text:
|Publication number||US2777783 A|
|Publication date||Jan 15, 1957|
|Filing date||Feb 9, 1954|
|Priority date||Feb 9, 1954|
|Also published as||US2844557|
|Publication number||US 2777783 A, US 2777783A, US-A-2777783, US2777783 A, US2777783A|
|Inventors||Pierre R Welch|
|Original Assignee||Pierre R Welch|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (5), Referenced by (47), Classifications (18)|
|External Links: USPTO, USPTO Assignment, Espacenet|
ited States atent Pierre R. Welch, Washington, D. C.
No Drawing. Application February 9, 1954, Serial No. 409,267
25 Claims. (Cl. 117-75) This invention relates to a coating composition, a coatl5 ing and a method of. applying said coating to a surface to be protected from corrosion, employing a dispersion of a fusible resin which is substantially insoluble in known solvents, in admixture with a second resin. More particularly it relates to coatings of the baked-film type comprising a polyhalocarbon resin and a non-polyhalocarbon resin compatible therewith and capable of withstanding fusion temperatures of the polyhalocarbon resin, said coating being built up by applying to a surface to be protected, an initial layer or layers containing from to about 70% of polyhalocarbon resin and applying successive layers of progressively increasing polyhalocarbon resin content to a final layer containing about 70% to 100% polyhalocarbon resin.
In relatively recent years a group of polymers have been developed which have come to be known as polyhalocarbons. These have been made by forming polymers of carbon compounds having an ethylenic linkage wherein the hydrogen has been completely replaced by fluorine, or by fluorine and chlorine, fluorine and bromine, fluorine and iodine or any combination of one or more atoms of fluorine with one or more of the other halogens. The methods of making such polyhalocarbon resins are well known and include straight polymerization of halogen-substituted ethylenes or the like. These have been further modified in certain instances by treating the polymers pyrolytically; and by treatment of polyhalocarbon polymers with fluorinating or other halogenating agents.
Dispersions or suspensoids of polyhalocarbon resins A of substantially colloidal size have been prepared, generally by grinding in water or various organic liquids, as the suspending medium. These have been used to bake-coat various surfaces particularly metal such as steel, steel alloys, aluminum, etc. The suspensions are applied in successive layers, being dried to remove the suspending medium and then pre-baked at a temperature at or above the melting point of the polyhalocarbon resin after each layer is applied. A final bake is given for a longer period of time after the final layer is applied in order to completely fuse the multiple coats applied thereon.
Although the polyhalocarbon polymers have many desirable characteristics such as a high dielectric strength, imperviousness to water, and the best resistance to corrosive materials such as acids, alkalies and the like, of any resin known, they are subject to several disadvantages which has limited their use as coating agents except in certain special instances. They have the disadvantage that the bond formed with the surface to be coated, whether it be metal, ceramic ware, or over another resin, is either non-existent or extremely weak, as witness U. S. Patent 2,562,117. Because they are insoluble in known solvents, and hence must be applied as suspensoids, they have poor covering properties and will not cover irregular surfaces such as rough weld seams, crevices, apertures or pits in the surface, or seams resulting from two pieces of metal meeting at an angle. They will not cover sharp edges and corners, having a tendency to crawl or pull away. If applied in too thick coats, they tend to muderack. Because of the poor bond, films consisting of polyhalocarbon resins are more like an envelope than a true coating having a good bond. Thus if a coating is imperfect, or if it is scored or scratched or otherwise damaged so that the metal is exposed, any corrosive fumes or solutions which come in contact therewith creeps between the film and the coated surface and substantially all of the bond is lost to such an extent that it may float away or can be lifted from the coated surface. Thus, it may be seen utility as coatings is limited to smooth, regular surfaces of articles that can be coated perfectly without a break and which in service is not likely to be damaged to the point of film penetration. Another disadvantage of the polyhalocarbon resins is their high cost compared with other commercially available bake-type coating resins.
Some of the polyhalocarbon resins such as Du Ponts Teflon (polytetrafluoroethylene) require a baking temperature of from about 680 to about 750 F. Others such as polytrifiuoro-chloroethylene (Kelloggs Kel. F)
have the advantage that lower baking temperatures of about 435 to about 485 F. may be used. Pro-baking.
times at these temperatures are about to minutes for the individual coats, with a five hour final-bake.
it is an object of the present invention to produce a coating having the advantages of the polyhalocarbon resins with respect to moisture impermeability, corrosion resistance, highdielectric strength and other desirable properties, while at the same time overcoming the disadvantages hereto encountered.
in one embodiment the invention comprises a coating composition comprising a uniform dispersion of a polyhalocarbon resin and a non-polyhalocarbon resin in a liquid dispersing medium, said polyhalocarbon resin comprising about 5% to about 95% of the total resin content and said non-polyhalocarbon resin being compatible therewith and capable of withstanding the baking temperature required to fuse said polyhalocarbon resin.
In another broad embodiment the invention comprises a coating consisting essentially of a substantially non laminated baked film of not more than 95% of a polyhalocarbon resin uniformly dispersed in a non-polyhalocarbon extender resin, the extender resin being compatible with and capable of withstanding the baking temperature required to fuse said polyhalocarbon resin.
In another embodiment the invention comprises a coating comprising a substantially non-laminated baked film of a polyhalocarbon resin and a non-polyhalocarbon extender resin, the latter resin being compatible with and capable of withstanding the baking temperature required to fuse said polyhalocarbon resin, said film having a concentration of 0% to about of polyhalocarbon resin at its under-surface, with proportions of polyhalocarbon resin progressively increasing from the under-surface to I the upper-surface, said upper-surface comprising about 70l00% of polyhalocarbon resin.
In another embodiment the invention comprises a method of coating a surface including the steps of conditioning said surface to make it susceptible to bond formation with non-polyhalocarbon resin-containing coatings, applying to said conditioned surface a plurality of coats containing not more than of polyhalocarbon resin uniformly dispersed in not less than about 5% of a nonpolyhalocarbon extender resin, said extender resin being compatible with and capable of withstanding the fusion temperature of the polyhalocarbon resin, pre-baking each of said coats before additional coats are applied, and then final-baking the composite coat at a temperature of at least the fusing point of said polyhalocarbon resin.
In a further embodiment the invention comprises a method of coating 21' surface to protect it from corrosion which comprises applying an initial coat to said surface, said coat having 0% to about 70% of a uniformly dispersed polyhalocarbon resin and 100% to about 30% of a non-polyhalocarbon resin compatible with and capable of withstanding the fusion temperature of the polyhalo carbon resin, pro-baking the initial coat at a temperature and for a time insufiicient to cure or polymerize said nonpolyhalocarbon resin, applying a plurality of additional coats of mixtures of said polyhalocarbon and said nonpolyhalocarbon resin, pre-baking each said additional coats at a temperature above the melting point of the polyhalocarbon resin before applying the succeeding coat.
In a further embodiment the invention comprises method of coating a surface to protect it from corrosion which comprises applying an initial coat to said surface, said coat having 0% to about 70% of a uniformly dispersed polyhalocarbon resin and 100% to about 30% of a non-polyhalocarbon resin compatible with and capa' bio of withstanding the fusion temperature of the poly halocarbon resin, pre-baking the initial coat at a temperature and for a time insuificient to cure or polymerize said non-polyhalocarbon resin, applying a plurality of additional coats of mixtures of said polyhalocarbon and said polytrifiuorochloroethylene, polydifiuoro-dichloroethylene,
and similar resins wherein one or both of the chlorine atoms is replaced with another halogen such as bromine or iodine; poly-polyhalocyclobutenes such as pentafluorochlorocyclobutene, tetrafiuorodichlorocyclobutenes and the like; the pyrolysis products of unsaturated fluoroor fiuorochloroethylenes such as trifiuorotrichloroethylene etc. them are disclosed in U. S. Patent 2,531,134.
The polyhalocarbon resins useful in the invention may be those which have been condensed or polymerized to an extent such that they are normally solid and can be dispersed in a liquid medium such as water or various organic suspending agents such as xylene, naphthenes, etc., usually by grinding in the presence of the suspending agent to a particle size of about 0.1 to 3 microns, most of the particles being about 1 micron in size. of forming the suspensions are well known and need not be described in detail since they form, per se, no part of my invention.
The added resins which for convenience I refer to as extender resins, must have the following characteristics:
1. They must be capable of forming a strong bond with the surface to be coated.
"2. They must be capable of withstanding baking temperatures at or above the fusing temperature of the polyhalocarbon resin for the time requisite for carrying out the various baking steps, these temperatures usually ranging from 400 to 750 F. depending upon the type of polyhalocarbon resin used. The thermosetting resins suitable for use in this invention cure at or below such temperatures. Suitable thermoplastic resins fuse at or be low such temperatures.
3. They must be compatible with the polyhalocarbon resin and with the polyhalocarbon resin suspensions. By compatibility it is meant that the extender resin must be soluble in or capable of forming dispersions in liquid Many of these compounds and methods of preparing Methods 1: media in which 5% to 95% of the resin content is dis persed polyhalocarbon resin, said dispersion being stable, and homogeneous, i. e., one which will not gel, fiocculate, settle out or otherwise change phase so as to prevent application of the final suspension to the surface to be coated. it must also be substantially unreactive with the polyhalocarbon resins, at least to the extent that any reaction occurring will not destroy the desired properties of either the added resin or the polyhalocarbon resin, either under the conditions at which the dispersions are made, or during formation of the coating, including the baking steps. 4. The extender resin should be of the kind that has good spreading and flow characteristics in a coating composition, being capable of bridging small apertures, holes, pits, seams, etc. and of retaining such properties after being admixed with the polyhalocarbon resins.
5. if thcrmosetting, they are used in the initial mixtures in the uncured form. If thermoplastic they should preferably be high polymers requiring high baking temperatures.
6. The extender resins should have corrosion resisting properties in and of themselves.
Specific types of extender resins which may be used are as follows:
Group A This group of extender resins are the condensation polymers of epichlorohydrin and bisphenol. These resins, a number of which are produced by the Shell Chemical Corporation and known as Epon resins, are high molecular weight solids. Resins of this type are available commercially from other manufacturers. Modified Epon resins may be used by esterifying with high molecular weight (C18) faty acids; resin acids; polybasic acids such as phthalic, maleic, sebacic, etc., and other modifying agents. Both modified and unmodified Epon resins are useful in the present invention provided they meet the above listed qualifications. Most of these are heat curing resins.
Group B This group comprises the phenolic resins which are condensation products of a phenol or an alkylated phenol, for example, butylphenol, cresol, resorcinol and the like, with aldehydes such as formaldehyde, furfural, etc; modified phenolic resins of which a great many are known may also be used as extender resins according to this invention. Typical modifying agents include rosin, rosin esters, polybasic acid esters, etc. These are generally heat curing resins.
Group C This group of extender resins include the silicone and modified silicones of which the silicone alkyd resins have been found particularly suitable. Among these are the Plaskon resins which include silicone alkyd resins ST 856 and ST 881, made by the Barrett Division of the Allied Chemical and Dye Corporation of Toledo, Ohio; Dow Corning 801 and others, and also General Electrics silicone resins used for coating purposes. These are heat curing.
Group D This group of resins are generically known as the furane resins. They are generally derived from furfural or furfuryl alcohol. They may be formed by resinification of furfuryl alcohol; by reacting formaldehyde with unsaturated aldehyde having a terminal furyl group, such as furylacrolein, furylpentadienal, etc.; or by condensing furfuryl alcohol with phenol or phenolic resins. A large variety of other resins of this group are known and the above are intended to be merely representative. Thesc too are generally thermosetting resins.
Group E This group comprises high polymers of vinyl compounds such as the polymers of vinyl chloride and vinyl acetate 5 among which Bakelite Corporations VYHH, VMCH and VAGH are typical. These also include copolymers of polyvinylalcohol and/ or polyvinylchloride and the like,
with modifying agents including polybasic acids or anhydrides (VMCH) etc. Many of these are thermoplastic resins and those which are particularly useful have high fusion points. Particularly suitable resin is VYNV-l, a very high molecular weight, high vinylchloride-content copolymer of vinylchlon'de and vinyl acetate.
Group F The urea-formaldehyde resins, which are thermosetting resins, may be used, providing they conform to the above specifications, for an extender resin. Among these are various Uformite resins of the Rohm 8: Haas Co. These are basically condensation products of urea and formaldehyde. These may also be modified by condensing urea, formaldehyde and aliphatic alcohol with 4 to 8 or more carbon atoms per molecule.
Group G This group comprises the high molecular weight resins formed by condensing melamine-urea, melamine-formaldehyde, or melamine, formaldehyde and urea. Melamine resins modified by various esterifying compounds such as higher alcohols, for example octyl, may be used.
Any other type of extender resin which is found to conform to the above listed characteristics may also be used. Mixtures of any of the above resins which conform to the aforementioned characteristics may be used providing, however, that they are compatible with each other as well as with the polyhalocarbon resin. The choice of the extender resin depends to a large extent upon the service which is expected of the final coating. While the principal protection is afforded by the polyhalocarbon resins, it is desirable that the extender resin also possess corrosion resisting characteristics since the overall effectiveness of the finished coating for any given service will be improved thereby. Thus, certain types of resins among those listed have good corrosion resisting properties under certain conditions of service but are poor under other conditions, and the choice is made accordingly.
The mixtures of resins comprising the coating compositions of this invention, can be made in one of several ways. Since the polyhalocarbon resins are insoluble they must be reduced to very fine particle size to produce the desired suspension, the particles generally being from 0.1 to 3 microns. in certain instances solid extender resin and polyhalocaroon resin can be mixed in the desired proportions and the mixture milled with the suspending agent. In many instances it is more practical to prepare separate suspensions of polyhalocarbon resin and either suspensions or solutions of the extender resin, and mix them in the desired proportions either before or at the time of use. This is particularly true when multiple coatings of progressively increasing polyhalocarbon resin content are to be applied. In the event the extender resin is soluble in a suspending or dispersing agent which is compatible with the polyhalocarbon resin suspensoid, a solution can be made of the former and this can be mixed with a suspension of the polyhalocarbon resin. The exact choice of methods is dependent upon the circumstances of use but as long as a stable suspension of the mixed resins is produced the method of combining is not important.
In certain instances mixtures of unlike extender resins are used, for example. an Epon with a phenolic or modified phenolic resin. These must be compatible with each other as well as with the polyhalocarbon resin. The proportions of the mixed extender resins must be within the range in which they arecompatible with each other as well as with the poiyhalocarbon resin. These ranges vary with different resins, and since this information is available as to the compatibility of various types of the extender resins, it need not be discussed in detail.
in some instances it is desirable to add a plasticizer for the extender resin, these being well known for the various useful types. The polyhalocarbons may be used in unplasticized form, or may be plasticized by means of polyhalocarbon oils or waxes of lower molecular weight than the polyhalocarbon resins.
The final suspension of polyhalocarbon resin and extender resin may be applied in any known manner. For many types of service, such as coating the inside of pipes, reaction vessels, fume ducts, storage tanks, vats and the like, where only one surface is coated, the suspension may be sprayed or brushed on. In other cases, particularly where all surfaces are to be coated and when the article is small enough, it may be dip-coated. In any event the proportion of total resin to suspending agent will be modilied to give a mixture of suitable consistency for the desired method of application. Thinners or diluents may be added to adjust the consistency, for example, aromatic or aliphatic hydrocarbons, including naphthenes; ketones, alcohols, esters, etc. Usually a relatively concentrated suspension containing, for example, up to 50% of suspended resins may be made up and a thinner added if required to cut down the viscosity. Suitable fillers and pigments may be added in the usual manner as required, either at the time the suspensoids are made, or at a later stage.
in coating an article, the surface is conditioned so that the extender resin will form a strong bond. It may be cleaned in the usual manner to remove dirt, oil, scale and the like which might interfere with a good bond. This may he done by any known method. In some cases the surface may be sandblasted or etched with acid to produce a slightly roughened surface. A coat containing a primer suitable for use with the extender resin, may be applied before applying the first coat of the composition of this invention. While priming coats are not always required, it is well known that improved bonds can be obtained in many instances between the surface to be coated and the coating film, when employing many of the types of resins which may be used as extender resins in this invention.
In some instances it is advantageous to apply one or more (e. g. 1 to 6 or more) coats of a baking resin having good flow-out characteristics, and possessing at least some degree of corrosion resistance in and of itself. This is preferably but not necessarily the extender resin used in the composition with which the ultimate protective coating is to be formed. In order to form a bond between the film thus formed, and the succeeding coats of compositions of this invention, these base coats are preferably pre-baked at a temperature and for a time less than that required to cure them. .A first coat of the composition of this invention is then applied and prebaked at or above the fusion point of the polyhalocarbon resin.
By following this procedure, it has been found that when the first coat of higher polyhalocarbon resin content is applied to the unpolymerized initial layers and this is followed by a pro-bake at the fusion temperature of the polyhalocarbon resin, the extender resins in the two layers copolymerize or cure, which may be accompanied by cross-linkage and a molecular rearrangement resulting in a single homogeneous non-laminated coat, in which the dispersed polyhalocarbon resin particles are entrapped. When succeeding layers of the composition of this invention are applied, entrapped particles adjacent the sur face fuse to particles in the adjoining added layer. In this way a monolithic structure is formed wherein are physically entrapped, particles of polyhalocarbon resin which-are fused together to form a three dimensional network .or lattice, anchored to the base surface through the medium of the extender resin.
If the surface to be coated comprises a cured resin of the non-halocarbon type, the surface may be roughened by sanding or sandblasting and compositions of this invention can be applied in the same manner as for other types of surfaces as herein described.
The first layer of my composition is applied in a relatively thin coat of the order of 1 mil more or less (dry film thickness), the suspending agent or thinner is evaporated under slightly elevated temperatures not above 200 P. if necessary and the article is pre-baked for about -20 minutes. The temperature of the pre-bake of the initial coat is preferably below that at which polymerization or thermosetting of the extender resin occurs, when the film contains less than about polyhalocarbon. If larger proportions of polyhalocarbon are present, the
bake temperature should be at or above the fusion point of the polyhalocarbon.
Although a single initial coat may be applied, I have found it advantageous to apply several coats, say two to six, of the same composition as that of the initial cost. When this is done the pre-bake operation is carried out between coatsas just described for the initial coat.
When'the desired initial coat or coats have been built up in this manner, one or more additional coats comprising up to 95% but preferably 25% to of polyhalocarbon resin and to 30% of extender resin are applied. Each of these coats is dried and pro-baked at a temperature of about the fusion point of the polyhalocarbon resin before application of the succeeding coat. The temperature of pre-baking ranges from 400 to 750 F., depending on the polyhalocarbon resin used. For proportions of polyhalocarbon resin below about 70% a time of about 10-20 minutes is used, but for those containing more than 70% the time is increased, being about 30-40 minutes.
One or more additional coatings containing increasing proportions of extender resin may then be applied, each coat being given a pre-bake of 10-20 minutes at or above the fusing point of the polyhalocarbon resin. As the proportion of polyhalocarbon resin increases, the number of points at the interface between succeeding layers at which the polyhalocarbon resin can fuse together increases tremendously, so that regardless of whether the extender resin bonds well to the cured extender resin, a complete bond is formed by fusionof the polyhalocarbon resin particles to each other. As the number of particles of polyhalocarbon resin increases in successive coatings, the particles tend to fuse together, not only in a vertical direction, that is, between the successive layers, but in a horizontal direction as well, thereby increasing the toughness of the bond between layers.
A further series of coatings, usually one to four in number, containing 70% to of polyhalocarbon resin. and usually of the order of 70% to 85%, is then applied in a like manner. Pro-bake temperatures at or above the melting point of the polyhalocarbon resin are used between coats, and the time is generally 10-20 minutes. Over this is applied from two to six coats, or more if desired, of polyhalocarbon resin containing no extender resin. Each of these coatings is likewise baked out at above the fusion point of the polyhalocarbon resin, the time being increased for the probakes between coats to about 30 to 40 minutes.
After the final coat of polyhalocarbon resin has been applied, the article is given a final-bake for a period of about two to four hours. The final-bake temperature employed depends upon several factors including thickness of the coating, and the fusion temperature of the polyhalocarbon resin employed. If t'rifiuorochloroethylene is used, a final-bake temperature of about 480 to 8 500 F. for two to four hours is employed when using coatings of 8 to 15 mils thickness over relatively light gauge metals.
The composite coating formed by this method not only has all of the advantages of the pure polyhalocarbon resin coating but the disadvantages heretofore discussed have been eliminated. It has been found that the composite coating effectively covers rough weld seams and other irregular surfaces. Crevices, apertures, seams, overlaps, sharp edges and corners are readily covered without crawling or mud-cracking. The initial coats containing the lesser amounts of polyhalocarbon resin formv good bonds and flow out readily, providing the extender resin, the proportions of components and the consistency of the composition is properly selected. By building up the composite coat by multiple application of coats containing progressively increasing amounts of polyhalocarbon resin, a positive bond is obtained, not only to the article itself, but throughout the entire crosssection without lamination or tendency of the final 100% polyhalocarbon resin layer to pull away. Mud-cracking is minimized by use of the modified formulation in the manner described, so that a thick composite coat can be built up with fewer applications, since thicker individual coats can be applied than can be done with the polyhalocarbon resins themselves. It has been found that loss of coating resulting from over-spray is greatly reduced. Likewise mist formation is reduced which results in more uniform films and less rough areas. It has been found that the period for pre-bakes and for the final-bake is substantially reduced. The time for pro-baking and finalbaking will, of course, vary somewhat depending upon the polyhalocarbon resin and the extender resin employed, but these are generally less than for pure polyhalocarbon resin films of comparable thickness.
The tendency toward creeping and lifting at any point of break, for which the polyhalocarbon resins are notorious, is substantially eliminated. Composite polyhalocarbon resin films of this invention have been applied, scored and kept in a hot solution of chlorine dioxide for more than four months with no tendency toward creepage or lifting of the film. Similar results have been obtained with hot nitric acid solutions, fuming nitric acid, acetic acid, mineral acids, hot and cold alkali solutions, and other corrosive materials. Similarly scored panels coated with polyhalocarbon resin alone fail under similar condi tions in a matter of a few hours.
My explanation for the improved results is as follows: When the initial coat of extender resin with a small amount of polyhalocarbon resin is applied, the minute particles of the polyhalocarbon resin are evenly and widely scattered through the extender resin and do not substantially interfere with the strong bond between the sur face and the extender resin. As I visualize it, a three-dimensional lattice or network of polyhalocarbon resin is built up which is physically anchored in a continuous phase of extender resin, becoming more complex and tougher as the proportions of the polyhalocarbon resin increases in succeeding layers. First, there are scattered individual particles, some of which have fused to other particles at the interface with the next coat. These in turn fuse to other particles and groups of particles in the next layer. This continues until, in the outer layer of low extender content, the network is so complex that the pure polyhalocarbon resin has an infinite number of points to which it can fuse and be held so strongly that it cannot be detached.
The coatings may be applied to any type of surface to be coated such as iron, steel, ferrous alloys, aluminum. copper, and the like as well as stone and ceramic ware and, as previously indicated, to plastic ware provided it will withstand the baking temperature. They are used to protect pipes, valves, reaction vessels, fume ducts, fittings, wire, etc, from the corrosive action of solutions or gases, acids, alkalies, salts and the like such as may be en- 9 countered in the chemical and paper industries, petroleum refineries, oil fields, etc., wherein the temperature conditions are not in themselves destructive of the resins.
The compatibility of the extender resins and the polyhalocarbon resin can often be determined by visual inspection of mixtures of dispersions 'and/ or solutions of the two types of resin in the proportions it is desired to use them, and containing any pigments or fillers that are to be added. The mixtures may be sprayed on a panel and then inspected for separation; For films which have passed these tests, a further useful test for determining compatibility is to form test panels by applying one or more andpreferably at least two to four coats of the mixtures and baking the panel between each coat at a temperature above the melting point of the polyhalocarbon resin. Do not apply the final 100% polyhalocarbon resin coating. The panels thus prepared are baked out and are partially immersed in a solution containing 10 to 15 milligrams of chlorine dioxide per liter and heated to a temperature of about 150 F. for a period of 8 to 12 hours. if the mixtures are incompatible the panel will develop a readily discernible mottled appearance showing that separation has occurred. If the mixtures are compatible the appearance of the coating is uniform in appearance, although it may undergo a change in color. It is important that the panel be completely coated and the coating be free of breaks or pin holes, since if there is bare metal exposed to the solution, the resulting corrosion products may give a false impression.
In the specification and claims the values given for proportions of extender resin and polyhalocarbon resin, are based upon total resin content of composition, exclusive of pigments, fillers and/or suspending agents, solvents, thinners, etc. which may also he used. The values therefore represent the ratios between one type of resin and the other. Unless otherwise indicated these ratios or percentages are by weight.
The following comprise examples of typical formulations which I have found useful in compounding the corn positions of this invention.
Polyhalocarbon resin dispersion Dispersion 13-1 (1 gallon) (M. w. Kellogg Co., Kel-F dispersion) Trifluorochloroethylene lbs 4 Particle size microns 0.1-3 Xylene lbs 6 Baking temperature F. 460-500 Dispersion D-2 (1 gallon) (Du Pont Co., Teflon dispersion) Polytetrafiuoroethylene lbs 5.2 Particle size, average microns 1 Water lbs 6.0 Baking temperature F.. 680750 Extender resin dispersion E-l Epon resins: Pounds Epon 1007 4.0 Chrome oxide 1.2 Acetone 0.8 Butyl Cellosolve 4.0
E-2 Phenolic resins plus vinyl-aldehyde resin: Pounds Phenolic R108 (phenol formaldehyde) 5.0 Butvar (poly vinylalcohol-butyraldehyde) 0.5 Chromeoxide 1.2 Toluene 0.4 Acetone 0.4 Phosphoric acid 0.25
E-3 Silicone resins: Pounds Silicone 856 4 Xylene 2 Chrome oxide 1.2 Acetone 2 E-4 Furane resins: Pounds Furane #1 5 Acetone 3 Chrome oxide 1.2 H2804 in alcohol (optional) 0.12
Mixed extender resins E-S Vinyl plus urea formaldehyde resins: Pounds VAGH (vinylchloride-acetate resin) 1.5 Uformite (urea-butanol-formaldehyde) 2.0 Diisobutyl ketone 4.0 Acetone 1.0 Chrome oxide 1.2
VMCH, a vinyl chloride-acetate-maleic anhydride resin or VYNV, a vinylchloride-acetate resin may be used in the above formulation in the proportions given for VAGH.
E 6 Epon plus phenolic plus vinyl-aldehyde resins:
Epon 1007 2.5 Phenolic R108 2.5 Butvar 0.25 Butyl Cellosolve 2.5 Chrome oxide 1.2
Acetone 0.4 H3PO4 0.15
E-7 Epon plus phenolic resins: Pounds Epon 1007 2.5 Phenolic P97 2.5 Chrome oxide 1.2. Butyl Cellosolve 2.5 Acetone 0.8
E-8 Epon plus silicone resins: Pounds Silicone 856 2.5 Epon 1007 2.5 Xylene 2.0 Acetone 1.5 Chrome oxide 1.2 E-9 Silicone plus phenolic resins: Pounds Silicone 856 2.5 Phenolic P97 2.5 Xylene 2.5
Chrome oxide 1.2 E-10 Furane plus phenolic resins: Pounds Furane #1 2.5 Phenolic P97 2.5 Xylene 2.5 Acetone 0.8 Chrome oxide 1.2 15-11 Furane plus silicone resins: Pounds Furane #1 2.5 Silicone 856 2.5 Xylene 2.5 Acetone 0.8 Chrome oxide 1.2 E-12 Furane plus epon resins: Pounds Furane #1 2.5 Epon 1007 2.5 Acetone 1.5 Butyl Cellosolve 1.5 Chrome oxide 1.2 15-13 V-inyl plus urea formaldehyde plus epon resins: Pounds VAGH 1.5 Uformite 210 1.0 Epon 1007 1.0 Diisobutyl ketone 3.0 Acetone 1.0 Butyl Cellosolve 1.0 Chrome oxide 1.2
In the above formula a like amount of phenolic P97 or Silicone 856 "or Furane #1 may be sub- 'stituted for Uformite 210.
E-l4 Urea formaldehyde plus epon resins: Pounds Uforrnite F210 2.0 Epon 1007 0.8 Butyl Cellosolve 0.8 Acetone 5.0 Chrome oxide 1.0
The following compositions were made up using each of the above formulations to which was added dispersion D-l in an amount to yield the designated proportion by weight of the polyhalocarbon resin to extender resin based on the total resin content.
Clean test panels of mild steel were successively spraycoated with two 1 mil coats each of the above compositions, beginning with composition No. 1 (dry film basis). The panels werev dried for ten minutes at 150 F., and then pre-baked at 485 F. for ten minutes before application of the next coat. Four 1 mil coats of dispersion D-l were then applied, the panel being dried and then pre-baked at 485 F. for -40 minutes between each application. After application of a final coating of dispersion D-1 the panel was given a final-bake at 485 F. for two hours. The resulting composite coat was l418 'rnils thick.
The resulting panels were then given one or two score marks with a knife point until :the metal was exposed. The panels were exposed to a chlorine dioxide solution (10-15 mg.ClO2/liter) at 150 F. and then examined at 12 hour intervals to ascertain whether the film lifted at the point of scoring. Although the metal exposed by scoring was corroded, there was no evidence of film failure or corrosion at any other point. Even immediately adjacent the score mark the film retained its bond.
Panels coated with dispersion D-l without any extender resin failed completely in less than 12 hours under similar conditions, the solution creeping between the film and the metal surface in both directions from the score mark so that film could be lifted off. The underlying metal was badly corroded.
Similar tests were made using fuming nitric acid solution at 70 F. The scored polyhalocarbon panels failed ina similar manner but the panels coated according to this invention remained intact, bonded to the metal, and showed no signs of creeping or failure of bond.
Many of the compositions have been tested in like manner in alkaline solutions at various temperatures with similar good results.
Similar formulations were made using dispersion D-2, tetrafluoroethyiene, and a dispersion of silicone resin 856 in xylene and acetone. Panels were coated as indicated for dispersion D-l. The pre-bake temperature was 700 F. for 8-10 minutes and the final-bake was 750 F. for five minutes. The coating showed the same excellent bonding, lack of creeping, and protection against corrosion observed for those made with dispersion D-l and the various extender resins.
Thev formulations presented are for purposes of illustration and intended to guide those skilled in the art. It is clear that an infinite variation in formulations can be made.
A more specific illustration of a coating designed to withstand the most severe corrosion conditions, such as contact with fumes and solutions of chlorine dioxide at 12 relatively high temperatures as is sometimes encountered in the paper industries, for example, is as follows:
A dispersion was made by mixing dispersion D1 with formulation E-7 in proportions to produce a composition wherein the ratio of polyhalocarbon to extender resins was 65:35. Eight successive coatings of approximately 1 mil thickness were sprayed on mild steel and stainless steel, the panels being dried and pro-baked for 15 to 20 minutes at 480 F. between coats. A second dispersion was made by blending the same two formulations wherein the ratio of the polyhalocarbon resin to the extender resin was :15. Two coats of this dispersion were then applied to the panels with drying and pro-baking between co'ats as previously described. Six coats of approximately 1 mil thickness of dispersion D-l were then successively applied with drying followed by pro-baking at 480 F. for a period of 30 to 40 minutes between coats. After addition of the final coat the panels were baked for two hours at 485 F. The coatings thus produced are extremely tough and could be scored with a knife point only by application of strong pressure. bond to the panels was strong. The coating could be chipped from the panels with a chisel but could not be pulled away. The upper layers of polyhalocarbon resin were strongly bonded to the under layers with no evidence that they could be removed except by chipping. This is in contrast to metal panels coated with the pure polyhalocarbon resin. Such films can readily be penetrated with a knife point and when this is done there is immediate evidence of lifting of the film from the panel at the point of the cut. if a small part of the pure polyhalocarbon film applied directly to the metal is detached, the entire coating can be removed with a slight pull. Of course, such polyhalocarbon resin films will resist corrosion indefinitely and will protect the metal providing there is no break or pin holes in the film. But when a break occurs the very slight bond between the film and the metal is rapidly destroyed and the metal is attacked over a large area.
The following is an example of a film that may be used where the corrosion resisting requirements are somewhat less severe, such as may be encountered with salt solutions, dilute alkali or dilute acid at normal room temperature or below. Steel panels were cleaned and six successive layers of formulation E-7 were applied. The panels were dried and pre-baked at a temperature of about 350 F. for 10 to 20 minutes between each coating. A mixture of dispersion D1 and E-7 was then made wherein the ratio of polyhalocarbon resin to extender resin was about 30:70. Four coats of this mixture were applied successively with drying followed by pro-baking at 485 F. for about 15 minutes. This was carried out between coatings. A second mixture comprising about 70% of the polyhalocarbon resin and 30% of the extender resin was made and six coats of this were applied employing a similar schedule of drying and pro-baking between coatings. This composition was then baked out for two hours at 485 F. The resulting coat was tough and adherent. Because of lesser requirements for corrosion resistance, it was found that this coat would withstand service in contact with acetic acid at about 100 F. for periods of four months without evidence of failure. Some panels were made in a like manner wherein the 100% polyhalocarbon resin final coatings were applied. These were, of course, even more effective. Compositions of this character, that is, those containing relatively high proportions of extender resin in the composite coat are far less expensive than compositions containing higher proportions of the polyhalocarbon resin and are therefore chosen where the service conditions permit.
Another type of coating which is particularly advantageous where severe corrosion problems are encountered and where improved electrical resistance and increased strength is desired is as follows:
Dispersion D-1 and formulation E-7 were mixed in The proportions to produce a composition having the ratio of polyhalocarbon resin to extender resin of 60:40. Two successive coats of approxin'iately 1 mil thickness each were sprayed on a sandblasted steel panel, the panel being dried and pre-baked in the manner described in the foregoing example. A single coat of 100% polyhalocarbon resin was then applied, dried and baked for thirty minutes at 480 F. Two additional coats of the 60:40 mixture were then applied, another coat of the 100% polyhalocarbon resin was then applied and two additional coats of the mixed resin applied thereafter. The coating was built up until a total of 12 coats had been applied in this alternating fashion, and then three coats consisting of polyhalocarbon resin were applied. Thus the third, fifth, seventh, ninth, eleventh and thirteenth to sixteenth coats inclusive, consisted of the 100% polyhalocarbon resin. The mixed resin coatings were prebaked between applications for 15 minutes at 480 F. The polyhalocarbon coats were pre-baked 30 to 40 minutes each. The final coating was baked for two hours at about 480 F. The panel was tested by exposure to the chlorine dioxide solution and to fuming nitric acid as previously described. The composite coat possessed greater physical strength, better corrosion resistance and greater electrical resistance than any of the coatings tested. It appears that the intermediate coats of the polyhalocarbon resin were responsible for these improvements.
The composite coatings of this invention can advantageously be applied to fabrics which will withstand the baking temperatures required. These include glass-fabric, asbestos-fabric, metal-fabric and the like. Coatings similar to those described can be advantageously applied to one side of the fabric to build up a composite coat of from to mils thickness more or less and the other side of the fabric can be coated with an adhesive whereby the resulting composition can be applied to surfaces such as the interior of tanks to protect them from corrosion. When'using a dispersion such as D1 on glass-fabric, attempts to coat one side of the fabric have failed. The particles of polyhalocarbon resin in the dispersion penetrate entirely through the fabric. This is because of the poor covering qualities of the dispersions previously referred to. As a consequence the adhesive cannot be applied.
However, by applying one or more initial coats of extender resin having good covering qualities, or of mixtures such as extender resin and polyhalocarbon resin, penetration of the fabric is negligible and does not interfere with the application of the adhesive to the opposite side. The composite coat can then be built up in the manner previously described. The usual pre-bake and final-bake is, of course, used.
I claim as my invention:
1. An article coated with a tightly adhering monolithic coating made up of a plurality of tightly adherent baked layers comprising a fused polyhalocarbon resin and a non-polyhalocarbon extender resin compatible with and capable of withstanding the fusion temperature of the polyhalocarbon resin, the layer adhering directly to the article containing 0% to about 70% by weight of polyhalocarbon resin, and at least one layer superimposed thereon containing about to about 70% by weight of fused polyhalocarbon resin, the surface layer of said coating comprising about 70% to 100% fused polyhalocarbon, said percentages being based on the total resin content of the coating, the proportion of polyhalocarbon resin in the superimposed layers increasing and the proportion of extender resin decreasing from the initial layer to the final layer.
2. An article coated with a tightly adhering monolithic coating made up of a plurality of tightly adherent baked layers comprising a fused polytrifiuorochloroethylene resin and a non-polyhalocarbon extender resin compatible with and capable of withstanding the fusion temperature of the polyhalocarbon resin, the layer adhering directly to the article containing from 0% to about by weight of said polytrifluorochloroethylene resin, and at least one layer superimposed thereon containing about 25% to about 70% by weight of fused polytrifluorochloroethylene resin, the surface layer of said coating comprising about 70% to 100% of said fused polytrifluorochloroethylene resin, said percentages being based on the total'resin content of the coating, the proportion of polytrifluorochloroethylene resin in the superimposed layers increasing and the proportion of extender resin decreasing from the initial layers to the final layers.
3. The article of claim 1 wherein the polyhalocarbon resin is polytetrafiuoroethylene.
4. The article of claim 1 wherein the extender resin is a thermosetting resin.
5. The article of claim 3 wherein the extender resin is a thermosetting silicone resin.
6. The article of claim 2 wherein the extender resin is a thermosetting resin.
7. The article of claim 2 wherein the extender resin is a condensation product of epichlorohydrin and bisphenol.
8. The article of claim 2 wherein the extender resin is a condensation product of a phenol with an aldehyde.
9. The article of claim 2 wherein the extender resin is a mixture of condensation polymers of epichlorohydrin and bisphenol and condensation products of phenol and an aldehyde.
10. A method of coating a surface to protect it from corrosion which comprises applying an initial coat to said surface of a composition comprising a liquid dispersing medium containing from 0% to about 25% of a polyhalocarbon resin and 100% to about of a non-polyhalocarbon extender resin compatible with and capable of withstanding the fusion temperature of the polyhalo' carbon resin, drying said coat, prebaking the resultant film ata temperature above the drying temperature, applying a plurality of additional coats of a composition comprising a liquid suspension medium, an extender resin compatible with and capable of withstanding the fusion temperature of the polyhalocarbon resin, and at least about 25 of a polyhalocarbon resin, drying and then prebaking each of said additional coats at a temperature of at least the fusion point of the polyhalocarbon resin but below that at which the extender resin is deleteriously affected, the resin content of the final coat being from about 70% to 100% of polyhalocarbon resin and about 30% to 0% of extender resin, at least one of the intermediate coats containing from about 25% to about 70% of polyhalocarbon resin; all percentages being by weight of the total resin content of the composition; and then curing the composite coating at a temperature of at least the fusion point of the polyhalocarbon resin for a time sufficient to fuse said polyhalocarbon resin but below that at which the extender resin is deleteriously affected.
11. A method of coating a surface to protect it from corrosion which comprises applying an initial coat to said surface of a composition comprising a liquid dispersing medium containing from about 5% to about 70% of a polyhalocarbon resin, and about to about 30% of a non-polyhalocarbon extender resin compatible with and capable of withstanding the fusion temperature of the polyhalocarbon resin, drying said coat, prebaking the resultant film at a temperature of at least the fusion point of the polyhalocarbon resin but below that at which the extender resin is deleteriously affected, applying a pinrality of intermediate coats of said composition in which the proportion of polyhalocarbon resin amounts to at least 25 of the total resin content thereof, drying and prebaking each of said intermediate coats at a temperature of at least the fusion point of the polyhalocarbon resin but below that at which the extender resin is deleteriously afiected, applying at least one overlying coat of said composition the polyhalccarbon resin content of which is from about 70% to about of polyhalocarbon resin, at
least one of the intermediatescoats containing from about" perature of at least the melting point of the polyhalocarbon resin for a time sufiicient to fuse said polyhalocarbon resin but below that at which the extender resin is deleteriously alfected.
l2. The processof claim 10 wherein the.-polyhalocarhon-resin is a normally solid polymer oftrifiuorochloroethylene.
13. The process of claim 11 wherein the polyhalocarbon resin is a normally solid polymer of trifluorochloro' ethylene.
14. The process of claim 10 whereindhenon-polyhalocarbon resin-is a thermal-setting-resin andthe initial coat is prebaked at a temperature and for a time insuflicient to curesaid resin.
15. The process of claim 10 wherein the'non-polyhalocarbon resin is a high molecular weight thermoplastic resin.
16. The process of claim 11 wherein thenon-polyhalocarbon resin is a thermoplastic resin.
17. The process of. claim 11 wherein the non-polyhalocarbon resin is a thermalsetting resin.v
18. The process of claim 10 wherein the proportion of polyhalocarbon resin increases progressively from the initial layer to the uppermost layer and wherein at least one final coat contains about 95% to 100% of polyhalocarbon resin.
19. The process of claim 11 wherein the proportion of polyhalocarbon resin increases progressively from the initial layer to the uppermost layer and wherein at least one final coat contains about 95% to 100% of polyhalocarbon resin.
'20. The process of claim 16 wherein the extender resin comprises a phen-olictype resin.
21. The process of claim 17 wherein the extender resin comprises a phenolic type resin.
22. A method of coating a surface to protect it'from corrosion which comprises applying an initial coat to said surface of a composition comprising a liquid dispersing medium containing from about to about 70% of a 16 polytrifiuorochloroethylene resin and about 95% to about 30% of *a .nonpo1yhalocarbon extender resin compatible with and capable of withstanding the fusion temperature of the polytrifluorochloroethylene resin, drying said coat, prebaking it at a temperature of at least-the fusion point of the polytrifiuorochloroethylene resin butbelow that at which the extender resin is deleteriously affected, applying an intermediate coat of said composition in which the proportion of polytrifiuorochloroethylene resin amounts to about 25% to about of thetotal-resin content thereof, drying and then prebaking at a temperature of at least the fusion point of the polytrifiuorochloroethylene resin but below that at which the extender resin is 'deleteriously affected, applying an additional coat of the composition containing from about 70% to about 100% by weight of polytrifluorochloroethylene resin, drying said additional coat and then prebaking at a temperature of at least the fusion point of the polytrifiuorochloro ethylene resin but below that at which the extender resin is deleteriously affected; said percentages being by weight of the total resin content of the composition; and then curing the composite coat at a temperature of at least the fusion point of the polytrifiuorochloroethylene resin for a time sufficient to fuse said polytrifluorochloroethylene resin but below that at which the extender resin is deleteriously affected.
23. The process of claim 22 wherein the extender resin comprises a thermal-setting phenolic type resin.
24. The process of claim 22 wherein the extender resin comprises thermal-setting condensation polymers of epichlorhydrin and bisphenol.
25. The process of claim 22 wherein the final coating contains from about to about of polytrifiuorochloroethylene.
References Cited in the file ofthis patent UNITED STATES PATENTS Vincent et al. Oct. 4, 1955
|Cited Patent||Filing date||Publication date||Applicant||Title|
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|US2686738 *||Dec 29, 1949||Aug 17, 1954||Kellogg M W Co||Dispersion of polymeric trifluorochloroethylene, method of preparing said dispersion, and method of coating a base therewith|
|US2719833 *||Apr 9, 1951||Oct 4, 1955||British Dielectric Res Ltd||Methods of processing polytetrafluorethylene and products therefrom|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US2844557 *||Oct 22, 1956||Jul 22, 1958||Pierre R Welch||Polyhalocarbon coating composition|
|US2904528 *||Dec 30, 1954||Sep 15, 1959||Minnesota Mining & Mfg||Composition comprising epoxide resin and trifluorochloroolefin copolymer and process of crosslinking same|
|US2907612 *||May 9, 1956||Oct 6, 1959||Charles S White||Barrier and bonding material for low friction surface|
|US2930677 *||Jan 31, 1955||Mar 29, 1960||Kaiser Aluminium Chem Corp||Method of handling liquors containing scale forming compounds|
|US2944917 *||Dec 8, 1955||Jul 12, 1960||Marc Gregoire||Method of coating a metal base with polytetrafluoroethylene|
|US2976257 *||Jan 24, 1958||Mar 21, 1961||Re-etfspersible dispersion of polytetra-|
|US3008601 *||Dec 8, 1955||Nov 14, 1961||Collette Gregoire||Polytetrafluoroethylene coated cooking utensils|
|US3010536 *||May 20, 1957||Nov 28, 1961||Commissariat Energie Atomique||Porous membranes and methods of manufacturing these membranes|
|US3011219 *||Apr 14, 1958||Dec 5, 1961||American Metal Prod||Method of forming a ball joint utilizing a fluorocarbon layer|
|US3023189 *||Dec 30, 1954||Feb 27, 1962||Minnesota Mining & Mfg||Trifulorochloroethylene polymerepoxy resin mixture|
|US3033623 *||Sep 2, 1958||May 8, 1962||John B Thomson||Fluorocarbon sleeve bearing|
|US3037893 *||Aug 3, 1959||Jun 5, 1962||Charles S White||Bearing element comprising fibrous fluorocarbon|
|US3048148 *||Mar 18, 1959||Aug 7, 1962||Sirianni Salvatore P||Ball point pen|
|US3074901 *||Dec 24, 1956||Jan 22, 1963||Du Pont||Composition comprising polytetrafluoroethylene particles admixed with polystyrene containing dimethyl phthalate|
|US3081644 *||Oct 5, 1959||Mar 19, 1963||Gemmer Mfg Co||Close tolerance anti-friction component assembly|
|US3082485 *||Apr 7, 1958||Mar 26, 1963||American Metal Prod||Elements having low friction material compacted on teh face thereof|
|US3087905 *||May 3, 1960||Apr 30, 1963||American Cyanamid Co||Durable fluorochemical-melamine resin textile finish|
|US3111426 *||Aug 4, 1961||Nov 19, 1963||Pennsalt Chemicals Corp||Application of polyvinylidene fluoride coatings|
|US3178321 *||May 29, 1961||Apr 13, 1965||Armco Steel Corp||Coating compositions for metals and method of heat treating metals|
|US3185179 *||May 5, 1961||May 25, 1965||Pharmaseal Lab||Disposable valve|
|US3218255 *||Jan 9, 1961||Nov 16, 1965||Glacier Co Ltd||Bearing composition containing polytetrafluoroethylene and ammonium manganese orthophosphate|
|US3223676 *||Jul 7, 1960||Dec 14, 1965||Johns Manville||Process for producing a molded gasket from polytetrafluoroethylene and a butadiene-acrylonitrile elastomer|
|US3231460 *||Mar 21, 1963||Jan 25, 1966||Raybestos Manhattan Inc||Sheet material|
|US3234128 *||Jan 9, 1961||Feb 8, 1966||Glacier Co Ltd||Plain bearings|
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|US3293203 *||Mar 26, 1962||Dec 20, 1966||Acheson Ind Inc||Thermosettable resin compositions and method for forming low friction surface coatings|
|US3304221 *||Apr 18, 1963||Feb 14, 1967||Dixon Corp||Polytetrafluoroethylene laminates and method of making the same|
|US3330884 *||Jun 19, 1964||Jul 11, 1967||Du Pont||Polymeric ultraviolet light-absorbers prepared by condensation of hydroxybenzophenones and carbonyl compounds|
|US3342667 *||Aug 23, 1963||Sep 19, 1967||Woodmont Products Inc||Dry fluorocarbon bearing material|
|US3344064 *||Jul 19, 1963||Sep 26, 1967||Du Pont||Fluorocarbon-modified polyurethane elastomeric compositions|
|US3502498 *||Aug 18, 1967||Mar 24, 1970||Dilectrix Corp||Metal-fluorocarbon adherent composite structures and process for preparing same|
|US3510455 *||Jan 16, 1967||May 5, 1970||Minnesota Mining & Mfg||Fluorinated amido resin prepolymers and products|
|US3798052 *||Jun 28, 1972||Mar 19, 1974||Sueddeutsche Kalkstickstoff||Polyvinylidene fluoride coating for metals|
|US3859120 *||Feb 28, 1973||Jan 7, 1975||Du Pont||Exterior siding of an aluminum substrate coated with a durable low gloss clear coating composition containing fluorocarbon polymer particles|
|US3934748 *||Aug 19, 1974||Jan 27, 1976||Racz Nick S||Cookware containers|
|US4074007 *||Mar 23, 1977||Feb 14, 1978||Hoechst Aktiengesellschaft||Coating composition|
|US4131711 *||May 8, 1978||Dec 26, 1978||Imperial Chemical Industries Limited||Coating process using dispersions of tetrafluoroethylene polymers and polyethersulphones and article|
|US4143204 *||Jan 24, 1974||Mar 6, 1979||E. I. Du Pont De Nemours And Company||Articles coated with fluorocarbon resins|
|US4169117 *||Nov 26, 1975||Sep 25, 1979||E. I. Du Pont De Nemours And Company||Aromatic polysulfone resin solution having perfluorocarbon polymer particles dispersed therein|
|US4180609 *||Feb 27, 1978||Dec 25, 1979||E. I. Du Pont De Nemours And Company||Article coated with fluoropolymer finish with improved scratch resistance|
|US4218362 *||Nov 17, 1977||Aug 19, 1980||Fuji Photo Film Co., Ltd.||Powder marking agent and marking method|
|US4237177 *||Nov 3, 1978||Dec 2, 1980||General Signal Corporation||Corrosion-resistant coated articles|
|US4347268 *||Aug 18, 1980||Aug 31, 1982||David Hudson, Inc.||Novel fluoroelastomer film compositions containing vinyl copolymers and method for the preparation thereof|
|US4347277 *||Aug 14, 1980||Aug 31, 1982||General Signal Corporation||Corrosion resistant coated articles which include an intermediate coating layer of a thermosetting polymer and non-siliceous filler|
|US4396744 *||Jul 26, 1982||Aug 2, 1983||David Hudson, Inc.||Novel fluoroelastomer film compositions containing vinyl copolymers|
|EP0219928A2 *||Jul 22, 1986||Apr 29, 1987||The Standard Oil Company||Epoxy fluorocarbon coating composition and process to make same|
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|U.S. Classification||428/422, 525/104, 525/109, 427/379, 525/165, 525/144, 29/898.12, 525/121, 525/160, 525/199, 427/375, 525/57|
|International Classification||C09D127/12, B05D7/26|
|Cooperative Classification||B05D7/26, C09D127/12|
|European Classification||B05D7/26, C09D127/12|

domain: chemistry


text:
Copper, a potential casualty of further dollar strength
Head of Commodity Strategy
Summary: Copper's impressive recovery from the March low, has paused on a combination of slowing momentum and signs of weakening fundamentals. The steep uptrend from the March low is currently being challenged with additional dollar strength the potential trigger for a deeper correction
What is our trading focus?
HG Copper - COPPERUSDEC20
COPA:xlon - WisdomTree Copper ETC (UCITS eligible)
Copper’s impressive recovery and momentum from the March low, has started to slow with the price struggling to extend its impressive gains beyond 3.10/lb on High Grade copper (COPPERUSDEC20). The rally seen across industrial metals, not least copper, in recent months has been driven by a post-pandemic recovery in Chinese demand supported by credit and scattered supply mine disruptions.
While the fundamental outlook remains supportive, the lack of fresh upward catalysts may now pose a short-term challenge to this poster-child of momentum. Something that has helped attract a substantial amount of speculative long positions from trend following strategies that many hedge funds and CTA’s adhere to.
Copper is currently challenging the uptrend from the March low, but in our opinion the price would have to break below $2.95/lb before it kicks off a correction/consolidation phase. Just like gold’s current correction has more to do with dollar strength than changed fundamentals, an extended period of dollar strength could be the trigger that for now could pause this classic momentum trade.
A key source of inspiration behind the rally has been the continued slump in stocks at warehouses monitored by the three major futures exchanges in New York, London and Shanghai. Not least the drop to a 14-year low in stocks monitored by the London Metal Exchange has supported the market. The tightness that it signaled drove the spot premium over the three-month benchmark to an 18-month high at $40/t last week before easing lower to $28/t yesterday.
During the past week stock levels have stabilized on LME while levels monitored by the SHFE has seen a steady rise since late June. This development combined with softer prices in Shanghai may potentially have shut the arbitrage window for profitably importing copper into China.
The reason why copper risks a non-fundamental supported correction can be found in the weekly Commitments of Traders report. The mention strong momentum has continued to attract an ever increasing net-long position held by speculators such as hedge funds and CTA. Given that many of these positions are purely based on technical analysis a break below $2.95/lb could trigger a correction.
Quarterly Outlook Q2 2022
Quarterly Outlook Q2 2022: The End Game has arrived
- Shocks from covid and the war in Ukraine have forced the global financial and political world to change, but what will the end game be?
Productivity and innovation have never been more importantAs the world economy hits physical limits and central banks tighten their belts, could equities be facing a 10-15% downside?
The great EUR recovery and the difficulty of trading itIf the terrible fog of war hopefully lifts soon, the conditions are promising for the euro to reprice significantly higher.
Tight commodity markets – turbocharged by war and sanctionsWith supply already tight, commodities keep powering on. But will it last for yet another quarter?
Between a rock and a hard placeGeopolitical concerns will add upward price pressures and fears of slower growth, while volatility will remain elevated.
The Great ErosionInflation is everywhere and central banks try to combat it. But will they get it under control in time?
Australian investing: Six considerations amid triple Rs: rising rates, record inflation and likely recessionWhile global financial markets are struggling in an uncertain world, the commodity-heavy Australian ASX index is poised to keep a positive momentum.
Cybersecurity – the rush to catch up with realityWith the invasion of Ukraine, governments and private companies are rushing to reinforce their cyber defenses.

domain: economics


Standard Dance Shoes for Boys
Welcome to our exceptional collection of Very Fine Standard Dance Shoes for Boys. Every dancer knows the essential role shoes play in enhancing performance, and we aim to provide just that with our thoughtfully designed and crafted range.
Our Very Fine Dance Shoes for Boys collection comes with a meticulously designed suede sole. This premium material helps to offer a reliable grip on the dance floor, ensuring your child can perform complex footwork and quick turns effortlessly. These shoes are designed to slide smoothly yet provide ample control, aiding in both speed and stability, indispensable elements in standard ballroom dancing.
Comfort doesn’t take a backseat in our shoes. Each pair comes equipped with a cushioned insole, expertly designed to absorb shocks and minimize impact. The additional comfort allows dancers to concentrate on their moves without worrying about potential foot discomfort or fatigue. Regardless of the dance style, Very Fine Boy’s Dance Shoes promise superior comfort, aiding in the ease of performance and boosting overall confidence.
We understand that dance is a passion that needs nurturing from a young age, and the right equipment makes a world of difference. With every pair from our Boy’s Standard Dance Shoes collection, we aim to offer young dancers the opportunity to experience comfort, functionality, and style simultaneously. Choose our shoes for a seamless dance journey.
Step into the world of standard dance with confidence. Our shoes are the perfect partners to glide, spin, and twirl with ease and comfort on the dance floor.


State-Wide Cannabis Revenue Is Down Due to Inflation
By TheNevadaGlobeStaff, October 6, 2022 2:22 pm
LAS VEGAS, Nev. (702 Times, NV Globe) -Statewide cannabis revenue is down, according to the state’s cannabis board.
People appear to be opting to spend their money elsewhere when petrol, food, and other necessities become more expensive.
According to a recent Cannabis Compliance Board report, marijuana taxable sales increased by 4% in fiscal year 2022 compared to fiscal year 2021.
According to the statement, the sector did suffer a drop in sales in the first half of the year, and cannabis firms are not immune to the impacts of inflation as customers shift their spending patterns.
The state education fund received over $150 million in income this year.
Copyright 2022 702 Times, NV Globe. All rights reserved.
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text:
so fuckin beast
I remember playing this game 2 years ago, friends competing who can get the farthest. A really good game. But you just need achievements, cause once you finish everything, it gets kinda boring
Great art, great concept, and i luv the upgrade menu!
great game ;D
A very good game!
I love this game. It's so fun and there are so many different things you can upgrade on your van, which is just great.
However, I will say, that I like the sequel better. :)

domain: game


text:
Tuesday, January 1, 2008
I neglected to finish posting the rest of the mini scrapbook made from Creative Cafe tags last year, so I will share it now whether you want to see it or not! LOL
I got the letters on the front using Queen & Co. Alphabettys - I love them, but sadly found out they're now all sold out at the place I bought them before :(
The shaped rhinestone bling just does not photograph well - it's so pretty and sparkly in real life! The KL over on the little tag are Maddie's friend's initials.
The brown tag is stamped with chalk ink and embellished with snowflake grosgrain ribbon, a Martha Stewart felt snowflake, chipboard, patterned paper from the Costco big pack by Wild Asparagus, some chipboard, glitter and more bling. Notice on the next picture the close up of the little acrylic charm that says "Frosty". We put a picture of the girls making their SNOWMAN on this page - it was sooooo dang cute!!
Next is a page with more felt snowflakes. This had the girls outside in the snow - talking. Because they have to talk about their private things outside - and look cute just in case any boys happen to go by - they will be seen.....yeah, right...not on my watch! I chase those boys away! LOL
Then the other page is a pocket for the Friendship tag.
I don't think I can load more than 5 pics at a time, so I have to set up another entry in a moment. Thanks for taking time to peek! I hope your New Year's Day has been wonderful!!

domain: artistic


text:
|2 schools re-open today |
By RACHAEL ESPIENT Monday, March 10 2014
PRINCES Town East Secondary and Williamsville Secondary schools will re-open today for the first time in weeks. This was announced on the weekend in a release from the Ministry of Education.
The Princes Town East has had a haphazard school term as teachers refused to attend school due to fears of mould spores and other microbials at the school compound. To date, teachers walked off the school’s premises three times after students and teachers reported feeling ill.
On January 13, teachers walked off the school’s compound stating that the building is unsafe due to suspicion of mould and other microbials growing in the air-conditioning vents. Teachers refused to teach on grounds that they were working in an unsafe environment, and would not return until the mould was removed.
On February 3, the school was reopened upon reassurance from the Ministry of Education that the area was cleaned and safe for students and teachers to return. That day four students of the school were rushed to the health facility after complaining about feeling dizzy, and having severe skin and eye irritations. These students were treated and discharged on the same day.
Teachers also complained of feeling dizzy but did not seek any medical treatment.
Results from air quality testing done by the Caribbean Industrial Research Institute CARIRI on Princes Town East reveal that there was no mould, and the air in the school was safe for the students and staff. Classes resumed on February 18; however, when school called that Monday, students and staff complained of itching.
Teachers chose not to attend school until repairs were done. Officials from the Ministry stated that they suspected that the agent causing the illness came from a specific area in the school and that part was isolated.
On Friday there was a meeting at the Princes Town East Secondary School, between Ministry of Education Officials, Trinidad and Tobago Unified Teachers’ Association (TTUTA) representatives and the Education Facilities Company Limited (EFCL).

domain: news


It took me the longest while to think of this, but one reason for his anger at Dr. Mayfield was that his original "victim" (the other doctor) was still alive, but "hanging in the balance." So for a change, Columbo wasn't just angry about something the other character HAD DONE, but about something else, that could be PREVENTED. So in a way, it was almost a one-of-a-kind scene for THAT reason too. Someone mentioned very mild cases of anger. In "Blueprint For Murder", Columbo goes from apologizing to Markham for those reporters (typical of him) to getting just a little mad when he finds out that Markham HIMSELF called the reporters (which is, of course, less typical).


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After reading the scenario, we know that the Woodson Foundation is a large nonprofit social service agency, which is teaming up with the public school system is Washington, D.C., to improve student outcomes. According to the textbook, I identify the stage of Woodson Foundation is in the norming stage, which is having close relationship develop and the group demonstrates cohesiveness. Team cohesion refers to the mutual attraction attractiveness of the team members, members of the team cohesion, and team members, team cohesion is not only a necessary condition for the existence of maintaining the team, but the team has the potential to play a very important role. If a team loses cohesion, it is impossible to complete the task entrusted to the organization itself will lose the conditions exist. A social psychologist has said that what the cohesion do is to enable members of the group to stay together in groups, which is a kind of interpersonal attraction, attraction it had some similarities mechanics, such as a personal in the play "meteor ball", the meteor ball turn around with center.
The primary question that the Woodson Foundation is facing is to figure out the conflict in the development team. Because each group has its own interests, and in some cases these are directly opposed to one another. The second problem is that how to distribute the job for different candidates. In the scenario, the development team is consisted of three individuals- HR representatives from the Woodson Foundation, the schools, and the NCPIE. However, they have some different opinions for controlling, I mean that parents want to know more about their kids in school, the school thinks that they should have the most power. In my point of view, I agree with what Victoria Adams said. She mentioned that the schools and the foundation need to have larger roles then the parents and communities, like Duane said, the class sizes get bigger, and scores and graduation rates go down,

domain: sociology


Occasional rain tapering to a few showers late. High 44F. Winds W at 5 to 10 mph. Chance of rain 60%..
Partly cloudy. Low 31F. Winds SSW at 5 to 10 mph.
Updated: January 24, 2020 @ 8:02 am
By GREGORY KATZ, Associated Press; Tribune News Service
By The Associated Press
By Max Foster, CNN
Get up-to-the-minute news sent straight to your device.


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Repositioning Unconscious Bias
12th November 2013
As I reflect on the number of enquiries received at Marshall ACM for programmes to deliver unconscious bias training and support, I can see that people have a basic desire to be fair to others. Of course, there are also those people who consider unconscious bias to be a cop out and that bias is bias and, as managers and employees, we should be more confrontational in an attempt to reduce and remove its impact from the workplace.
Yet whether conscious or unconscious, I’m firmly in the camp that says bias is not something that should be tolerated. And with this in mind, I appreciate that it can be tricky for HR and training managers to position training and development programmes to help employees recognise and address bias.
Too often employees can feel told off’ and challenged by such programmes and it’s possible to create an atmosphere of alienation among those who are signed up for courses. Here the company is considered to be completing a box ticking exercise that seeks to absolve them of any responsibility should a member of the workforce display biased behaviour.
Perhaps, then, we need to try to re-define its concept?
It’s easy to position training as a process to help avoid employee litigation and ensure compliance. Yet if this is the rationale behind it, it’s little surprise that employees don’t feel engaged and on board with the underlying objectives of a programme. Maybe then we need to reposition our own thinking about training and put employees back at the centre of things. So, in the case of unconscious bias training, what’s in it for the employee?
Well, for starters, if it’s good for the business which you’ve already said it is then a profitable, high performing and focused organisation is good for the employee. Not only does this let you hire the best talent thereby creating a good working culture and environment but you can also help to evolve and sustain a meritocratic culture that contributes to a genuine reputation for being a good place to work and somewhere that employees want to stay. And surely that benefits everyone.

domain: psychology


Fuel hose is the exact size of the molded fuel line that goes from the fuel filter to the pump on 1Z, AHU & ALH motors. Plus, on BEW & BRM motors this size line goes from the fuel filter to the hard lines on the cylinder head.
OEM hoses are molded to a certain shape, this hose is just straight but is flexible enough to be close to OEM routing. 1 meter is enough to replace the lines between the filter and the pump on most models.
Sold in 3.5' lengths, however if you order more than one we will ship one, continuous piece - up to 17.5'. Using this hose rather than the OEM hose can save a ton of money.
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US: Macy's extends Destination Maternity apparel deal
Department store retailer Macy's Inc is extending its exclusive maternity wear deal with Destination Maternity in a move that will see its brands carried in over 615 Macy's locations by the end of February 2011.
The leased department relationship currently operates in 113 Macy's locations in the US, which sell the Motherhood Maternity and A Pea in the Pod brands.
"We are very pleased that A Pea in the Pod and Motherhood Maternity will be the exclusive brands offered in our maternity collection," said Jeff Gennette, Macy's chief merchandising officer.
"With this expansion, we are able to offer expectant moms across the country merchandise that is fresh and fashionable."
The lines for moms-to-be sell at price points ranging from $7.50 to over $200.
The following is a general roundup of US apparel and shoe chains' November 2010 sales results. The list will be updated as new results become available....
US dress maker Taylor Dress has entered talks to distribute its collections in China. ...
Madonna and Iconix Brand Group has entered into its first international partnership with Hudson's Bay Company (HBC or the 'Bay') to manufacture and distribute its junior brand of 'Material Girl'....
Department store chain Macy's will build a major new fulfillment near Martinsburg in Berkeley County, West Virginia, to support continued growth of its online business....
- Under Armour Lighthouse will disrupt production
- Will new Vietnam wage hinder competitiveness?
- How TAL Apparel is staying ahead of the game
- Ethiopia violence undermines sourcing strategies
- Where next for retailers in a saturated market?
- Marks & Spencer top for modern slavery reporting
- Bangladesh garment workers rally for higher wages
- MAS Holdings shares commitment to sustainability
- H&M CEO named sustainability leader
- Gap to shutter all UK Banana Republic stores
- Africa-Med strategic sourcing review – comparing East Africa, North Africa and Turkey
- REPORT BUNDLE: Africa-Med, Southeast Asia and Central America strategic sourcing pack
- Southeast Asia strategic sourcing review – a focus on Cambodia, Vietnam and Myanmar
- Apparel (GLOBAL) - Industry Report
- Global Sports and Fitness Wear Market 2016-2020

domain: geography


How To Free Download and Guide To Install Magic Black Piano Faded App on Windows PC 32/64bi & macOS
Here is the proper guide to free download Magic Black Piano Faded software for PC as an alternative to EXE/DMG. Also, the installation method with the best Android engine like Bluestacks mobile emulator or Nox Android APK App player. These engines are highly recommended to run the APK of Magic Black Piano Faded on Windows 10, 8, 7 (all edition), computers, desktops, laptops, and Mac.
- Download any emulator below. The official landing pages are below.
- Best free mobile emulators are here: BlueStacks.com and BigNox.com
- Download & open any on above and use Google ID as an Android device.
- Play Store contains Magic Black Piano Faded app. So easily took it
- Tap via the mouse on the install point below the Magic Black Piano Faded logo to start download
Q & A Of Magic Black Piano Faded With Features & Using Method
Have you ever dreamed of becoming a professional pianist like Beethoven, Chopin or Mozart? Have you ever dreamed of playing classical songs like Little Star, Canon or Jingle Bells on a piano?
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HOW TO PLAY:
Magic Piano: Music Tiles is very easy to play. The rule is simple. Tap on the piano black tiles continuously to play the music. Watch out for the white tiles and never miss any piano black tiles to complete every song!
*** Awesome graphics and sound effect. You will feel like you are playing a real luxurious classical piano made with expensive mahogany.
*** High quality piano music soundtracks. Features a large collection of piano songs from Mozart to Beethoven
*** Hit songs including: Little Star(Mozart), Jingle Bells, Canon, Fur Elise(Beethoven)
*** Simple to play, difficult to master. Tapping only the black tiles in some high speed songs can be a real challenge!
*** Smooth gaming experience. We tried our best to turn your mobile phone into a magic piano with real sound effects.
*** Regular Updates! We are frequently updating Magic Piano: Music Tiles to fix any bugs and come up with new awesome features that every player will love.
*** After you play the whole piano song, you can enter the ENDLESS mode directly by tap the fast play button.
*** You can save your favorite piano songs. Easy to access your favorite songs and songs recently played.
What’s New Added On The Latest Edition Of Magic Black Piano Faded Software
Disclaimer for Magic Black Piano Faded App
Ksniffer.org is the not the owner of the Magic Black Piano Faded software. Also, Ksniffer.org is not doing an affiliation for it. The following properties such as the app, logo, trademarks & SS all are the owner is its honorable developer.
Even, we are not directly uploading Magic Black Piano Faded apps on our website. Every install will be started from the official software store of the Magic Black Piano Faded app.


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Healing Minds…Encouraging Recovery…and Restoring Hope!
The mission of Century Health is to provide quality mental health and substance abuse treatment and education to residents of Hancock County and nearby communities. Century Health strives to provide effective, evidence-based services which promote recovery and coordinates with other community resources to enhance the health and well-being of our clients dealing with Addiction and Mental Health Disorders.
Who We Work With:
Century Health Provides:
Century Health is committed to providing a range of behavioral medicine to address individual concerns. We are dedicated to our goal of Healing Minds…Encouraging Recovery…and Restoring Hope!
Century Health, Inc.
1918 N. Main Street
Findlay, Ohio 45840
For more information visit our website at: Century Health


This article is 2 years old. It was published on June 8, 2020.
ST. LOUIS, Mo. – Mayor Lyda Krewson today signed Executive Order 67 to lift the citywide curfew that was enacted last Tuesday. This is effective immediately.
Mayor Krewson thanks all City residents and businesses that chose to respect the curfew over these past several nights, and the individuals who continue to exercise their rights to protest non- violently.
Mayor Krewson will have her regularly scheduled 2 p.m. digital briefing on Facebook today. You can watch here: https://www.facebook.com/LydaSTL/
Office of the Mayor
Law, Safety, and Justice


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Out the Window by Freewaves
Freewaves commissioned and presented 60 two minute artists’ videos and 75 youth-made videos exploring specific locales throughout Los Angeles County. The videos were presented on 4,400 screens on 2,200 L.A. Metro buses with approximately 1,200,000 boardings per day. Each artist’s work was shown 16 times over the 16 daily hours of Metro Bus operation. In addition to the Metro bus screenings, videos were also presented on www.out-the-window.org, cross-referenced by locale, keywords and artist. Freewaves also presented screenings at Inner City Arts, Occidental College, KAOS Café and Self-Help Graphics. Freewaves coordinated a free panel discussion about the cultural effects of technology as part of the L.A. Public Library’s Aloud series.
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domain: library


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You must see the Coloseum, Rome, Italy
According to the chronicles, the inauguration of the Coloseum was marked by a hundred-day free game. More than 9000 animals and nobody knows how many men were murdered in the arena in the time of the ‘games’. I always wondered, why and when one part of the building fell. Well it’s the Southern side and it was damaged by a great earthquake in the middle of the 9th century.
Also, during the late Middle Ages a lot from the material of the Coloseum was used for other buildings that were in construction at that time. Even Saint Peter’s Basilica has got some pieces of it built in, so attractions in Rome are almost literally linked. ;)
Coloseum is amazing. Much larger than we imagined, its arches of 4 levels totally dominate the center of Rome. It’s even more amazing from the inside as we stood in the arena and looked around, we could almost see the 50,000 spectators shouting at us. It was actually a little creepy as well, knowing about the unimaginable massacres that took place right where we were standing.
There are always long lines for tickets in front of the Coloseum, but if you just walk down a little bit, to the Palatine Hills, you can buy the same ticket (the ticket includes the Coloseum, the Palatine Hills and the Forum) immediately, no queues there. You can also join a tour for a couple of extra Euros and get a lot of great, professional information about the history of the building.
Things about Rome you may be interested in
1. Aug 25, 2004 You must see the Coloseum (Rome) ( 5)
2. Aug 28, 2005 St. Peter Basilica in Rome is a must see (Rome)
3. Aug 29, 2005 Favorite attraction in Rome (Rome)
Start from beginning | 1 - 3 Journal overview
Read about Rome in our travel-guide
Attractions in RomeSt. Peter Basilica in Rome is a must see
Recommended Rome Guide
And if one wants to experience a nightlife that is something out of the ordinary, then it’s high time to pay a visit to the Centri Sociali which is known as a collective melting pot of different cultural and night chilling activities such as film/art exhibitions, concerts and live music trips. Lastly, nightlife in Rome is not complete without the taste of ‘cornetto’ with a soothing cup of cappuccino on your way home. During summer, a number of clubs, pubs and bars close to give way to outdoor summer events to hype the nightlife of the capital. During these times, more people will prefer to spend time outdoors. Nevertheless, whenever you... Read more »
Recent reviews for Rome
Favorite attraction in Rome - Apr 30, 2009, by cipristb
The Pantheon was built for the first time in the year 27 AD bt Agrippa, but suffered a serious fire in year 80 so that was rebuilt in the same form by the Emperor Hadrian in 127. In the year 609 the Pantheon came into the custody of the... Read more »
Few words about the International Cuisine - Mar 26, 2008, by lindamura
European Cuisine is one of the finest Italian cuisine as the national cuisine known today has evolved through centuries of social and political change. Its roots can be traced back to the 4th century BC. Ingredients and dishes vary by... Read more »
Reise nach Ravensburg - Jun 11, 2009, by mary
Wir standen um 6.30 Uhr auf, aber frühstückten nicht. Caro und Flavia ließen wir schlafen. Nur Fillipo war schon wach und half uns unsere Sachen ins Auto zu bringen. Wir bedankten uns bei ihm und verabschiedeten uns und... Read more »
On the way to Rome - Jun 13, 2009, by MadSuh
I got home from Romania at around 11:30pm, threw my dirty clothes in the laundry bin and immediately packed for my next trip... Rome. Work is work, but enough of that... I had enough of my regular life and just had to escape for a short... Read more »
Top things to see in Rome - Jun 13, 2009, by MadSuh
I really think that walking around in the city is probably the most relaxing. Wherever you look, you see history and not just any history. We started out at the Pantheon and I was probably again the most amazed about this building that was... Read more »
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An altercation at a Golden State Warriors practice this week made headlines, as Draymond Green punched Jordan Poole in the face. There were plenty of questions that remained after reports of the fight started circulating, and then, TMZ published the video of the incident, which showed that the two went chest-to-chest at a practice, Poole shoved Green, and Green responded by throwing a right hook.
Thanks to TMZ, we now know what is alleged to have happened — and what was said — between the two in the lead-up to the punch being thrown. While Steve Kerr and Steph Curry both stressed that Poole’s attitude has not caused headaches during camp, TMZ claims that Poole’s expected big-money contract extension led to him carrying himself “in a cocky manner” in the days leading up to the altercation. This rubbed a number of teammates, including the extension-eligible Green, the wrong way.
When practice rolled around on Wednesday, TMZ reports that Green called Poole a “b*tch” on several occasions due to Poole calling fouls while the team scrimmaged. Then, they got into it over some chirping between the pair.
Things escalated when Poole allegedly said, “You know what it is, Draymond.” — seemingly bragging over the contract situation — and Draymond got in Poole’s face, allegedly saying, “No I don’t know, what is it?”
The Warriors have already launched an investigation to figure out the source of the video leaking to TMZ.


Minot AFB airmen to host Minot teen on ‘Hero for a Day Tour’
MINOT AIR FORCE BASE – Airmen from the 69th Bomb Squadron, 23rd Bomb Squadron and the 54th Helicopter Squadron will host a “Hero for the Day Tour” today to honor Isabella Lynn Knupp of Minot who is suffering from cancer.
Isabella, 14, is the daughter of retired Tech. Sgt. Damon and Ashley Knupp. Damon Knupp was an aero space propulsion specialist in the Air Force.
The event will include a walk-thru of a B-52 and a helicopter as well as an opportunity to take the controls of a B-52 on a flight simulator.
The event will conclude with a visit to the 5th Bomb Wing commander’s office for a meet and greet with staff.
Isabella is currently suffering from osteosarcoma, a bone cancer. Osteosarcoma is found in about 400 young people in the United States each year, most often during the growth spurt of the teen years.
According to St. Jude Children’s Research Hospital, the month of September was designated Childhood Cancer Awareness Month to bring awareness to childhood cancer, which remains the leading cause of death by disease for children under the age of 14.


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The popularity of online casinos has increased in recent years, thanks in large part to the convenience and accessibility they provide. Crypto casinos, that operate using digital currencies such as Bitcoin, Ethereum, and Litecoin are now a popular choice for gamblers on the internet. These platforms provide users with a thrilling gaming experience, while simultaneously offering an unprecedented amount of discretion and security. In this report, we will explore the pleasure and freedom that comes with playing safe online crypto casinos. We will also provide a financial disclaimer at the end.
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Rapid Transactions and Low Fees
Cryptocurrencies offer the benefit of quick transactions with minimal fees. They use a decentralized platform to handle transactions, meaning that payments are processed faster as traditional methods of banking. This allows for instant deposits and withdrawals, enabling players to have a great gaming experience without having the stress of waiting for long transaction processing time.
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Additionally, the transaction costs associated with cryptocurrencies are typically less than conventional banking techniques. This means that players can keep more of their winnings and reduce the cost of transaction costs, which makes the overall gaming experience more rewarding financially and enjoyable.
Provably Fair Gaming
One of the most important characteristics that sets crypto casinos apart from traditional online casinos is the implementation of proven fair gaming systems. These systems use cryptographic algorithms to ensure that the outcome of each game is honest and transparent. This eliminates the risk of fraud or manipulation by the casino or other players, giving confidence and trust to the experience of gaming.
Provably fair gaming gives players the opportunity to verify the fairness of every game themselves, fostering the feeling of control and engagement that is not available in traditional online casinos. Transparency not only increases the enjoyment of playing but also helps to create a feeling of autonomy and freedom associated with crypto casinos.
Crypto casinos permit gamblers to gamble online without the limitations of geographic boundaries. Since cryptocurrencies aren’t dependent on any particular location or region, gamblers from around the world can play online with a level playing field. This international accessibility encourages a diverse and vibrant community of players, fostering the feeling of camaraderie and the global connection.
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Crypto casinos are known for offering unique and innovative gaming options that differentiate them from conventional casinos online. It offers a broad range of games like roulette, slots, poker blackjack, roulette, and even customized games that are based on crypto. These new offerings do not just offer players a new and exciting gaming experience, they also help to increase the fun and enjoyment that is associated with crypto casinos.
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In order to attract new players and keep existing ones, crypto casinos often provide generous promotions and bonuses. They can offer deposit bonuses, cashback offers, free spins, and even bonuses with no deposit requirements which let players play the games and platform without having to put in money initially. These incentives not only enhance the excitement of playing but also provide an opportunity for players to boost their winnings and enjoy more of the platform.
Joining safe online crypto casinos can be an exciting and a liberating experience for those who play. The benefits that these casinos offer, including anonymity, rapid transactions, guaranteed fair gaming, unrestricted accessibility, new gaming options, and attractive bonuses, all contribute to the excitement and liberation that crypto casinos offer. In turn, these platforms are well-suited for gamers who are concerned about security, speed, privacy, and innovative gaming experience.
This report is for informational purposes only and should not be taken as financial advice. Gambling online, which includes gambling at crypto casinos, carries inherent risks and the potential for financial losses. Players should always gamble responsibly and within their means and ensure they are aware of and adhere to local laws and regulations.

domain: hobby