proteins to form SiOz films. The resultant SiO_z film is hard, impervious, and adherent ranging in thickness around 2 microns. The film is not deposited in a uniform thickness; rather, it has been shown to fill surface morphology to exhibit a smoother surface after coating, free from pits. The net result is a surface that is believed to be less susceptible to adhesion of foreign materials, easier to clean, and easier to keep clean.

[00179] Substrates coated to date include glass, plastics, and metals. Potential applications germane to the animal health and agriculture industries include SS trays, surgical instruments, caging, food preparation equipment, and dairy processing equipment. Another potential surface to explore is coatings for implants used in animal orthopedic procedures. An SiO_z film matrix insulates the coated surfaces from the environment and is impervious to the rigors of exposure to a variety of environmental conditions thereby extending the life of products while sealing off areas to prevent pathogen attachment and/or bacterial growth. Additionally, chemical formulations that allow the facilities to maintain the level of cleanliness for the SS surfaces that have been "deep cleaned" are contemplated. Current cleaning practices focus on soap and water scrubbing, and in many cases combined with autoclaving. A new chemistry based on citric acid that can be used in the field, in the dairy barn, remove all foreign material including corrosion products, biomass and soap residue is proposed. For each of the above mentioned embodiments of the surface engineered solutions, there are significant commercialization driven objectives required.

Experimental Protocol

[00180] The ability of multiple species of bacteria to adhere to SS is well documented in the scientific literature (e.g. 4-6) and significantly impacts multiple aspects of animal health, food safety and human health. Depending on any number of variables, including the species of bacterium, physical properties of the SS, oxygen tensions, nutrient conditions and temperature, bacterial populations in excess of a million per cm² can be measured bound to the abiotic SS surface (7). Furthermore, in many instances, such adherence and colonization is a prelude to the formation of a biofilm of bacteria, a community of bacteria with altered properties such as enhanced resistance to antimicrobial and disinfectant treatments. In recognition of their important threat to animal and human health, the pathogens Staphylococcus aureus and various serovars of Salmonella enterica are particularly well studied with respect to their ability to bind SS and to form biofilms on metal surfaces (8, 9). Since the primary focus of this proposal is to use validated procedures to ascertain the effectiveness of the novel cleaning and sealing methodologies, these pathogens will be employed in the proposed studies. In addition to their importance to animal health/ food safety, these two species also represent one of each of the phylogentically distinct Gram-positive and Gram-negative lineages (categorized by cell wall structure) and reflect bacterial cells with either spherical or rod-shaped morphology, which through surface area considerations, may also impact SS binding.

Validation of Effectiveness on Field Stainless Steel Articles

[00181] The cleaning process is constantly being fine-tuned as additional early adopter site customer sites are secured, and those SS tools and instruments are cleaned. It has been observed that the cleaning process is long-lasting, and is highly effective to restore the SS surface to the original protective luster. There is a need to gain access to other early-adopter clients in order to generate the tools to allow for the integrative process necessary for improved processes.

[00182] To investigate the efficacy of the cleaning protocol, SS coupons will be used as an abiotic substrate for bacterial attachment and subsequent biofilm development. These experiments will be performed both in the absence of additional organic load and in the presence of the biologically relevant fluids, blood and milk. These complex, protein-containing liquids are pertinent because of the anticipated downstream translational application of the proposed research in the treatment of equipment in dairy parlors and in animal welfare. Following incubation under established conditions for biofilm formation, the number of adherent viable bacteria will be determined by removal of adherent cells by bead vortexing and enumeration by the counting of bacterial colonies that form on solid growth medium after plating (9). This will reflect the level of bacterial colonization in the absence of any cleaning treatment. Parallel samples will be subjected to the deep clean and then the number of remaining viable bacteria determined, As a standard benchmark, a conventional detergent washing procure will be used for comparison.

[00183] Although this protocol is fully anticipated to reveal the number of viable bacteria that have been removed by the treatment, it will not disclose the number of non-viable bacteria that may remain attached. Three different approaches will be used to determine the level of non-viable bacteria. These are (i) the differential staining of live and dead bacteria using a 2 color fluorescence assay (10), (ii) polymerase chain reaction assay for pathogen DNA that is an indicator for the presence of dead or lysed bacteria (11 ) and (iii) the visualization of bacteria or bacterially derived biomaterial by scanning electron microscopy (to be performed at the MU EM core facility).

[00184] While assessing the adherence of bacterial pathogens to SS, the binding and subsequent removal of protein to metal surfaces will also be determined. Green fluorescent protein (GFP) will be assessed for binding to SS coupons. This widely used and commercially available "reporter protein" has the advantage that it can be monitored by its fluorescence (readily visualized by microscopy) and by immunological detection by specific anti-GFP antibodies (12). Furthermore, GFP has a pH of 6.18 which should be compatible with electrostatic interactions with the positively charged metal surface. In addition a biotinylated synthetic peptide encompassing residues 128-144 of the Pseudomonas aeruginosa pilin receptor binding domain will be used as a model peptidic substrate, since it is reported to bind SS with high affinity (13). Binding and subsequent removal will be assessed through sensitive chemilurninescent detection of the biotin tag.

[00185] Another methodology includes the ability to shield the SS surface and reduce colonization following exposure to bacterial pathogens and minimize adherence of foreign material. In this series of experiments, SS coupons that have been subjected to the seal technique will be incubated in the presence of either Salmonella enterica serovar Typhimurium or S. aureus. For the latter species, a characterized bovine mastitis isolate, plus both community-acquired and hospital acquired strains of MRSA will be tested. Adherence will be monitored and compared to that which occurs on the surface of untreated coupons. Since the sealing procedure both reduces the number of "rough," pitted sites that might be focal points for the accumulation of bacteria or other foreign material and changes the surface properties of the metal surface, it will be important to determine the effect that this procedure has on prevention and reduction of microbial and protein contamination.

[00186] The cleanliness of surgical instruments is paramount to safe conditions for health care. Most surgical instruments are made of some variant of stainless steel. Cleaning and sterilization techniques for these instruments are well- established and fairly standard in the medical services industry. However, our recent studies indicate that these standard procedures can corrode the surfaces of the many surgical instruments that are reused repeatedly exposing tissues to metals with altered chemical properties and that presently used cleaning procedures can actually leave deposits of foreign material adhered to the surfaces of the instruments that could to transferred to tissues during surgery. Current medical practice is based on the assumption that these changes in the surfaces of the instruments have no negative consequences as long as the instruments are "sterile". However, this assumption has no basis in empirical research. Changes in the surface composition of these instruments may have serious health consequences as may the sloughing off of foreign materials from the instruments into surgical wounds.

[00187] Economical methods have been devised that remove corrosion and foreign materials from the surfaces of surgical instruments and coat the instruments such that they are restored to a "like new" condition after each use. This new method has the potential for preventing many complications of surgery. A second embodiment of the technology involves coating the instruments with a seal that has been initially shown to decrease adhesion of foreign material, making them easier to clean and keep clean. We propose to improve and document the efficacy of these techniques for cleaning and sealing surgical instruments and to bring a product to market for surgical instruments.

[00188] Stainless steels are preferred for surgical instruments for both their corrosion resistance (not corrosion proof) and the ability to be sterilized for reuse. However repeated exposure to standard cleaning techniques will initiate corrosion sites, cause formation of corrosion termed "rouge" and the development of micropits. Additionally, adhesives and other polymeric materials used in surgical procedures are tenaciously attached to stainless steels and are not removed by most currently used cleaning and sterilization procedures, as shown in Fig. 1. These surface materials can act as potential attachment points for pathogens or other undesirable materials, or may themselves slough off during surgery. Additionally, specialty steels are used as an electticallead for heart pacemakers that suffer from similar corrosion problems. In vitro corrosion of pacemakers is the highest reported replacement problem for this device, and is a global problem.

[00189] A recent study has identified corrosion and foreign material on health care stainless steel instruments that were in current use at a number of medical facilities. The foreign materials identified are proposed to be from four distinct sources, 1 ) corrosion (rouge, pitting, & exfoliation), 2) biomass remaining on instruments that have undergone accepted decontamination procedures, 3) adhesives that are used in surgical processes, and 4) soap residue clinging to "clean' surgical instruments from the current cleaning procedures, as shown in Fig. 2.

[00190] Awareness of this information is likely to create a market for methods to improve the overall cleanliness of surgical instruments. The applicants have developed processes and materials to clean stainless steel surfaces of virtually all foreign materials and remove corrosion. The first embodiment of the technology is a multi-step process using novel citrus-based chemistry. The following SEM image and spectra from the above mentioned study is of the same sample after cleaning with processes and materials (Fig. 3) according to the present disclosure. [00191] There is evidence that pathogens and other foreign materials adhere to stainless steel surfaces to varying degrees depending upon the surface treatments. There are a number of technologies described in the literature that endeavor to reduce adherence or reduce potentially threatening biofilm through metal surface modification (poult Sci. 2000 Dec; 79(12):1839-45. M Ignatova et al ACS, Langmeir 2006, 22, 255-262).

[00192] The applicants have prototyped a follow-on technology to treat cleaned stainless steel surfaces in order to reduce the likelihood and opportunity for foreign materials to attach. The innovative and proprietary process results in a thin film coating of silicon dioxide to render the surfaces more resistant to corrosion and adherence of foreign materials. The seal technology is based on emulating a natural phenomenon of thin film deposition in diatoms. Organic molecules meditate the formation of inorganic silica nanospheres in a protein matrix. The applicants' seal process uses an engineered procedure that mimics the biomineralization process found in simple diatoms to form S1O2 films. The resultant S1O2 film is hard, impervious, and adherent ranging in thickness around 2 microns. The film has a smooth surface from pits, filling irregularities in the substrate metal. The net result is a surface that is believed to be less susceptible to adhesion of foreign materials, easier to clean and keep clean.

[00193] Substrates coated to date include glass and plastics, in addition to stainless steel surgical instruments. Another potential surface to explore is coatings for implants used in orthopedic procedures. An Si02 film matrix insulates the coated surfaces from the environment and is believed to be impervious to the rigors of exposure to a variety of environmental conditions that might cause corrosion thereby extending the life of products while sealing off areas to prevent pathogen attachment and! or bacteria growth.

[00194] Additionally, chemical formulations are planned that allow medical facilities to maintain the level of cleanliness for the stainless steel surfaces that have been "deep cleaned" and preferably "sealed". Current cleaning practices focus on soap and water scrubbing, usually combined with autoclaving. We propose a new chemistry based on citric acid that will remove all foreign material including corrosion products, biomass and soap residue.

[00195] In further embodiments of the disclosure, the particles are friable. Without wishing to being bound to any theory or explanation, it is though that the instant invention uses not only the ultrasonic wave to accelerate the particles, but also uses the nergy release reaction of the bubble implosion to send particle potentially ricocheting through the bath thereby increasing the ceaning action, or nanoscrubbing by bombardment of the surface tih "hits" and potentially repeated "hits" from the instant nanoparticle and microparticle ingredients. The action serves, in some embodiments, to break up the particle into smaller and smaller particles, increasing cleaning action. Without wishing to being bound to any theory or explanation, this bombardment, microbombardment, and nanoscrubbing action decreases the time required to achieve a clean substrate by a factor of 5 or 10 or more, in one embodiment reducing the time from 30 minutes to 3-5 minutes, and then to 1 minute.

[00196] Furthermore, the addition of cleaners, surfactant and the like is well know in th art. The instant invention adds nanoscrubbing via inert particles such as silicone dioxide, variations of naturally occurring or synthetically produces inert particles, of regular or irregular, or jagged shapes. The particles may also be agglomeration os even smaller particles which are intended to break up into many particles in the instant invention.

[00197] Delivery of the cleaners with the nanoscrubbing inert particles would be accomplished in conventional plastic dispensing jugs, pumps, or vacuum delivery.. In one embodiment, the delivery of the cleaner and nanoscrubbing particles would be via a sealed chemical pack (so called pillow pack) encased in a water soluble film, made of natural or synthetic polymer. The active and/or nanoparticles could either be liquid or power or solids, or emulsions of liquid and solid and/or powders.

[00198] Deployment of the instant invention would be advantageous for food processing including meat and produce at the supplier/processor, wholesaler, retail, food processing, or in-home use. In one embodiment, the food articles are cleaned at the point of harvest, in another embodiment, the food articles are cleaned at the point of use, or could be cleaned anywhere in between. In one embodiment of the invention, vessels conveying ultrasonic energy may be small as to sit on a kitchen counter, or large as to receive an entire animal carcass. The ultrasonic machines may be stand-alone, or may be integrated into other cleaning utility areas. In one embodiment of the invention, an ultrasonic vessel is integrated into a sink arrangement with automatic or semiautomatic filling with water and/or cleaning formulations, and automatic or semiautomatic, or manual discharge of the used solutions.

[00199] Without wishing to being bound to any theory or explanation, the instant invention indicates a marked reduction in time for all cleaning surfaces, includes, metals, vegetables, and meat.

[00200] Experiments were conduced with tomatoes, peppers, and beef. Articles were contaminated with surrogate staining and then exposed to standard cleaners. The stains were removed with ultrasonic energy in 30 minutes. The tests were repeated with the instant invention. The time to complete removal was reduced to 3-5 minutes. The contaminant was substantially completely removed as evidenced by SEM/EDS spectra, as well as visual observation.

[00201] With regard to stainless steel surgical instruments, experiments were conducted. SEM/EDX data that indicates 1 ) evidence of found chemical evidence bioburden on autoclaved instruments, and 2) the instant invention cleaning removes all chemical fingerprints not associated with base stainless steel. IN the case of 1 ), the analysis found chemical fingerprints not associated with base stainless steel. In the case of 1 ), the analysis found chemical evidence of presumed bioburden and/or proteinacious materials not unlikely from blood or tissue residue (Nitrogen fingerprint) on the surface of pre-cleaned instruments. After cleaning, 2) the same instrument was completely clean from all contaminnatne (including Nitrogen) and returned to a SEM/EDX spectra identical to virgin stainless steel.

[00202] It should be noted that the disclosure is not limited to the embodiment described and illustrated as examples. A large variety of modifications have been described and more are part of the knowledge of the person skilled in the art. These and further modifications as well as any replacement by technical equivalents may be added to the description and figures, without leaving the scope of the protection of the disclosure and of the present patent.

Claims

CLAIMS WHAT IS CLAIMED IS:

1 . A cleaning solution comprising an inert particle in a liquid medium, wherein the medium allows propagation of ultrasonic waves through the medium.

2. The cleaning solution of claim 1 used in combination with ultrasonic energy wherein the resultant explosion propels the particle, thereby imparting kinetic energy to accomplish nanoscrubbing.

3. The cleaning solution of claim 1 , wherein the inert particle is a metal oxide having a low solubility in the liquid medium selected from the group consisting of titanium dioxide, silicone dioxide, and colloidal silica.

4. The cleaning solution of claims 1 , wherein the liquid medium comprises a liquid or mixture of liquids, the mixture of liquids comprising other additives that allow prorogation of ultrasonic waves through the medium.

5. The cleaning solution of claim 1 , wherein the cleaning solution is for use with a cleaning apparatus capable of emitting ultrasonic energy.

6. The cleaning solution of 5, wherein the apparatus is a tank, a wand, or a tray.

7. A method of cleaning a surface to remove foreign materials comprising providing a cleaning solution comprising an inert particle in a liquid medium and a cleaning apparatus that emits ultrasonic energy.

8. The method of claim 7, wherein the surface is a metal, food, plastic, and printed circuit boards.

9. The method of claim 8, wherein the metal is a stainless steel surgical instrument.

10. The method of claim 8, wherein the food is a vegetable.

1 1 . The method of claim 8, wherein the food is meat cuts.

12. The method of claim 1 1 , wherein the foreign material is prions.

13. The method of claim 7, wherein the foreign material comprises bioburden.

14. The method of claim 7, used in industrial application, commercial applications, or home applications.

15. The method of claim 7, further comprising a precleaning step comprising providing a solvent, an acid, or an alkali.

16. The method of claim 15, wherein the solvent is a natural solvent.

17. The method of claim 16, wherein the natural solvent is selected from the group consisting of methyl soyate and d-limonene.

18. The method of claim 15, wherein the solvent is a petroleum-based solvent.

19. The method of claim 7, further comprising a step of providing a heat source.