WO2012012349A2 - Nouveaux procédés pour améliorer des caractéristiques de surface - Google Patents

Nouveaux procédés pour améliorer des caractéristiques de surface Download PDF

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Publication number
WO2012012349A2
WO2012012349A2 PCT/US2011/044403 US2011044403W WO2012012349A2 WO 2012012349 A2 WO2012012349 A2 WO 2012012349A2 US 2011044403 W US2011044403 W US 2011044403W WO 2012012349 A2 WO2012012349 A2 WO 2012012349A2
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Prior art keywords
cleaning
cleaning solution
silica
medium
corrosion
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WO2012012349A3 (fr
Inventor
Robert Heimann
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Enginuity Worldwide LLC
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Enginuity Worldwide LLC
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/20—Water-insoluble oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/46—Specific cleaning or washing processes applying energy, e.g. irradiation

Definitions

  • 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.
  • 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.
  • 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.
  • the instant invention is directed to nanoscrubbing via inert particles such as silicone dioxide and the like.
  • 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;
  • Figure 2 is a SEM/EDX spectra illustrating analysis of spots #1 -3;
  • Figure 3 is a SEM/EDX spectra illustrating analysis of spots #1 -3 after cleaning.
  • the present disclosure is directed to a novel cleaning solution and method of nanoscrubbing.
  • 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.
  • 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.
  • 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.
  • a sealed chemical pack so called pillow pack
  • the action and/or the nano could either be liquid and/or powder.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Cleaning is defined as removing all foreign material, which may include inorganic and organic materials.
  • this invention also relates to passivating of metals.
  • it relates to overcoating or treating with novel silicon materials.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • passivating it is meant processes and materials to alter the surface from active to the environment to passive to the environment.
  • 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.
  • 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.
  • 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.
  • the predominate oxide would be an oxide of chrome.
  • the protective passive film of stainless steel can be comprised.
  • 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.
  • 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.
  • Solvent is effective for precleaning to remove heavy oils in mechanical scrubbers, spray systems and ultrasonic devices.
  • natural 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.
  • 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.
  • 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 H 2 0 byproducts to be pumped out of the plasma chamber.
  • the oxygen/room air plasma is more of a chemical cleaning process.
  • argon plasma cleaning occurs mainly through ion bombardment and physical removal of contaminants on the sample surface.
  • 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.
  • 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.
  • 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.
  • 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. .
  • BSE bovine spongiform encephalopathy
  • CJD Creutzfeldt-Jakob disease
  • 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.
  • 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
  • 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.
  • 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).
  • CJD Creutzfeldt- Jakob disease
  • 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.
  • NIH has reported the current decontamination methods as ineffective in cleaning surgical tools for the reduction of prion transmission.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the novel processes and formulations are made available for use in a machine to clean soiled articles.
  • 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.
  • 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.
  • the invention is used to maintain the cleanliness of the articles that have been cleaned and/or sealed with the instant invention.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.)
  • 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;
  • 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
  • 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.
  • 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% .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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%.
  • 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%.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the inventive seal fills voids, pores, draw lines, machine grinding lines, and electropolish etching, among other surface anamolies.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a data acquisition system to monitor and record each process event is included.
  • 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.
  • each process or partial process could be contained in an automated closed system module.
  • 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.
  • 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.
  • 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.
  • 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.
  • the cleaners, alkali or acidic would be filtered through suitable membranes or cartridge filters before return to storage vessel or accumulation vessel.
  • 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.
  • 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.
  • 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.
  • 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.
  • additives can be used in the silica-containing medium to alter surface texturing with benefits of paint adhesion by mechanical attachment.
  • 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.
  • 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.
  • Water-borne thin silica films 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.
  • 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.
  • 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.
  • grey veil carbonate and silicate compounds
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the inventive process can form a thin film or seal comprised of amorphous silica, i.e. colloidal silica on conductive or nonconductive surfaces.
  • 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.
  • 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.
  • inventive process can be used over passivates, phosphates, and the like to improve performance in a symbiotic manner.
  • inventive process produces a stand alone sealer on stainless steel and other metals for medical, culinary, dental or food and blood processing devices.
  • 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.
  • 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.
  • 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.
  • nonmetals it is meant, naturally occurring oxides, deposited oxides, polymer coatings, polymers, glass and the like.
  • 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.
  • 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.
  • 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. ⁇
  • the medium can be a fluid bath, gel or spray, among other methods for contacting the substrate with the medium.
  • 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.
  • 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.
  • lithium hydroxide can be added to colloidal silica to enhance film forming.
  • silica it is meant silicone dioxide.
  • 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.
  • 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.
  • 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, E
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • vagrant is meant a portion is not integral to the coating.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the inventive process consists of contact of a surface with a medium in a one or two 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.
  • 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.
  • 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.
  • CFP Critical Flocculation Point
  • 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.
  • 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.
  • 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.
  • 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.
  • silica-based flattening agents may be added to mitigate "picture framing" i.e. pull back of coating around edges of panels.
  • 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%.
  • 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.
  • Stainless steels 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.
  • SS corrosion resistance
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • GFP has a pH of 6.18 which should be compatible with electrostatic interactions with the positively charged metal surface.
  • 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.
  • Another methodology includes the ability to shield the SS surface and reduce colonization following exposure to bacterial pathogens and minimize adherence of foreign material.
  • 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.
  • Salmonella enterica serovar Typhimurium or S. aureus.
  • S. aureus 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the particles are friable.
  • 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.
  • 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.
  • cleaners are 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.
  • Delivery of the cleaners with the nanoscrubbing inert particles would be accomplished in conventional plastic dispensing jugs, pumps, or vacuum delivery.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the instant invention indicates a marked reduction in time for all cleaning surfaces, includes, metals, vegetables, and meat.

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Abstract

La solution de nettoyage selon l'invention comprend une particule inerte dans un milieu liquide, ledit milieu permettant la propagation d'ondes ultrasonores dans le milieu. Un procédé de nettoyage d'une surface par élimination des matériaux étrangers à l'aide d'une solution de nettoyage qui contient une particule inerte dans un milieu liquide et un appareil de nettoyage qui émet une énergie ultrasonore est également décrit.
PCT/US2011/044403 2010-07-17 2011-07-18 Nouveaux procédés pour améliorer des caractéristiques de surface Ceased WO2012012349A2 (fr)

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