WO2006094285A2

WO2006094285A2 - Surface treatment methods including metallization, apparatus for carrying out the methods, and articles produced thereby

Info

Publication number: WO2006094285A2
Application number: PCT/US2006/008053
Authority: WO
Inventors: Robin L. Pointer
Original assignee: Global Tech International, Inc.
Priority date: 2005-03-04
Filing date: 2006-03-06
Publication date: 2006-09-08
Also published as: WO2006094285A3

Abstract

The present invention provides numerous embodiments of new surface treatment methods, their apparatus for carrying out those methods, and articles made thereby. Numerous embodiments are disclosed which provide for a novel surface treatment for substrates to provide various properties, including but not limited to wettability, electrical conductivity, , improved adhesion, metallizability, sanitization, lubricity, abrasion resistance, static resistance, thrombo-resistance, anti-microbial, paintability, strengthening, vapor barrier properties, reflectivity, and voidless coverage of the treated article. The surface treatment is effected by subjecting a substrate, whether it is a polymeric sheet, some powder, a foam sheet, yam, or a fabric, to at least a sulfur containing gas for a relatively short period of time to provide a sulfonated surface treatment. Additional gases may be reactive or non- reactive in partial pressures effective within the range of the sulfur containing gas.

Description

SURFACE TREATMENT METHODS INCLUDING

METALLIZATION, APPARATUS FOR CARRYING

OUT THE METHODS, AND ARTICLES

PRODUCED THEREBY

CROSS REFERENCES TO RELATED APPLICATIONS

This patent application claims the benefit of three prior filed copending priority dates, as follows, U.S. Provisional Patent Application 60/658,647 filed on March 4, 2005; U.S. Provisional Patent Application 60/671,647 filed on April 15, 2005; and U.S. Provisional Patent Application No. 60/695,900 filed on June 30, 2005, which Provisional Patent Applications are incorporated herein by reference.

TECHNICAL FIELD

This patent application relates to surface modification of a substrate, and more particularly relates to surface treatment methods, apparatus for carrying out the methods and the articles made thereby.

BACKGROUND OF THE INVENTION

In conventional material science, there has always been a search for various surface modification treatments, including a desire for a technology that would adhere two materials to one another completely and forever. It would be desirable to provide a method and apparatus to produce any type of substrate with any type of material permanently bonded to its surface, i.e. plastic substrate with a bonded outer layer of metal; or a fabric with a wicking agent; or an anti-raicrobial bonded to a surface that won't wash off; or a surface treated particulate that is then formed into an article with the desired properties.

It is also a desired result to have materials with a completely corrosion-resistant surface in order to be utilized in any number of environments. In the past, surface treatments have included chrome plating, plastic coating, dipping and spraying of various exterior layers, and the like onto a substrate. Many of these methods have proved to be very unfriendly to the environment, including the use of toxic solvents for spraying and dipping, and toxic by-products resulting from chrome plating and metallization. This has caused a great problem for many industries, and the Environmental Protection Agency is especially loathsome of chrome plating by-products.

Environmentalists would like to see reinvented manufacturing techniques that use environmentally friendly techniques and methods that do not produce any toxic by-products oi^¬ fumes that are released into the atmosphere. In the recent past, many companies have done research in order to provide coatings that have superior adhesion to the surface of various articles. As one knows, electroplating has provided a good method of coating conductive metallic substrates, although electroplating is more difficult for nonconductive substrates, such as plastic.

It would be veiy desirable in the manufacturing industry to provide new methods and articles produced thereby which can be coated with a material mat is wanted in order to provide certain desired properties. Such desired properties may include adhesion enhancement, static reduction, surface tension reduction, wettable surfaces, wickability, flexibility of the substrate, sanitization, shiny metallization, which is very popular for automotive pails, and the like. In addition, metallization of surfaces would provide conductivity, thermal dissipation, magnetic feasibility, as well as any other desired physical characteristic properties.

Therefore, various industries have been seeking new methods for surface treatment in order to facilitate coatings that produce the desired physical properties, hoping that such coatings will adhere strictly to the surface, without the requirement of any dimension change if the coating is sufficiently thin. However, under conventional coating methods, such thin coatings easily flaked off or were susceptible to removal by solvents or adverse environmental conditions.

The coatings industry is especially looking for new surface treatment methods, which can be universally used to adhere any number of exterior surfaces coatings, plating, and the like to a substrate. Previously, metal substrates could be electroplated in an electroplating bath in order to place new metallic coatings ionically bonded onto the metal substrate. However, this procedure generally did not work for plastics and non-conductive substrates, so an entirely different set of equipment and operational methods were required. Furthermore, very thin coatings were not possible in many circumstances because the procedures utilized were unable to provide a strongly adherent coating that would stay on the surface of the substrate. Adhesion was provided by applying a certain mass of coating material, which then would form its own substantial material coating.

Therefore, the present inventor has endeavored to provided new surface treatment methods, apparatus for carrying out the various methods, and articles that are produced thereby, which incorporate the use of a surface modifying treatment onto various surfaces, including the surfaces of powdered plastics, the surface of a metal substrate, the surface of a pre-form metal cast piece, the surface of a preformed plastic substrate, and other such surfaces and substrates as will be described in more detail hereinbelow.

SUMMARY OF THE INVENTION

In accordance with the above-noted advantages and desires of the industry, the present invention provides numerous embodiments of new surface treatment methods, their apparatus for carrying out those methods, and articles made thereby. Numerous embodiments are disclosed which provide for a novel surface treatment for substrates to provide various properties, including but not limited to wettability, electrical conductivity, , improved adhesion, metallizability, sanitization, lubricity, abrasion resistance, static resistance, thrombo-resistance, anti-microbial, paintability, strengthening, vapor barrier properties, reflectivity, and voidless coverage of the treated article. Basically, the surface treatment is effected by subjecting a substrate, whether it is a polymeric sheet, some powder, a foam sheet, yarn, or a fabric, to at least 0.001% to about 50% of a surface modifying gas for a relatively short period of time to provide a modified surface treatment. Additional gases may be reactive or non-reactive in partial pressures effective within the range of the sulfur containing gas. Thereafter, the substrate is preferably neutralized, whether by contacting with a neutralizing base agent, or by contacting with a metallic bath so that the metal ions can act as the neutralizer. Other embodiments are disclosed for metallization of a substrate surface. Transfer gases may be preferentially utilized to cany the surface treatment deeper into the surface of the substrate, for instance to depths of over 100 microns.

To assure proper gaseous treatment, a gas/air monitoring system is disclosed which monitors the concentration of the sulfur-containing gas after a gas treatment has been performed. The monitor is advantageous so that the operator can know how much elemental constituents of the gas may need to be replenished by the gas generator for raising the values of the various elements back to an effective percentage before the next gas treatment.

For advantageous treatment of fine particulates, powders, small pieces, and dust, a method and an apparatus has been disclosed which includes a fluidized bed for homogeneous surface contact of the particulate to the gaseous surface treatment. Once the particulate has been treated, any article made thereafter from the particulate exhibits the same properties throughout the bulk of the material as the surface.

In yet another embodiment of the present invention, a metallization method, apparatus and articles produced by the method and apparatus is disclosed which is suitable for all types of substrates, whether rigid, flexible, powdered, or finely detailed. This metallization method is amenable to producing conductive substrates, conductive molds, flexible computer boards, cell phones, circuits and electronics, etc.

Although the invention will be described by way of examples hereinbelow for specific embodiments having certain features, it must also be realized that minor modifications that do not require undue experimentation on the part of the practitioner are covered within the scope and breadth of this invention. Additional advantages and other novel features of the present invention will be set forth in the description that follows and in particular will be apparent to those skilled in the art upon examination or may be learned within the practice of the invention. Therefore, the invention is capable of many other different embodiments and its details are capable of modifications of various aspects which will be obvious to those of ordinary skill in the art all without departing from the spirit of the present invention. Accordingly, the rest of the description will be regarded as illustrative rather than restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

For a further understanding of the nature and advantages of the expected scope and various embodiments of the present invention, reference shall be made to the following detailed description, and when taken in conjunction with the accompanying drawings, in which like parts are given the same reference numerals, and wherein:

FIG. 1 is a schematic drawing of a gas trap made in accordance with the present invention;

FIG. 2 is a cross-sectional side elevational view of a mechanical embodiment of the present invention in its environment with a fluidized bed attached;

FIG. 3 is a cross-sectional side elevational view of the automated surface treatment machine constructed in accordance with the present invention, in a close-up view of the working parts of the invention;

FIG. 4 is a cross-sectional view of another view embodiment including a conveyor- less automated surface treatment machine; FIG. 5 is a fundamental description of a Hall Effect or pressure sensitive monitor;

FIG. 6 is a an apparatus for generating a reagent of sulfur containing gas or mist in a reagent generator ;

FIG. 7 is a side elevational cross-section of the embodiment of the present invention located in the gas/air stream;

FIG. 8 is a cross-sectional view of the mechanical embodiment of the gas/air monitor;

FIG. 9 is a close-up view of a partial side elevational cross-section of the electronic embodiment of the present invention.

DETAILED DESCRIPTION OF DRAWINGS

In accordance with a first embodiment of the present invention, there is provided a new surface treatment method, which includes the contacting of one or more reactive gases to a substrate. Notably, in this embodiment, a sulfur-containing gas is contacted onto a surface substrate as a pre-treatment for adhesion of a later material to be contacted with the modified surface. The sulfur-containing gas for contact is preferably sulfur trioxide, which may be generated from elemental sulfur, sulfur oxide, sulfur dioxide or may be purchased as sulfur trioxide itself. Although the basic methods for generating sulfur trioxide gas are the subject of numerous expired prior art patents, any method of delivering sulfur trioxide gas to the chamber is acceptable. Regardless of how the sulfur trioxide is created, one of the main benefits that will arise is that adhesion is encouraged on a molecular level with other materials that thereafter contact the same article surface.

It is postulated that the sulfur-containing gas molecules bond to the first contacted article surface which then acts as an ionic carrier to attract and ionically bond the second contacted material onto the first surface. Conventional surface treatment methods have used various adhesion layers including nickel coating and the like, although this particular surface modification method disclosed as a preferred embodiment in the present application acts to adhere, on a molecular level, a second material onto the first contacted material, lending itself to perfect coatings and very thin adherences without any further intermediary components.

1. SURFACE TREATMENT CHAMBER AND FLUIDIZED BED

In practicing the method of the present invention, it is especially useful to utilize a fluidized bed in order to surface modify small particulates, including powdered plastic, pellets, and small metal powders, ceramic powders, ceramic whiskers and fluff, or any other type of material that can be fluidized. The material to be fluidized is put into a fluidized bed chamber, and is subjected to an environment of at least one gas including a sulfur-containing gas. The chamber is preferably airtight, and the sulfur containing gas may be recycled and reused for further sulfonation of particulates.

It has been found useful to incorporate a particular system for sulfonation the fluidized bed in accordance with the present invention. The inventor believes a maximum efficiency comes from the use of a new and novel gas trap.

Looking first to Figure 1, a gas trap is shown generally denoted by the numeral 10 which includes a gas inlet 12 allowing a source for sulfur-containing gas to enter into the fluidized bed chamber. Stainless steel fittings 14 provide an ingress for the sulfur-containing gas through gas inlet 12 and penetrates the fluidized bed chamber wall 16 via stainless tubing 18. A stainless steel sheet 20 is suspended a desired effective distance from the egress of stainless tubing 18 and is held at that distance by wire supports 22. Therefore, in practice, as the sulfonating gas enters into fluidized bed chamber through chamber wall 16, any condensate will predominantly form on the stainless steel sheet 20 and will precipitate as droplets 24, generally of oleum, and may be removed from the interior of the fluidized bed chamber via valve drain 26.

Looking next to Figure 2, there is shown gas trap 10 in fluid communication with fluidized bed chamber 30. Although Figure 1 showed the gas trap elements in detail, Figure 2 shows a broader scope of gas trap lOas it communicates with fluidized bed chamber 30. As one can see, gas trap 10 includes gas inlet 18 and the backing plate sheet 20 for collecting the droplets of condensate 24, and includes egress 28 to cany a substantially dried gas 32 into fluidized bed chamber 30 in order to fluidize particulates 34. This gas trap configuration substantially removes the liquid oleum from the sulfur-containing gas, which can act as a contaminant that adheres particulates 34 together, which presents a disadvantageous situation. Particulates 34 are preferably subjected to a dried sulfur-containing gas as it fluidizes a bed of particulate 34 in order to provide a solid sulfur-molecular bond to the surfaces of the various particulates 34 within the fluidized bed chamber 30.

As particulates 34 become subjected to sulfur-containing gas, the sulfur molecules will bond to the individual surfaces of the particulates, for instance the carbon molecules in plastic particulates. The sulfur molecules will adhere to any other material which may be the chosen particulate in the fluidized bed, and will provide an ionic free radical which will form an ionic bond with the next material that it comes into contact with.

Looking next to Fig. 3, an automated surface treatment machine generally denoted by the numeral 40 includes a dry air chamber 42, for initially exposing the fluidized bed particulates for drying purposes. Once the particulates have been dried, they are transported through a dry air conduit 44 into a first fluidized bed chamber 46. Fluidized bed chamber 46 acts as a fluidized container for the particulate, and further includes a hood 48 in order to allow a path for exhaust gases through conduit 50. The exhaust gases travel through conduit 50 into scrubber or mist eliminator 52 which is exhausted into atmosphere 54 by an exhaust tube 56.

A sulfur-containing gas source 58 is shown as an SO₃ generator 58 which is in fluid communication via conduit 60 into the treatment fluidized bed chamber 46. In essence, dried particulate material, such as polymer powders, metal powders, ceramic powders, or any other particulate material, may be drawn into the fluidized bed chamber 46 and then sulfonated by contacting those particulates with a sulfur-containing gas in a fluidized bed configuration. Thereby, each individual particulate material will have come into contact with the sulfur-containing gas, and the entire surface of each individual particulate will be sulfonated substantially on the entirety of its surface.

Looking back to Fig. 3, the particulate, once sulfonated by contacting with the sulfur-containing gas, may be drawn through the surface treatment machine 40 by conveyor 84 into the next chamber, the neutralizing fluidized bed chamber 66. The neutralizing chamber may utilize any suitable neutralizing agent, but preferably provides aqueous ammonia or gaseous ammonia 62 in order to neutralize the ionic surface generated by the step of sulfonation. The neutralizing agent may be recirculated by recirculation pumps 64 attached to the bottom of neutralized fluidized bed chamber 66. As the ammonia 62 is neutralizing the sulfonated particles that have been drawn into fluidized bed chamber 66, the ammonia gas and F fluent will be exhausted through conduit 68 upwardly into the scrubber 52 and exhausted to atmosphere 54 through exhaust tubing 56. Once the fluidized bed has been inactivated, and the particulates fall back down onto the floor of the fluidized bed chamber, the particulate may thereafter be moved to the next station of surface treatment machine 40, again by conveyor 84. Conveyor 84 may be a single conveyor or may be a series of individual conveyors depending upon the application and the desired situation.

Referring again to Fig. 3, it may be most advantageous to rinse the neutralized particulate after it has been neutralized in fluidized bed chamber 66. A rinsing station 72 may most advantageously be utilized with a simple water rinse 70 that is recirculated with a recirculation pump 64. Water rinse station 70 may include a hood 72 for collecting exhaust steam and contaminated water vapors through conduit 74 up into scrubber 52 for exhausting to atmosphere 54.

After the water rinse, which may occur either in a fluidized bed situation, or with a simple water rinse tank such as shown in Fig. 3 as numeral 70, the conveyor 84 may take the wet neutralized and sulfonated particulate into a drying station 76 where heated air is used to dry the particulate. A hood

78 may be utilized with an exhaust 80 as egress from the hood to impart water vapor which has dried off the particulate into atmosphere 82.

The preferred method utilizing the surface treatment machine 40 as disclosed in Fig.

3 preferably includes the steps of exposing drying particulates to a sulfur-containing gas, for a desired dwell time at a desired concentration of sulfur-containing gas. The exposure may include exposing the particulate to a sulfur-containing gas from about 1 second to about 20 minutes, depending upon the desired amount of sulfonation to occur on the surface of the particulate. A concentration of the sulfur-containing gas may be from about 1 part per million to about 500,000 parts per million, unless a stronger concentration is desired, i.e. 0.001% to 50%. The sulfur- containing gas may include a gas selected from the group consisting of sulfur dioxide, sulfur trioxide, combinations thereof, or any other suitable sulfur-containing gas. After the contact with the sulfur-containing gas, it may be preferable to again expose the sulfonated particulate to dry air in order to rinse off some of the excess sulfur-containing gas from the particulate before neutralization. The next step is preferably to neutralize the sulfonated dried particulates in order to ionically neutralize a now ionically charged surface of the particulate. Again, any neutralizing agent may be utilized, but for efficiency and cost reasons, it is most expedient to utilize either aqueous or gaseous ammonia for desired dwell time and at a desired concentration. Again, a sulfonated particle may be contacted with the neutralizing agent for a time period from about 1 second to about 20 minutes in order to affect the neutralization. The concentration of neutralizing agent may be from about 1 part per million to about 10,000 parts per million, or in the case of aqueous ammonia from a 0.001 molar concentration to about a 10 molar concentration in aqueous solution.

A preferred final rinse with water is intended to remove any excess neutralizing agent which may cling to the surfaces of the particulates. A heavy water vapor or steam may also be utilized for rinsing the neutralizing agent, in the fluidized bed situation. However, it is easiest, most efficient and most cost affective to just rinse the neutralized particulate in a fresh water rinse, followed by drying the wet particulate with heated air in a fluidized bed.

Looking now to Fig. 4, there is shown a surface treatment machine without a conveyor generally denoted by the numeral 90, including similar aspects to the invention shown in Fig. 3, but without the use of a conveyor. Particulate transport may be achieved through any known method, including batches, and/or individual transfer stations. Again, the particulate material which is desired to be surface treated may include any type of particulate, including polymeric powders, metal powders, ceramic powders, or any other particulate material which is desired to receive the surface treatment. All polymers are suitable as are any other particulate materials light enough in weight to be fluidized. Some experiments have been done on crumbed rubber, wooden whiskers and chips, and a multitude of other materials which may be most advantageously treated with a sulfur-containing gas to provide adherence properties to the individual particulates when combined with other materials into a composite material. For instance, it has been shown that sulfonated crumbed rubber tire material can be incoiporated into a concrete matrix to yield a bendable concrete which can be nailable and/or energy absorbent for shock resistance and load traffic wear-resistant. There are so many possibilities for utilizing sulfonated particulates in combination with other materials to create a new composite that the list is too long to be mentioned in this patent application.

Fig. 4 illustrates the surface treatment 90 as including a diy air generator 92 using a conduit 94 to expose the dry air into the fluidized bed chamber 96 which includes the particulate matter. Fluidized bed chamber 96 may also include a hood 98 attached to a conduit 100 in order to allow fluid communication for the dry air to be exhausted into a scrubber or mist eliminator 102 which is exhausted to the atmosphere 104 via an exhaust egress 106. Optional air scrubber and/or air treatment devices may be incorporated into the scrubber 102 or exhaust conduit 106. As described hereinbefore with reference to Fig. 3, a sulfur trioxide or sulfur-containing gas source 108 may allow for the transport of sulfur-containing gas through conduit 110 into fluidized bed chamber 96. After the particulate has been dried within fluidized bed chamber 96, the sulfur-containing gas from the source 108 is allowed to ingress into fluidized bed chamber 96 through conduit 110 in order to expose the particulate in a fluidized bed configuration to a sulfur-containing gas, yielding a sulfonated particle concentration.

As described hereinabove, it is preferable to neutralize the sulfonated particulates after sulfonation, and the sulfonated particulates may be transferred into a neutralizing fluidized bed chamber 116. Again, a neutralizing agent 112 is introduced into the fluidized bed chamber 116, and tussled around via typical fluidized bed configuration in order to allow the neutralizing agent to contact the entire surface of the sulfonated particulate, thereby yielding a neutralized surface on substantially all the surface of the particulates. As the neutralizing agent is preferably aqueous or gaseous ammonia, it is preferable to include an exhaust or conduit 118 to allow fumes to be traveled into a scrubber 102 for release into an exhaust treatment center 106 for exposure to the

I l atmosphere 104. Thereafter, it is preferable to wet rinse, with water, the neutralized and sulfonated particulates in order to remove any excess neutralizing agent in a water rinse 120. A hood 122 is preferably attached to water station 120 with an exhaust conduit 124 for releasing exhaust into scrubber 102. Then, the wet, sulfonated and neutralized particulate is transferred through any known means into a particulate dryer 126 with a optional hood 128 attached to an exhaust egress 130 for release of dried steam by product fumes into atmosphere 132.

In addition to the surface treatment apparatus described above, a special SO₃ sensor and feed mechanism may be included which should allow for precise measurements of the amounts and concentration of the SO₃ throughout the treatment chamber to measure the proper partial pressure percentage by volume of gas which is being exposed to the surface of the articles being contacted by the sulfur containing gas along with any other reactive, non-reactive or transport gases mixed in with the polymers.

In yet another embodiment, a gas/air sensor is disclosed for monitoring concentrations of sulfur containing gas, whether remotely or not, and related methods of manufacturing same, and methods of using same. More particularly, the invention relates to a reactor apparatus that will convert a source sulfur such as raw sulfur, anhydroussulfur dioxide, sulfuric anhydride, chlorosulfonic acid, sulfur trioxide, and other known sulfur containing liquids, solids and gases, into a sulfur-containing gas for the purpose of modifying the surface of a polymeric material or a metallic material, or a rubber material, in such a way that the substrate material become endowed with such properties as improved adhesion, barrier, water wettability, antistatic, hydrophilic, reflective, hardened through metallization and other bonded materials, antimicrobial, hypoallergenic, thromboresistant, etc.

A sensor for monitoring gas concentrations, relative humidity, air temperature, source sulfur concentrations, and other relative functions of the gas modification chambers may be constructed utilizing initially a Hall effect gas/air sensor in mechanical, electromechanical and electronic versions is used as a sensor/control module for increasing the dilution of sulfur containing gas, and sensing and controlling the temperature and level of dry air needed for the desired dilution in the gas/air mixture that is conveyed into a treatment chamber by a finned gas heating exchange devise. This sensor could also utilize piezoelectric power, conventional AC/DC electrical current, SAW principles, RF signals, etc to communicate with the monitor or operator as well as with remote solenoids that opens and closes valves that will allow more sulfur containing gas, dry air, or heat to be released into the system, as well as a sensor that it sensitive to the desired dwell time for the specific surface modification desired, and will discharge the gas/air mixture into the air scrubber system.

Surface modification of particulate polymers may include sulfonation of powdered polymers by a process of exposing the surface of the polymer to about 0.001% to 50% of sulfur trioxide gas in dry air for a prescribed period of time. After the polymer has been exposed to the sulfur trioxide gas, the polymer is preferably neutralized with an fluid having a positive ionic charge to form a polar field on the surface of the polymer. The level of penetration into the bulk of the individual powder particle is usually dependent on the time of the exposure of the sulfur trioxide on the polymer surface, but may also be enhanced, or sped up, by the introduction of a non-reactive transfer gas in conjunction with the sulfur trioxide. Such transfer gases may include, but are not limited to, nitrogen, helium, hydrogen, or any combination thereof in partial pressures which are effective. Other transfer or reactive gases may be utilized that include oxides, carbides, nitrides, and the like. The observed maximum depth of penetration is 25 microns without a transfer gas, and penetration is much greater, in some instances to the core of the particulate when a transfer gas is utilized.

The above described transfer gases may be utilized in partial pressures ranging, individually and/or collectively, from about 0.001% to about 80% of the resulting total pressure including the sulfur containing gas. It is preferred that these gases should also be as dry as possible, so as to minimize the reaction with water vapor with the sulfur, as this is generally an extremely exothermic reaction. The preferred partial pressure transfer gas contains from about 4% helium, 1% hydrogen and 1% nitrogen, the balance being sulfur trioxide. This reactive/transfer gas combination provides particles, after subjecting to this gas, that become sulfonated throughout the bulk of the particle. Consequently, when the polymer particle is used for plastic forming, the resulting article includes the characteristics of the sulfonated surface, even if the polymer is expanded or injection molded. If no transfer gas is desired, for instance if only the surface is desired to be affected, leaving the properties of the polymer still attractive for its relative application, then the above described sulfonation method will produce a polymer that will likely have the following properties: wettability, electrical conductivity, vapor barrier properties, improved adhesion, metallizability, lubricity, abrasion resistance, static resistance, thrombo resistance, antimicrobial, paintability, strengthening, reflectivity, and voidless coverage of the treated article, in addition to other properties.

In certain applications, it may be advantageous to pre-etch the substrate with an SO₃ etching procedure so that the SO₃ provides the surface preparation required to achieve electroless copper or nickel deposition and to promote acceptable adhesion of subsequent electrodeposited. In this embodiment of the present invention, polymers are prepared by etching with solutions of chromic/sulfuric acid or pure chromic acid. Contact is from about 1 second to about ¹A hour in an aqueous bath, and is dependent on the substrate material itself.

Optional pre-etching provides polar molecular groups on the surface of the article to be sulfonated, and it also plays an important role in catalyst absorption and the adhesion mechanism. It is a strong cation-exchange surface. The most commonly used commercial catalytic system for sulfated plastic surfaces is a Pd/Sn catalyst in water. Sulfamate (Dull) nickel can be used as a barrier layer.

2. Metallization of a Surface

As metallization is desired for many applications such as chrome fenders, toys, car parts, home consumer goods, along with many others, an experiment was performed to provide a superior method of adhering a metallic composition to a polymeric substrate. As it is especially useful for adhering two dissimilar materials, sulfonation is preferred for this application, as the adhesion properties become so great that it is nearly impossible to break them apart. The first step consists of contacting a sulfur-containing gas to a surface, preferably a carbon-containing polymeric surface. The sulfur atoms bond to the carbon atoms, and provide a negatively charged polar surface. Thereafter, the surface is preferably neutralized to provide a surface that is antimicrobial, gas impermeable, adhesion-ready for dissimilar materials, and exhibits a great deal of other wonderful properties listed below.

If further surface modification is desired, such as metallization or adhesion to particulates, the surface may be etched and metallized by the following procedure. Almost any metal may be applied to the surface of plastic by first etching, and then contacting with an aqueous metallic solution. Especially useful are nickel sulfates, nitrates, copper solutions, among many others.

Polymers are currently prepared by etching with solutions of chromic/sulfuric acid or pure chromic acid. This conventional chrome plating acid etch is generally considered to be an environmental hazard, so a new way to etch is especially desirable. SO₃ provides the surface preparation required to achieve electroless copper or nickel deposition and to promote acceptable adhesion of subsequent electrodeposited coatings. Any other suitable metallic may be used. The present invention proposes the use of a gaseous etch, whether using a sulfur-containing gas, or utilizing a plasma etching procedure with any suitable etching gas. Polar groups on the surface play an important role in catalyst absorption and the adhesion mechanism. It is a strong cation- exchange surface. The most commonly used commercial catalytic system for sulfated plastic surfaces is a Pd/Sn catalyst in water.

Example 1 Surface modification & metallization of a polymeric substrate made of polypropylene was effected by beginning with a room temperature water rinse of the substrate, followed by contact with a colloidal Palladium catalyst for about 1-4 min @ approximately 130° F, followed by another water rinse, and contact with an accelerator/conditioner for about 1 -4 min @ approximately 115° F. Thereafter, the substrate was submersed into a nickel bath for about 4-10 min, followed again by a water rinse. Example 2

A polypropylene substrate was metallized after following the below described proceduire, which began with a room temperature water rinse. The substrate was then moved to a bath of conditioner (1% polyoxyethylene glycol for about 1 min @ 70° F, and followed with a water rinse. Then the substrate was placed in an alkaline cleaner (Sodium Carbonate % Trisodium Phosphate pH-11) for about 1 min @ 130° F, and rinsed with water. Then, the substrate was dipped in a neutralizer of 30% Hydrochloric Acid, and then put into a catalyst bath with colloidal Palladium/Tin catalyst (30 ppm) for about 2.5 min @ 85° F, and rinsed with water. An acid Accelerator (10% Hydrochloric Acid) was used for aboutl.5 min @ 105-110° F₅ and then rinsed with water, followed by the electroless nickel bath at room temperature. This metallization procedure resulted in a nickel surface adhered to the substrate that was resistant to any delamination, and exhibited excellent tape adhesion per ASTM Test B-3359.

Example 3 A polypropylene substrate was rinsed with water, then subjected to a bath of conditioner of (1% Polyoxyethylene glycol) for about 3 min @ 70" F, then water rinsed. An alkaline cleaner of Sodium Carbonate & Trisodium Phospate at a pH of 1 Hasted about 30 min @ 90°F, then water rinsed, and followed by a neutralizer dip of 30 % Hydrochloric Acid. Then, the substrate was put into a bath of colloidal Pd/Sn Catalyst (Palladium/Tin catalyst = 40ppm) for about 3 min @ 100° F, and water rinsed. Next, the substrate was moved into a bath containing an acid accelerator of 10% Hydrochloric Acid for about 1 min @ 115° F, and water rinsed. To metallize, the substrate was then placed in a bath of electroless nickel for about 1 min @ 130^° F. Excellent adhesion was individually noted after a cadre of strength tests consisting of a chisel and hammer, a scraper and extreme bending.

3. Gas/ Air Monitoring System for Checking Gas Concentrations

In the recent past, conventional gas sensors were made from ceramic, steel, or thin walled tubes that measured the density of the gases that passed through the sensor and would send an electrical signal to the display monitor for understanding volumes only. This invention would use conventional sensor technology, Hall effect sensors, RF transmitter gas/air monitors, SAW device sensors, and other sensors that are well known in the art. The novel application of this embodiment is that the sensor will act as gas concentration sensor and also signal various control valves and heating units to open and close, or to increase heat and air flow or to shut down heat and air flow, depending on the desired concentration of gas and the desired temperature for processing the source sulfur into a gas form. Also the sensor will modulate the rate of gas/air mixture that is evacuated from the treatment chamber by increasing or decreasing air pressure and opening or closing the discharge valves at each exhaust port.

Although an alternative embodiment of the invention, calls for a RF transmitter device to communicate the signal to various valves, there have however been problems inherent with each of those prior art methods and apparatuses, in that most of them included a radio communication device with a central radio receiver powered by normal electrical current or a battery. The present inventor has found that there is potential for a release of sulfur containing gases if a power failure should occur. Battery powered devices as a back up system are prone to failure if and when the battery wears out, rendering the device unreliable, or at worst providing a lack of reliability on an intermittent basis which would be undetected by the operator. In addition, many of the devices which utilize a SAW device and/or piezoelectric pulsing, and the older type of reed switches, are easily corroded and damaged by the sulfur containing gas as it passes through the sensor. Although all of the prior art devices are technically feasible in principle, they also have several serious drawbacks. One of them is the sheer complexity of the device, which makes it susceptible to reliability issues.

Besides the complexity of the prior art systems, there are other issues relating to the reliability, which include the fact that most prior art systems do not accurately monitor the amount of sulfur containing gas being introduced into the treatment chamber, the amount of dry air used as the carrier for the sulfur containing gas, and the temperature that must be maintained for the proper marriage of the sulfur containing gas and the dry air so as not to solidify the sulfur into a solid that is almost impossible to purge from the system. This desired monitor controlled system allows for consistent concentrations of sulfur containing gas so as to consistently affect the substrate material to the degree so as to cause a permanent modification to the surface of the substrate material or ready the material for further modification such as metallization. This feature would dramatically increase the reliability of modification process so as to make this process commercially viable.

And finally, the high cost and complexity of the presently available gas treatment and monitoring systems is so great that many manufacturers resist utilizing them, and are actively looking for alternatives that provided both a high level of reliability combined with cost effectiveness. Therefore, it would be most advantageous to provide a sulfur gas based modification system and gas/air mixture monitoring system which simple, reliable, less inexpensive.

Further, it would also be a great advantage to make the system easier to manage the sulfur containing gas generator and treatment chamber system. By utilizing the full monitoring system, the sulfur containing gas would be much easier to store as it would be generated only on demand as needed, thus dramatically reducing the risk of a gas release into the atmosphere, that even if such a release should occur due to leaks in the system, the amount of gas released would me minimal, and pose very little danger to workers or the environment.

In accordance with the above-noted advantages and desires of the industry, the present invention provides numerous embodiments of a sulfur containing gas generator, a treatment chamber whereby various materials may be modified by adequate exposure to sulfur containing gas, an gas/air monitoring system that could be magnetic-based utilizing at least two magnets, i.e. a sensor magnet attached affixed in a restricted housing, and a pressure sensitive magnet actuator which is mounted within the sensor housing and suspended in place by being attached to a small spring and/or a diaphragm. Once the pressure sensitive magnet moves significantly away from the fixed magnet because of incorrect pressure determined by the mole weight of the gas/air mixture passing into the sensor housing the magnetic field is interrupted and a signal is initiated to a remote solenoid controlled valve that allows the passage of source sulfur such as Anhydroussulfur dioxide to enter into a reaction chamber to be converted into SO3 and channeled into a treatment chamber for the purpose of modifying the surface of the substrate material in the chamber. In another embodiment of the invention, the sensor is made up of at least one thin film material and one solid. As the gas moves horizontally through the tube containing the film, it keeps the film in place. If the pressure changes from its preset specifications, the film moves and the signal, either magnetic, or static, or RF or other type of signal, is triggered, and sent to the solenoid that controls the release of the source sulfur and a solenoid determines if the valve should open or close. A tiny micro-processor may be utilized to interpret the signal.

Regardless of how the signal is created, through the various embodiments discussed herein, the scope of this invention includes a sensor that acts as the control mechanism for the release or closing off of the source sulfur or dry air. Also a thermostat and a hydrostat device is used to communicate with the sensor and determine if the saturation of dry air and the temperature of the gas/air mixture, as well as the source sulfur, which must be kept at a constant temperature of no less than 80 degrees F and no more than 110 degrees F. The sensor will monitor the information received from all these devices and apply the data to automatic devices that will open and close valves, increase or decrease temperature, and increase or decrease dry air saturation.

Additionally this invention includes a method of effecting various surface materials in said treatment chamber for the purpose of modifying said surfaces so as to endow the modified surface with such properties as water wettability, adhesion, barrier, metallization, conductivity, antistatic, encapsulation, hypo allergenic, thromboresistance, reflectivity, material compatibility, hardening, oxidation resistant, antimicrobial, sterility, anti fogging, super cleaning, and wicking hydrophilic properties.

In the preferred embodiment of this invention, the magnets for the sensor may either be permanent magnets or electromagnets as described more fully hereinbelow. The magnets will preferably utilize the Hall effect in order to provide a signal which can be transmitted to a valve system at each port that the sensor/control unit communicates with, as well as a lighted display panel on the face of the sensor. The pressure sensitive magnet mounted along the air/gas stream acts as an actuator, while the other magnet or magnets mounted in very close proximity .5 to 50 mm from each other, and housed in a stainless steel housing threaded on both ends with a stainless steel conduit leading from to the inlet solenoid valve of the source sulfur are signaled to release or close a valve or valves to allow for more gas or dry air to be infused into the reagent generation system. The actuator is in contact with the gas/air mixture by being encased in a stainless steel housing that is connected to a threaded stainless steel conduit pipe on two sides of the sensor housing, one for entrance of the gas/air mixture, and one for an exit port leading to multiple entry ports of the treatment chamber. That gas/air monitor is in communication with a piston which is urged against a spring or an electronic pressure sensor, depending on the embodiment. The position of the piston is a function of the gas/air pressure and is sensed by the Hall effect sensor mounted within a restricted housing in the stream of gas/air as it passes through the sensor in route to the treatment chamber. The sensor is simply switched off when the pressure is higher and on when the required increase of pressure is prescribed by the desired treatment. As the gas or dry air concentrations vary, a sensor will switch on a solenoid that will open and close the control valve of the apparatus that allows for the gas portion of the gas/air mixture to pass into the treatment chamber.

After installation, there will be a small gap of from about 0.01 mm to about 50 mm between the actuator and the sensor which can be set by using a spacer bar or a feeler gauge in the initial installation. An optional gap adjuster may also be included preferably on the sensor side. In the first mechanical embodiment, the pressure sensitive magnet actuator that is encased in the stainless steel housing attached to the inlet portion of the sensor housing that conveys the gas/air mixture into the treatment chamber, along with other sensors that include a permanent magnet attached to a piston, spring or diaphragm that signals a solenoid at various control valves for increasing or decreasing the gas or dry air pressure as needed. A diaphragm is attached to the piston, and the combination of the diaphragm and piston makes the assembly very sensitive to minute changes in molecular weight and pressure with a very low hysteresis, rendering the device very reliable.

The magnetic actuator will adjust with the constant flow of the gas/air mixture as it passes through the stainless steel conduit into the treatment chamber and comes into close proximity to the sensor, including a silicon chip or semi-conductor permanently mounted in the sensor housing that in the preferred embodiment will be made of stainless steel, or glass, or

Teflon, or some other chemically resistant material. The changes in the pressure will induce a voltage, the Hall voltage, thereby producing a voltage that can be used as a signal to indicate the presence or the absence of the magnet.

One specific preferred embodiment of the present invention utilizes a ferrous or rare earth magnet mounted in the sensor housing as either a magnetic disc, or magnetized thin film material to provide a pass/fail or on/off system to provide a exterior monitor dashboard indication. Another preferred embodiment has other features including the use of electromagnets, and/or electronic devices for measuring gas pressure in a gas/air mixture.

Although the invention will be described by way of examples hereinbelow for specific embodiments having certain features, it must also be realized that minor modifications that do not require undo experimentation on the part of the practitioner are covered within the scope and breadth of this invention. Additional advantages and other novel features of the present invention will be set forth in the description that follows and in particular will be apparent to those skilled in the art upon examination or may be learned within the practice of the invention. Therefore, the invention is capable of many other different embodiments and its details are capable of modifications of various aspects which will be obvious to those of ordinary skill in the art all without departing from the spirit of the present invention. Accordingly, the rest of the description will be regarded as illustrative rather than restrictive.

In accordance with the most preferred embodiment of the sensor aspect of the present invention, there is generally disclosed a Hall effect sensor as shown in concept form in FIG. 5 where the actuator 1 includes a magnet 4 having a magnetic field to induce a voltage 5 in a sensor 3. Sensor 3 preferably includes a semi-conductor, or silicon chip 8, generally, but may be any other type of magnetic sensor. Essentially, a gas/air pressure 6 is exerted against magnet 4 which is held in back by spring pressure 7. If the gas/air pressure 6 becomes too slight due to the difference in molecular weight of the various gases such as sulfur trioxide having a molecular weight of 89 vs. air at 29, the spring pressure 7 will push magnet 4 away from Hall effect sensor 3, and the voltage 5 which is generated by magnetic field 2 will decrease to a point where it is noted that the treatment chamber requires more or less gas for the desired concentrations, depending on the desired modification and for operation. In the most basic form of the present invention, there are two components to this part of the invention, an actuator and a sensor. The actuator is mounted in line with the source sulfur or other surfaced modifying gas or liquid, and it opens or closed depending on the sensor stationed inside the sensor housing in line with the conduit leading into the treatment chamber. The sensor is stationary and is mounted permanently on a part of the overall system. It can be used to transmit either a radio frequency signal to the actuator or just a simple electrical impulse signaling the actuator to open or close a solenoid controlled switch that will call for more or less surface modifying gas, as well as another actuator that will operate a similar solenoid controlled switch for increasing or decreasing a dry air supply. The same system could be used to signal the discharge of the treatment chamber once the desired concentration of surface modifying gas as satisfied the desired dwell time for exposure inside the treatment chamber. A sensor could signal the exhaust fan to come on at a programmable time; thereby making the entire operation fully automatic. The actuator gives out a magnetic signal proportional to the gas in air pressure, or temperature, and the sensor picks up that information, turns it into a useful signal, and communicates that information to the sensor at the various solenoids in the system.

In a preferred embodiment, a gas/air pressure monitor and information communicator is disclosed for use in the operation of a surface modification treatment chamber to relay information to the automated system or operator about the internal gas/air pressure by molecular weight or temperature level of each functional valve in the system. The gas/air pressure monitor includes at least one movable magnetic actuator in communication with the fixed magnet indicating the need to operate the desired solenoid valve.

A gas/air pressure transducer is included within the at least one magnetic actuator in a parallel relationship with the convection of the gas/air mixture as it passes into the treatment chamber. The gas/air pressure transducer generates a magnetic flux density proportional to the internal gas in air pressure by transforming an input signal of said gas/air pressure of from about .01 % concentration to about 20% concentration to a detectable output signal for communicating gas/air pressure information to the automated system or operator. At least one stationary field sensor is permanently mounted in a face-to-face relationship with the movable magnetic actuator, where it maintains a physical distance gap between the movable magnetic actuator and the field sensor of from about 1 mm to about 50mm, preferably about 1 to 2 mm apart. The field sensor detects the signal generated by the movable magnetic actuator as the gas/air mixture passes through the system and converts that information into a signal emitted for communicating the information about the gas/air concentration, temperature and pressure. Whenever the gas pressure goes outside of a predetermined concentration level, such as when the sulfur containing gas pressure goes below .01 % or more above the predetermined level, preferably 0.001% to 50% concentrations, a movement outside of the ranges described will create or disrupt the magnetic charge and be inteipreted as a signal to either open or close specific valves. Also, if the thermostat indicates to the main microprocessor that the temperature of the source sulfur falls below 80 or 90 degrees F, the sensor will signal the heating elements to turn on. If the temperature goes above 110 degrees F, the sensor will signal the heating elements to shut down. Similarly, if the heater for the ANHYDROUSSO2 should fall below 700- 900 degrees F., the sensor would signal the heating units to come on, or turn off, depending on the thermostat reading and the desired sulfur containing gas. For example, if the desired modification requires a sulfur containing gas concentration level of 2%, and gas/air mixture is , indicating that it is below the 2% required because perhaps the system is in a dry air purge mode of operation. Once the moisture has been completely removed from the treatment system and all in-feed lines, as indicated by specific instruments that indicate that the air in the system has dropped to -100 dew point; then the gas/air sensor will respond to its programmed information and signal the sensor stationed at the valve to open until the actuator magnet moves into the desired position to the other magnet that will indicate that the gas/air concentration has become sufficiently densified with sulfur containing gas to complete the electromagnetic circuit and thereby signal the stationary sensor at the solenoid valve, to close and the dry air unit will function in a similar way. A similar function will occur when either the same or an additional set of magnets or an additional thermostat system triggers the solenoid sensor to increase or decrease the temperature of the heating unit.

These embodiments will be disclosed in that order, but they do not all utilize the Hall effect sensor, but rather an alternative, commercially available proximity sensor, or field induction sensor. The following embodiments can utilize any of these sensors as long as they are facing one another, are non-chemically sensitive as in the case of a material that can withstand prolonged exposure to sulfuric acid, and are generally in a proximity to one another that the sensing system can be utilized. In the preferred embodiment, the sensor utilizes a magnetic within the actuator utilizes at least one magnet selected from the group consisting of permanent ferromagnets, permanent rare earth supermagnets, electromagnets, rechargeably powered electromagnets, electromagnets powered by a capacitor, electronically controlled electromagnets, combinations of electromagnets for operations and recharging if needed and combinations thereof. Multiple magnets may be necessary if a recharging system is desired.

As is well known, when two magnets come into proximity to one another, a current is generated, and this current can be used to recharge a battery in the actuator, if it is used. Preferably, though, this current would be generated to accumulate a charge in a capacitor which is favored now for most applications. Batteries are disfavored because they will eventually wear out, and reliability is the name of the game for this device.

Embodiments may also include the obvious standard current found in most industrial facilities, or lasers, sound waves (sonar), radar, photoelectric cells, or any other know sensor rather than the Hall effect sensor. The at least one stationary field sensor is selected from the group consisting of a Hall effect sensor, a piezoelectric sensor, an electronic sensor, a proximity sensor, a field effect induction sensor, a strain gauge, a magnetically operated sensor, and combinations thereof. While this invention discloses those sensors, the scope of the invention will not be limited thereto.

I. Gas/ Air Mixture Sensor Embodiment

A mechanical embodiment is constructed in accordance with the present invention placing an actuator within the sensor housing along with a movable magnet that when out of range of the actuator magnet breaks the magnetic circuit and signals another sensor to open or close a valve leading to a source sulfur material. The embodiment includes a mechanical sensing device wherein a small piston is urged against the diaphragm in one direction by a spring, and in the reverse direction by the gas/ air molecular weight and pressure. The piston has a magnet adhered thereto. Generally, so long as the internal pressure from inside sensor housing pushes against the diaphragm at a certain level, the spring will hold the piston and the magnet in a predetermined spatial relationship from the Hall sensor itself to provide a signal, which can be communicated to the vehicle operator. Looking now to FIG. 5, the combination of the actuator and sensor is generally denoted by the numeral 3, including two basic components, i.e. an actuator and a transducer.

The gas/air pressure transducer of the magnetic actuator is a mechanically sensitive device preferably includes an elastic member retaining a piston adhered to a magnet. This elastic member may be a spring-piston combination attached to a diaphragm that is exposed to the gas/ air pressure. This elastic member may be selected from a group consisting of a helical spring, a compression spring, an expansion spring, a rubber plug, an elastomeric material, and an elastic bar of material having a suitable durameter strength to support the diaphragm. A foam rubber piece that is preselected for its compression strength would be the easiest way to provide a set resistance against the diaphragm urged out by the gas/air pressure.

Fig. 7 illustrates an actuator 11 suspended in place by the concentration of the gas/air pressure, sensor 12 picks up the signal being sent regarding the concentration ratio of the air/gas mixture due to the increase or decreased molecular weight of the air pressure. In essence, if there is no signal from the actuator, sensor 12 picks up that fact and can relay a signal of low or high molecular weight in the gas/air pressure to the receiving interrogation system that contains a microprocessor that subsequently signals the solenoid to open or close the inlet valve from the source sulfur container. If, on the other hand, actuator 11 gives out a signal that the gas/air pressure is at the programmed and desired concentration then the actuator 11 gives out a signal that the valve may be closed and no further gas need be introduced into the gas/air reactor. The magnet incorporated into the gas/air pressure transducer of the magnetic actuator needs to only move from about 5 mm to about 15 mm, on the order of 12.7 mm away from the stationary sensor in order to cut off the signal, thereby triggering the transfer of that information to the secondary sensor solenoid or the machine operator. Actually, the commercial tolerances for the production of 2% concentration of sulfur containing gas to air mixture is approximately +/- 0.010 inches for the gap distance. With this tolerance, the maximum difference in low-pressure set points when the gas to air ratio needs to be decreased is approximately +/- 0.4 psi As this tolerance is subject to change depending on the material used as a source sulfur, the present invention may rely on that tolerance for the determination of gap 20 between sensor 12 and actuator 11 when using anhydrous sulfur dioxide as a source sulfur only. The piston travel of about 0.025 inch (0.635 mm) per degree of psi pressure changes in the system. In order to properly calibrate the appropriate gap setting a commonly used predetermined gap of 20 commonly used in a Hall effect sensor, is used as the stalling point, and adjusted by degree depending on the desired concentration.

With combined reference now to FIGS. 5, 7 and 9, it can be seen that a standard Hall effect sensor 12, commonly available from Micronas Semiconductor of Zurich, Switzerland, Lake Shore Cryotronics, Inc., of Westerville, Ohio, and Sypris Corporation of Orlando, Florida, is permanently mounted onto a non-moving portion of the sensor housing assembly in a predetermined distance apart of from about 0.01 mm to about 50 mm, preferably on the order of 1 mm to 10 mm and most preferably of from 1 mm to about 3 mm.

FIG. 7 is a close-up view of the gas/air pressure sensor 11 of the present invention, and includes the description of actuator 11, which is permanently mounted in the sensor housing, and the stationary field sensor 12. The internal gas/air pressure from inside the system is open in the cavity defined by housing 21. Diaphragm 23 is subjected to the air pressure from inside the sensor housing and pushes against piston 26.

Adhered to piston 26 is magnet 27, and both are held in place by end housing 25. A retainer 24 holds end housing in place with its integral very thin end piece 28 to prevent oleum build-up or, grease and grime from contacting the magnet in the spring. Piece 28 is preferably from about 0.5 mm to about 5 mm thick.

Therefore, as one can see, the gas/air pressure from inside the system will be conducted into the sensor housing and push against the diaphragm which in turns pushes against piston 26, and consequently urges magnet 27 into position against the very thin end piece 28. If the gas/air pressure from inside the reactor chamber gets too low, spring 29 will push piston 26 into the cavity created by the housing 21, whereby magnet 27 will be pushed away from very thin end piece 28, thereby reducing the magnetic field density which can be sensed by the field sensor 12. Field sensor 12 is permanently mounted to axle assembly 13, and is held in place by bracket or keyway 32 in Fig. 7 and held in rotational securement by pin 33. Jam nuts 34 hold sensor 12 in place, while connector 31 can be used to relay information, whether electrical or not, to the vehicle operator.

Looking next to FIG. 8, there is shown a slightly different embodiment of the invention of FIG's. 7 and 9, but include a sonic welded plastic construction with the inclusion of a cylinder magnet in between spring 29 mounted within a different configuration of piston 26. As disclosed hereinabove, a permanent magnet is suitable for this task, but any type of magnet may be utilized, when calibrated against the sensor and predetermining the appropriate gap distance between the actuator and the sensor. Air pressure from interior of the gas stream comes down through the top of the actuator and enters into a chamber immediately adjacent to the diaphragm 23. In this embodiment, housing 25 is an integral piece, and does not consist of a separate retainer and end housing.

With reference to FIG. 6, it can be seen that an electronic board 26 acts as the gas/air mixture pressure sensor, and may be a solid state pressure sensor, such as a piezoelectric transducer. The sulfur containing gas/air mixture pressure comes down through housing 21 attached to the gas stream rim via pipe nipple 22. The air pressure comes into compartment 23 within housing 24 and applies pressure to the pressure sensor 26. In this embodiment, pressure sensor 26 is an electronic board, preferably piezoelectric or solid state, and may also include an amplifier to send a signal through wires 29 to the electrical power source 27 which in turn dictates the amount of electricity supplied to the electromagnetic coil 28.

In another embodiment of this invention, there may be at least one electromagnetic coil 28, where a first coil 28 is used to generate a magnetic field to be sensed by actuator 12 across gap 22, and the second coil may be used to recharge a battery if necessary or to provide power to a capacitor. It is well known that the electrical circuit attached to the actuator, when coming in contact with a rotating magnet 28 will generate electricity, to create a back voltage which will either recharge battery 27 or to accumulate charge in a capacitor 27. Similarly to the above-mentioned mechanical embodiment, actuator 12 is permanently attached to the sensor housing, by keyway 32 in Fig. 7, which is held in place by pin 33. Jam nuts 34 hold the actuator in place, and may include an optional magnet 20 in Fig. 5 or 54 in FIG. 6, whether permanent or electromagnet, in order to induce the back voltage as described hereinabove. Again, electrical connector 31 is utilized to communicate information to the solenoid control valves or operator in any of the methods described above. It should be noted that any power supply which is economical, reliable and always ready to supply electricity to the electromagnetic coil 28 is suitable for use in this embodiment.

The actuator 11 is preferably made of a non-corrosive injection molded plastic such as acetyl, but may also be milled from stainless steel, or it may be rubber and Teflon over-molded. The various components need to be isolated from the environment, in order to keep sulfuric acid build-up, grime and dirt off of the working components. Any suitable covering is anticipated by the present inventor.

It may further be noted that in this embodiment, actuator 11 may be a "smart" actuator, or sensor 12 may be a "smart" sensor. An electronics engineer of ordinary skill in the art would be able to determine which is most economically and reliably feasible for this application. In other words, the actuator may be the "smart" end of the gas/air pressure monitor system herein, wherein a varying degree of information can be determined by the amount of the electromagneticity experienced by electromagnetic coil 28. On the other hand, sensor 12, utilizing its semi-conductor or silicon chip, may be the "smart" end of the present gas/air pressure monitor.

II. Apparatus for conversion of liquid SO^_or elemental sulfur to a gaseous form of SO^

The present embodiment of this invention provides an apparatus for generating a reagent of sulfur containing gas or mist in a reagent generator identified in Fig. 5 in its entirety as number 14. The reagent generator has associated therewith means for introducing a source of sulfur, (gas, liquid, or raw sulfur) into the reagent generator, means for introducing a continuous flow of diy air into the reagent generator. The reagent generator also includes means for contacting the sulfur containing gas with a substrate for the purpose of modifying the surface of said substrate material in order to enhance and attribute properties of said substrate with desired increased adhesion, barrier, water wettability, thrombo- resistant catheters that are also anti-microbial, antifogging, antistatic, antimicrobial surface, metallized, and conductive surfaces.

Additionally, the system includes a sensor for adjusting and monitoring sulfur containing gas and regulating temperatures of the storage containers, liquid to gas generator, conveyance lines, and treatment chamber.

In a preferred embodiment, the system for generating the reagent also includes, in conjunction with the reagent generator, a sensor device used to monitor the concentration of a sulfur containing gas or fluid, or raw sulfur, a treatment chamber for the surface treatment of polymer resins, metal components including those made of aluminum and magnesium, polymeric foams of all sorts, medical products which have polymeric resin material on exposed surfaces thereof. Thus, the invention embodies an apparatus for producing a sulfur containing gas on demand, by regulating the amount of source sulfur (ANHYDROUS SO2, SO3, Oleum, raw powdered sulfur) heated in the reagent generator, limiting the sulfur containing gas to less than 20% by volume diktted appropriately with air dried to -100 dew point.

Additionally in a preferred embodiment, the containers are equipped with a thermostat that communicates with the sensor device and external heaters that keep the contents of the storage container and reagent generator at a constant temperature of no less than 100° F and no more than 140° F. A flow meter is positioned between the source sulfur storage container and the reagent generator. Heat tape is wrapped around all of the conduit in order to maintain the source sulfur and sulfur containing gas at a constant temperature of no less than 100° F and no more than 14O⁰ F.

In a preferred embodiment, the reagent generator is made of stainless steel, glass, ceramic, UHMW or Teflon surfaced material. The source sulfur container should be continuously heated with exterior heaters in order to maintain a constant temperature of no less than 100° F and no more than 140° F. The storage container of the source sulfur should be vertically mounted above the reagent generator so as to feed the system by means of gravity thru a flow meter into the reagent generator as demanded by the sensor device. The reagent generator may made of stainless steel, glass, ceramic, UMHW, or Teflon, and may be heated by exterior mounted electric heating devices. It may also be heated by means of heating coils wrapped around the reagent generator, or through out the generator, or generator housing. This may be more efficiently accomplished if the reagent generator is made from a ceramic material encased in a stainless steel vessel. The sulfur containing gas may also be generated by using a microwave, radio frequency, or even a small laser devise.

If anhydrous sulfur dioxide is used as a source sulfur as in the case of Fig. 2, the source sulfur should be contained in a stainless steel pressurized vessel. This assists the movement of the source sulfur into the treatment chamber to be converted into a sulfur trioxide gas.

If a liquid source sulfur is used as in the case of Fig. 5, then the reagent generator should be filled with a ceramic, or glass medium such as Rashig Rings for proper gas distribution. It should also have a thermostat that communicates with the sensor device, a screen at the bottom of the vessel, and a drain for discharging oleum condensate at the bottom.

In another embodiment the reagent generator may be heated through the use of a ratable finned heat transfer device situated above or below the apparatus, heating the dry air feed and causing the dry ari to be drawn into the device at a temperature of no less than 100° F and no more than 140° F. A similar ratable finned heating device could be used at the exit portion of the gas/dry air conveyance line in order to push the heated gas/diy air into the treatment chamber, while maintaining a constant temperature of 100° F and no more than 140° F.

The present embodiment of this invention provides an apparatus for generating a reagent of sulfur containing gas or mist in a reagent generator identified in Fig. 5 in its entirety as number 14. The reagent generator has associated therewith means for introducing a source of sulfur, (gas, liquid, or raw sulfur) into the reagent generator, means for introducing a continuous flow of dry air into the reagent generator. The reagent generator also includes means for contacting the sulfur containing gas with a substrate for the purpose of modifying the surface of said substrate material in order to enhance and attribute properties of said substrate with desired increased adhesion, barrier, water wettability, thrombo- resistance, antifogging, antistatic, antimicrobial surface, metallized; and conductive surfaces.

In a preferred embodiment, the system for generating the reagent also includes, in conjunction with the reagent generator, a sensor device used to monitor the concentration of a sulfur containing gas or fluid, or raw sulfur, a treatment chamber for the surface treatment of polymer resins, metal components including those made of aluminum and magnesium, polymeric foams of all sorts, medical products which have polymeric resin material on exposed surfaces thereof. Thus, the invention embodies an apparatus for producing a sulfur containing gas on demand, by regulating the amount of source sulfur (anhydrous SO2, SO3, Oleum, raw powdered sulfur) heated in the reagent generator, limiting the sulfur containing gas to less than 20% by volume diluted appropriately with air dried to -100 dew point.

Additionally in a preferred embodiment, the containers are equipped with a thermostat that communicates with the sensor device and external heaters that keep the contents of the storage container and reagent generator at a constant temperature of no less than 100° F and no more than 140° F. A flow meter is positioned between the source sulfur storage container and the reagent generator. Heat tape is wrapped around all of the conduit in order to maintain the source sulfur and sulfur containing gas at a constant temperature of no less than 100° F and no more than 140° F.

In a preferred embodiment, the reagent generator is made of stainless steel, glass, ceramic, UHMW or Teflon surfaced material. The source sulfur container should be continuously heated with exterior heaters in order to maintain a constant temperature of no less than 100° F and no more than 140° F. The storage container of the source sulfur should be vertically mounted above the reagent generator so as to feed the system by means of gravity thru a flow meter into the reagent generator as demanded by the sensor device. The reagent generator may made of stainless steel, glass, ceramic, UMHW, or Teflon, and may be heated by exterior mounted electric heating devices. It may also be heated by means of heating coils wrapped around the reagent generator, or through out the generator, or generator housing. This may be more efficiently accomplished if the reagent generator is made from a ceramic material encased in a stainless steel vessel. The sulfur containing gas may also be generated by using a microwave, radio frequency, or even a small laser device.

In another embodiment the reagent generator may be heated through the use of a rotatable finned heat transfer device situated above or below the apparatus, heating the dry air feed and causing the dry air to be drawn into the device at a temperature of no less than 100° F and no more than 140° F. A similar rotatable finned heating device could be used at the exit portion of the gas/diy air conveyance line in order to push the heated gas/dry air into the treatment chamber, while maintaining a constant temperature of 100° F and no more than 140° F.

1. An apparatus for generating a reagent of sulfur trioxide in a gas/air mixture comprising: (a) a reagent generator as described in Fig. 5. or Fig. 2. having associated therewith means for introducing sulfur containing gas such as sulfur trioxide from a source of sulfur containing liquid or a pressurized gas source such as Anhydrous sulfur dioxide, and a carrier selected from the group consisting of non-reactive dry air made from a generator, and means to contact sulfur trioxide and dry air into a treatment chamber containing various materials for variable times and thereby affecting the surface of said materials for the purpose of improved adhesion, metallization, barrier, antistatic, water wettability, thromboresistivity, antimicrobial, and generally amorphous behavior of the surface up to a range of .01 to 100 microns in depth of penetration, depending on the desired surface modification or substrate material use, thus bonding to existing atoms to create a true composite surface.

Or an apparatus for generating a reagent of sulfur trioxide in a gas/air mixture comprising:

(a) a source sulfur material in the preferred embodiment this is a pressurized container filled with Anhydrous sulfur dioxide as in Fig. 2, having associated therewith means for introducing sulfur containing gas such as sulfur trioxide from a source of sulfur containing liquid or a gas such as Anhydrous SuIfIu- dioxide, and a carrier selected from the group consisting of non-reactive diy air made from a generator, and means to contact sulfur trioxide and diy air into a treatment chamber containing various materials for variable times and thereby affecting the surface of said materials for the purpose of improved adhesion, metallization, barrier, antistatic, water wettability, thromboresistivity, antimicrobial, and generally amorphous behavior of the surface up to a range of .01 to 100 microns in depth of penetration, depending on the desired surface modification or substrate material use, thus bonding to existing atoms to create a true composite surface.

(b) gravity feed means a method for removing said reagent phase from a sulfur sourced container into said reagent generator, or liquid to gas converter.

(c) pressure feed means a method for removing said sulfur containing reagent from a pressure vessel while containing said source sulfur inside a series of conduits and reaction chambers; (d) means for feeding and heating said reagent from said reagent phase to a treatment chamber and for treating a surface with said reagent,

(e) means for monitoring sulfur containing gas as it enters a treatment chamber.

(f) means for monitoring and controlling temperature of sulfur containing gas in reagent generator or liquid to gas converter

(g) means for monitoring and controlling temperature of liquid or pressurized gas or solid sulfur source such as elemental sulfur, anhydrous sulfur dioxide, sulfur trioxide, sulfuric acid, oleum, etc.

(h) means for adjusting feed of sulfur containing gas into treatment chamber (i) means for adjusting dilution level of dry air with sulfur containing gas into treatment chamber

Q) means for removing excess oleum condensate from said reagent generator, or liquid to gas converter

(k) means for heating stored source sulfur such as a sulfur containing fluid, gas, or solid or powdered elemental sulfur, (ANHYDROUS SO2) or sulfuric acid

(1) means for heating all lines for conveying source sulfur containing liquid and sulfur containing gas

(m) means of controlling temperature of reagent generator, or liquid to gas converter

(n) means of adjusting flow of dry air into treatment chamber

(o) means of supplying additional oxygen atoms to sulfur containing gas using a catalytic reactor such as a vanadium catalyst

(p) means of diffusion of combined sulfur containing gas and diy air in treatment chamber

(q) means of diverting condensate oleum from treatment chamber

(r) means of measuring flow of source sulfur as a liquid, gas, powder, or solid, into reagent generator or liquid to gas generator

2. The apparatus of Fig. 2 and Fig. 5 of claim 1 including sulfur containing gas sensor means positioned between said reagent generator and said treatment chamber for controlling all flow of sulfur containing gas, diy air, and sulfur containing liquid or raw sulfur from said reagent phase. In the preferred embodiment, a sensor and control unit in one will accomplish the following: (a) means of controlling flow of source sulfur into reagent converter or liquid to gas generator

(b) means of controlling air/gas mixture into treatment chamber

(c) means of controlling air/gas mixture as it is exhausted from treatment chamber

(d) means of controlling temperature of source sulfur container (e) means of controlling temperature of reagent generator or liquid to gas generator monitor displaying exact concentrations of sulfur containing gas flowing into treatment chamber

The apparatus of claim 2, the gas sensor/control unit will adjust the flow and temperature of the sulfur source, liquid to gas generator - apparatus of claim 1 and effectively provide for the source sulfur to sulfur containing gas generator of claim 1 to only make sulfur containing gas on demand so as to prevent excessive waste of acid into the waste stream.

The concentration level of sulfur containing gas/air when at optimum levels will trigger a switch to produce more sulfur containing gas in the reagent generator, or liquid to gas generator, or to slow down or stop the production of sulfur containing gas based on the desired concentrations the temperature of the gas/air mixture when passing thru the gas sensor/control unit along with a signal from the thermostats positioned in the sulfur source container and the reagent generator or liquid to gas generator, will trigger a switch to increase or decrees the temperature of the source sulfur container, reagent generator or liquid to gas generator, and the various line heating devises, for example heat tape

4. The apparatus of claim 2 including means for controlling temperatures for all containers and conveyance lines for the apparatus.

5.. The apparatus described in Fig. 5 of claim 1 wherein said means for introducing said source sulfur into said reagent generator includes means to introduce a source of sulfur trioxide into a separate contact chamber containing rushing rings, a screen, an oleum train, a temperature control mechanism, and a temperature sensing unit.

6. The apparatus described in Fig. 5 of claim 1 includes a thermostat in both the storage container of the sulfur containing liquid or gas or raw sulfur, and a thermostat in the reagent generator or liquid to gas generator, that will automatically send a message to the apparatus of claim 2, so as to send a signal to a heating mechanism to increase the temperature of the reagent generator or liquid to gas generator, keeping the temperatures between 100⁰F and 14O⁰F at all times. 7. The preferred embodiment of the apparatus described as Fig. 2 of claim 1 would be to introduce a source sulfur of anhydrous sulfur dioxide in either a liquid or pressurized gaseous form. The tank should be inverted onto a holding rack if the sulfur source is liquid; but can remain in an upright position if it contains a gas under pressure. The tank of the source sulfur should be kept heated at all times either with heated plates, and/or heat tape that keeps a constant temperature 100° F and 14O⁰F at all times.

8. The source sulfur will be coupled to a control valve solenoid that will open or close depending on the signal sent from the gas/air sensor, but will also have an emergency override hand operated valve to shut off the flow of the source sulfur manually if needed.

The apparatus of claim 2 includes a signal to the apparatus of claim 1 so as to control the flow meter in line of the source sulfur of apparatus of claim 1 so as to properly meter the gravity feed system of conveying the sulfur containing liquid or sulfur containing gas into the reagent generator.

9. In the preferred embodiment of the invention, the apparatus described in Fig. 2 of claim 1 and 2 will include a chamber in which a vanadium catalyst is held and through which the sulfur containing gas is conveyed by the pressure of the compressed gas or liquid and the fan-like fins of the gas/air heater. A gas/air sensor to determine how much sulfur containing gas and heated air are moved through the catalyst container/reactor controls all.

10. The apparatus of claim 2 includes sensors for monitoring and adjusting temperatures and volume of dry air into apparatus of claim 1 and into the treatment chamber

11. The apparatus of includes a treatment chamber whereby a small concentration of a sulfur containing gas of anywhere from .01% to not exceed 20% by volume, is introduced into the chamber a long with dry air down to -100 dew point for a specified residence time (varies with different materials) whereby a product or substrate material has been moved into the treatment chamber and exposed to the sulfur containing gas and dry air

12. The treatment chamber apparatus of claim 11 must be equipped with a scrubber system that will properly neutralize the sulfur containing gases that are exhausted through the system. This is accomplished through the use of ammonia, caustic soda, or calcium solutions. 13. The apparatus of claims 1 and 2 includes a monitoring devise that will adjust concentrations of sulfur containing gas and dry air to less than 20% in the apparatus of claim 11

14. The apparatus of claim 11 includes devises that will trap and condensate excess oleum at the inlets of the apparatus of claim 11 where the sulfur containing gas is introduced and includes by reference all claims of provisional patent identified by Express Mail Label ED 48248953 US filed with the Provisional Patent Office PCT on April 15^th, 2005

15. The apparatus of claim 1 and 2 may include discharging the sulfur containing gas into a fluidized bed container whereby sulfur containing gas at a concentration level of less than 20% and dry air is moved into a treatment chamber in order to treat small parts, powders, and other batch-type components. This treatment is described in greater detail in the Provisional Patent filed with Provisional Patent Office PCT on April 15^th, 2005 by Robin Pointer, identified by Express Mail Label ED 48248953 US and is included by reference in it entirety herein.

16. The apparatus of claim 2 includes a monitoring device that will perform all of the same functions described in monitoring the apparatus of claim 1, 2, and 11 for the apparatus of claim 13 and includes by reference all claims of provisional patent identified by Express Mail Label ED 48248953 US filed by Robin L. Pointer (the author of this same invention) with the Provisional Patent Office PCT on April 15^th, 2005

17. The method of modifying a substrate such as a polymer is accomplished by the natural attraction of SO3 molecules to the Oxygen, Carbon, and Hydrogen molecules of the substrate causing them to bond permanently to one another.

18. The method of claim 1 and 17 includes causing a polar reaction on the surface of the substrate so as to attract a negatively charged molecule to the surface and allow for such modifications to the surface as a metal to SO3 to polymer bond, or an adhesive, such as a rubber- based, solvent-based, or water-based adhesive to S 03 to polymer bond, or a polymer to S 03 to another polymer bond.

19. A treatment chamber for claims 1 and 18 to include:

(a) means for feeding said reagent from said reagent phase to said treatment chamber and for treating a surface of said polymeric resin material with said reagent, (b) means for purging spent reagent from said treatment chamber or fluidized bed treatment chamber with said dry air and sulfur containing gas from said source of sulfur containing gas,

(c) means for removing said oleum phase from said reagent generator,

20. This invention relates to an apparatus described in Fig 1 and 5 and reference in claims 1-19 for the generation of a sulfur containing gas - reagent in a liquid to gas generator, or a gas to gas generator, or a raw sulfur to gas generator, and, more particularly, to a system incorporating such sulfur containing gas into a substrate polymeric, metal, or other carbon based materials.

21. Sulfonation of polymeric resins, that is, the introduction of the — SO.sub.3.sup.- or — SO.sub.3 H functional group onto the surface of polymeric materials is generally known. See, for example, Walles patents No. 2,832 in Fig. 5 or 72 in Fig. 2,696; 2,937,066; 3,592,724; 3,613,957; 3,625,751; 3,629,025; 3,770,706; 3,959,561; 4,220,739; and 4,615,914. Typically, the sulfonation is carried out by using gaseous mixtures of dry air containing from 2 to 8% sulfur trioxide which are then reacted with the polymeric material. Several known systems may be used to produce the sulfur trioxide. For example, oleum (concentrated sulfuric acid containing sulfur trioxide) (H.sub.2 S.sub.3 O. sub.10) has been used as a source of sulfur trioxide gas. This system is described as Fig. 5 and referenced in Claims 1-11. In such a system, dry air is passed through the oleum to facilitate sulfur trioxide stripping of the oleum by mass transfer.

22. Cameron et al, U.S. Pat. No. 4,663,154 (included in its entirety herein by reference) discloses a continuous process for the generation of sulfur trioxide from oleum which introduces oleum feed to a sulfur trioxide desoiption tower to form a gaseous mixture of diy air and sulfur trioxide. Masse et al, U.S. Pat. No. 4,673,554 (included in its entirety herein by reference) teaches a process and apparatus for the generation of sulfur trioxide using microwave energy. A sulfur trioxide-rich oleum feed is subjected to microwave energy for a time sufficient to produce a sulfur trioxide vapor which is then mixed with dry air. In both processes, large amounts of spent acid are produced which must be disposed of or recycled in some manner. Incorporated by reference, see also, Walles U.S. Pat. No. 4,615,914, which teaches conversion of solid pills of polymeric sulfur trioxide into an air-sulfur trioxide gas mixture via microwave energy. Patents 4,663,154 This process leaves no residue.

23. This invention claims that in all claims One use of sulfur trioxide has been the surface treatment of a variety of polymeric resins to chemically modify their surfaces by a sulfonation reaction. For example, such surface sulfonated polymers are useful as substrates for painting and metal coating and are also useful as enclosure members for containing hydrocarbons such as gasoline and the like. Exemplary uses include containers such as gasoline and other fuel tanks, fuel barrels and drums, oleaginous food containers such as bags, tubs and cartons; fibrous materials for use in carpets, clothing and other fabric; plastic substrates and metal-clad plastics such as capacitors, auto parts and the like; and plastic substrates for use in electrostatic spray painting and the like.

24. Likewise, various medical devices are fabricated of or contain a variety of polymeric resins such as polycarbonates, polyurethanes, polysiloxanes and polyolefins. These polymeric resins are used to form housings, tubes, valves, and the like. Many of these medical devices are designed to come into contact with blood or other body fluids, either during removal from the body, during treatment of the fluid, or during the return of the fluid to the body. For example, such devices may include blood filters, blood oxygenerators, dialyzers, tubing and the like. One basic requirement for all such medical devices is that the surfaces which contact the blood or other body fluid of a patient be water wettable.

Wettability is needed to prevent air bubbles from sticking to a surface and ending up in a patient's blood, or causing irregular flow through a tube or the like. Wettability is also important for preventing blood from sticking to or coagulating on a surface. However, most, if not all, of the plastic resins utilized in such medical devices have hydrophobic surface properties. Sulfonation of such surfaces becomes necessary to modify the surface properties of such resins to make those surfaces hydrophilic.

However, because such devices are to be used in medical applications and are designed to come into contact with body fluids, the sulfonation reaction must be controlled carefully. The strength of the sulfur tiϊoxide reagent must be maintained within strict limits. If the strength of the reagent varies during treatment, the surfaces of the devices may be inadequately sulfonated necessitating the discarding of such devices. Additionally, the presence of even trace amounts of water may cause the formation of sulfuric acid which may adhere as small droplets to the surfaces of the plastic to be treated and cause local irregularities. Finally, the generation of sulfur trioxide reagent as well as treatment of the surfaces of these products requires large volumes of the highly dilute sulfur trioxide reagent to be passed through the system. This results in large volumes of acid waste which must be properly disposed of or recycled in some manner.

Accordingly, there remains a need in the art for a system for generating sulfur trioxide in controllable concentrations, and with an absolute minimum of impurities for the surface treatment and sulfonation of polymeric resin materials, particularly those used in medical devices. Further, there remains a need for a system which minimizes the amount of waste acid which requires disposal.

25. What is claimed:

SUMMARY OF THE INVENTION

The present invention meets those needs by providing a system for the production of sulfur containing gas reagent and the use of the sulfur containing gas reagent so generated for the surface treatment of polymeric resin materials. The apparatus of the present invention produces and delivers on demand, a stream of sulfur containing gas such as sulfur trioxide reagent or Anhydrous sulfur dioxide and maintains the reagent stream within narrow, but adjustable concentration limits. Further, the apparatus of the present invention receives and upgrades a waste stream of spent reagent, and discharges only a very small stream of waste to a scrubber system that neutralizes the acid before expending it into the waste stream.

The sulfur trioxide reagent is a reagent of sulfur containing gas and dry air. The dry air specified by this invention as the preferred embodiment is an inert gas.

In either eyent, associated with the reagent generator is a means for introducing a source of trioxide in a liquid vehicle, such as oleum containing 10-90% sulfur trioxide. The introduction means may be a means for introducing a source sulfur trioxide into a separate contact chamber. The reagent generator also has associated with it a means for introducing the carrier to the reagent generator. That may be either a means for introducing a liquid halocarbon or an inert gas.

In the reagent generator, the source sulfur such as anhydrous sulfur dioxide, or sulfur trioxide and carrier are brought into contact by the mixing which may occur by reason of the force of the introduction of these materials, and a sulfur containing gas in carrier reagent is produced. There is a means for removing the reagent to a treatment chamber. There is also a means for removing oleum from the reagent generator for the purpose of regeneration or recycling, or disposal once neutralized.

4. Medical Waste Sanitation and Recyclability

The exothermic reaction exhibited by water contacting the sulfur-containing gas is impressive in the amount of heat that is given off. Consequently, the extreme heat can be used to sterilize fluidized particulate medical waste that has been ground to a particle size of from about 1000 mesh size to about 5" in mean average diameters. In addition, the sulfonation reaction renders the medical waste adhesive toward itself and other materials to be formed into consumable products, such as fibreboards, any plastic building materials, road construction pieces, decking, automotive parts, industrial equipment parts, and the like.

The foregoing description of a preferred embodiment of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Obvious modifications or variations are possible in light of the above teachings with regards to the specific embodiments. The embodiment was chosen and described in order to best illustrate the principles of the invention and its practical applications to thereby enable one of ordinary skill in the ait to best utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. The present invention finds particular utility in the manufacturing sector, and finds a special utility for desired surface treatments in the computer industry, the automotive industry, the garment industry, and the plastic forming industries, among a long list of others. The present invention includes a controlled gaseous surface treatment method, controls therefore, and the resulting articles.

Claims

What is claimed is:

L A surface treatment method for treating substrates, comprising: contacting a substrate with at least a sulfur containing gas; monitoring the concentration of sulfur in the gas stream with a Hall Effect pressure monitor; and neutralizing the substrate with a metallic salt bath.