text:
|Publication number||US4551486 A|
|Application number||US 06/552,300|
|Publication date||Nov 5, 1985|
|Filing date||Nov 16, 1983|
|Priority date||Nov 16, 1983|
|Publication number||06552300, 552300, US 4551486 A, US 4551486A, US-A-4551486, US4551486 A, US4551486A|
|Inventors||Louis H. Tateosian, W. Donald Wilson|
|Original Assignee||Dentsply Research & Development Corp.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (26), Non-Patent Citations (3), Referenced by (24), Classifications (33), Legal Events (10)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This invention provides hardenable compositions useful as construction media for a wide range of applications. Particular utility is found in the dental and medical arts where such compositions are highly suitable for the formation and construction of denture base, denture baseplates, denture liners, denture repair, custom trays, veneering for crowns and bridgework, artificial teeth, veneers and repair for natural teeth, and tooth restorative fillings.
More particularly, the invention relates to polymeric compositions comprising one or more multifunctional crosslinking oligomers capable of addition polymerization, crosslinked polymers swellable in said oligomers, inorganic fillers, and optionally, less than 2 percent of monofunctional monomers which form composite blends capable of being formed or molded and caused to polymerize to provide articles possessing superior physical and physiochemical properties.
In general, the novel compositions of this invention are useful as the formation and construction media for a wide range of applications where custom-shaped articles are required without the use of a mold. Alternatively, low cost molds, that need not withstand heat or more than moderate pressure, may be used to form such shaped articles. These compositions are particularly useful with dental and medical arts in the formation and construction of denture base, denture baseplates, denture liners, denture repair, custom trays, veneering for crowns and bridgework, artificial teeth, veneers and repair for natural teeth, and tooth restorative fillings.
In accordance with a preferred form of the present invention, hardenable dental compositions are provided which may easily and conveniently be molded and shaped by hand by known techniques into prosthetic dental appliances possessing chemical and physical properties which are significantly improved over those of conventional prior art acrylic dental appliances.
Briefly stated, the hardenable dental compositions of the invention comprise a blend of components which, when combined in certain proportions and permitted to age or mature, produce a blend that is moldable into prosthetic dentures and other dental devices. The blend is formed in accordance with the invention by combining a crosslinked polymer, crosslinking oligomers capable of addition polymerization, and an inorganic filler and/or an initiator and/or a monofunctional monomer, and by allowing said combination to age or mature. The crosslinked polymer is in the form of discrete particles having average diameters ranging from about 0.001 micron to about 500 microns. Preferably, at least 50 percent by weight of said particles have diameters less than about 150 microns, and more preferably, less than 100 microns. If desired, a mixture of two or more different crosslinked polymers may be used. A characteristic of the crosslinked polymer is that it will be insoluble in, but will be swollen by the liquid components used in the preparation of the blend.
The liquid polymerizable component of the compositions of the invention is one or more multifunctional oligomers having the capacity to swell the particles of crosslinked polymer used in the practice of the invention.
It has been discovered that the relative proportions of the components of the blend produced in accordance with the invention are critical in preferred embodiments to the attainment of the desired properties in the unhardened state including slump resistance, packability, freedom from tackiness, penetration, flow, viscosity stability, and modelability. Also, the relative proportions of components are critical to the attainment of the desired properties in the final hardened or cured product produced therefrom, notably flexural fatigue, transverse strength, wear resistance, impact resistance, resistance to solvents, stain resistance, thermal stability, and hydrolytic stability. Thus, it has been discovered that blends of from about 10 to about 70 weight percent of the crosslinked polymer, from about 10 to about 70 weight percent of multifunctional oligomers, from about 3 to about 80 weight percent of inorganic filler, and less than about 2 weight percent of polymerizable monomer, together with minor amounts of initiator and in some cases activator or accelerator for the initiator, provide blends which are particularly useful in the production of denture bases characterized by properties far superior to those of conventional systems not used in the art.
Preferably, the multifunctional vinyl crosslinking composition or agent or multifunctional crosslinking oligomer capable of addition polymerization is preferably present in an amount of 10 to 70 weight percent, more preferably 20 to 60, and most preferably 30 to 65 weight percent. Preferably, the crosslinked polymer in the form of discrete particles is present in an amount of 3 to 70 weight percent, more preferably 5 to 70, and most preferably 8 to 55 weight percent. The inorganic filler is preferably present in the amount of 3 to 80 weight percent, more preferably 5 to 50, and most preferably 8 to 30 weight percent. The most preferred ranges are especially preferred for the preferred denture base composition, but not in general for some of the other aspects of the present invention.
Surprisingly, it has been found that in the composition of the present invention, the addition of silane monomer to the composition gives a special and advantageous effect on the strength and integrity of the cured composition. Especially the flexural fatigue and transverse strength are greatly enhanced by blending the silane into the composition. The characteristics of the homogeneity of the filler distribution throughout the composite composition is also enhanced. The physical mixing process is also made easier and faster. (Gamma)-methacryloxypropyl trimethoxysilane is soluble in the composition of the present invention prior to curing or polymerization and gives excellent results. Any vinyl functional silane having proper solution characteristics is preferred, and especially preferred are the acrylic functional silanes. The silane is preferably included in the composition in an amount of 0.001 to 2 weight percent, more preferably 0.01 to 1.5 weight percent, and most preferably 0.05 to 1 weight percent.
In general, the crosslinked polymers which are useful in the practice of the invention are formed from monomers or blends of monomers together with crosslinking agents in proper proportion. The monomers suitable for use in the production of the crosslinked polymers useful in the practice of the invention, will generally comprise any of a wide variety of monomers such as, for example, acrylic and lower alkyl acrylic acid esters, N-vinyl lactams, acrylamides, acrylonitriles, styrenes, alkenes, and urethanes. Similarly, mixtures of two or more monomers may be employed to provide these crosslinked polymers.
Preferred monomeric species useful in the preparation of the crosslinked polymers of the invention include acrylic and lower alkyl acrylic acid esters which generally conform to the structure: ##STR1## where R1 is hydrogen or an alkyl group including from 1 to about 6 carbon atoms, and where R2 is either (a) an alkyl or cycloalkyl group including from 1 to about 20, and preferably from 1 to about 6 carbon atoms; (b) phenyl; and (c) substituted phenyl in which the alkyl groups include from 1 to about 6 carbon atoms. Various substituents may be present on either or both of the groups R1 and R2. Thus, hydroxyl, amino, thiol, and halogen (e.g., fluorine, chlorine, etc.) functionalities may be present, with the latter being preferred. Fluorine is an especially suitable and useful substituent.
Especially preferred examples of monomers useful in the production of the crosslinked polymers used in the practice of the invention include methyl-, ethyl-, isopropyl-, tert-butyl, octyl-, dodecyl-, cyclohexyl-, chloromethyl-, tetrachloroethyl-, perfluorooctyl-, hydroxyethyl-, hydroxypropyl-, hydroxybutyl-, 3-hydroxyphenyl-, 4-hydroxyphenyl-, aminoethyl-, aminophenyl, and thiophenyl-, acrylate, methacrylate, ethacrylate, propacrylate, butacrylate, and chloromethacrylate, as well as the homologous mono-acrylic acid esters of bisphenol-A, dihydroxydiphenyl sulfoxide, and 2,2-bis(4-hydroxy-2,3,5,6-tetrafluorophenyl)propane. Other suitable species will be apparent to those skilled in the art. If desired, mixtures of two or more different monomers may be used to provide the crosslinked polymers useful in the practice of the invention.
The crosslinking agents which are useful in the production of the crosslinked polymer component of the invention comprise a wide variety of di- or polyfunctional moieties which are capable of crosslinking. In general, the reactive functionalities which serve as active sites for such crosslinking are ethylenic functions, but other reactive and effective crosslinking functions are similarly useful as will be hereinafter described. The use of crosslinking agents in the formulation of polymers is well known to those skilled in the art, who similarly recognize that it is necessary for such agents to have at least two reactive functionalities.
Suitable crosslinking agents may be selected from numerous families of polyfunctional monomers such as acrylic and lower alkyl acrylic acid diesters, acrylic and lower alkyl acrylic acid esters formed from alcohols, which alcohols have a second reactive function, urethane diacrylates and dimethacrylates, polyvinylic compounds, divinyl aromatic compounds and others, as will be apparent to those skilled in the art.
Preferably, the crosslinking agents comprise esters of unsaturated acids, e.g., acrylic, methacrylic, ethacrylic, propacrylic, butacrylic, etc., maleic, fumaric, citraconic, mesaconic, itaconic, malonic, or aconitic, etc., acids. Other unsaturated acids will be readily apparent to those skilled in the art. These acids are preferably reacted with either unsaturated or polyhydroxylic alcohols to form esters which are effective polyfunctional crosslinking agents useful in the formulation of the crosslinked polymers of the invention. In general, these alcohols have one or more hydroxylic functionalities and have from 2 to about 30 carbon atoms. Thus, useful alcohols include allyl, methallyl, crotyl, vinyl, butenyl, isobutenyl, and similar unsaturated alcohols as well as polyols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, glycerol, 1,3,3-trimethylolpropane, pentaerythritol, dihydroxyphenol, and alkylidene bisphenols such as bisphenol-A, 1,1-bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, dihydroxydiphenyl ether, dihydroxydiphenyl sulfoxide, resorcinol, hydroquinone, etc.
Crosslinking agents preferred for the practice of the invention include the esters of a mono- or dibasic unsaturated acid with an unsaturated monohydroxylic alcohol such as allyl acrylate, allyl methacrylate, vinyl acrylate (methacrylate and C1 to C20 homologs), dimethallyl fumarate, N-allyl acrylamide, crotyl acrylate, allyl crotonate, allyl cinnamate, diallyl maleate, etc. Other preferred species are the di-, tri, and higher esters of polyhydroxylic alcohols such as ethylene "glycol" diacrylate (dimethacrylate and C2 -C40 homologs), trimethylolpropane trimethacrylate, and the diacrylate and dimethacrylate esters of bisphenol-A as well as acrylate and alkyl acrylate esters which correspond to the general formula ##STR2## where R3 and R4 may be the same or different and are hydrogen or alkyl groups containing from 1 to about 6 carbon atoms and n is a whole number from 1 to about 10. Alternatively, the crosslinking agent may conform to the formula: ##STR3## where R5 and R6 may be the same or different and are hydrogen or alkyl groups containing from 1 to about 6 carbon atoms and A is an aromatic moiety selected from the group consisting of (a) biphenyl, diphenyl alkylidene having from 1 to about 6 carbon atoms in the alkylidene portion thereof, diphenyl sulfone, diphenyl sulfoxide, diphenyl ether, and diphenyl sulfide; (b) the diglycidyl derivatives of group (a); and (c) the diurethane derivative of either group (a) or group (b). In addition, the crosslinking agent may be a glycidyl acrylate or allyl acrylate, divinyl (trivinyl or higher homologs) benzene, substituted divinyl benzenes, and analogous compounds. Furthermore, mixtures of two or more crosslinking agents are useful in the practice of the invention.
Compounds such as bis-GMA and the urethane diacrylates formed by reacting hydroxyethyl acrylate, hydroxypropyl acrylate, and their methacrylic homologs with 2,2,4-trimethylhexyl-1,6-diisocyanate are especially useful, as are diallyl maleate, ethylene "glycol" dimethacrylate, trimethylolpropane trimethacrylate and the dimethacrylate ester of bisphenol-A.
The crosslinked polymers are produced by polymerizing a mixture of the monomer or monomers and crosslinking agent or agents described above. The amount of crosslinking agent employed in the production of the crosslinked polymers used in the practice of the invention is a critical factor. It has been found that the capacity of particles of polymers so produced to swell with or to imbibe the liquid components forming the compositions of the invention, is directly related to the amount of crosslinking agent used in the production of such crosslinked polymers.
The physicochemical properties of the crosslinked polymers useful in the practice of the invention determine the relative proportions of monomer and crosslinking agent used to formulate said suitable crosslinked polymers. Such crosslinked polymers must be sufficiently well crosslinked as to maintain substantially their structural identity when exposed to the liquid components of the compositions of the invention. At the same time, they must not be so thoroughly crosslinked as to be incapable of swelling with or imbibing such liquid components. Thus, it is convenient to describe the proportion of crosslinking agent by what it does rather than by what it is. In view of the fact that the crosslinked polymers are utilized in finely particulate form, as will be more fully explained, it is convenient to define the minimum amount of crosslinking agent used therein as being that amount which is sufficient to cause the particulate crosslinked polymer not to lose its particulate discreteness upon exposure to the liquid components of the invention. Similarly, the maximum amount of crosslinking agent used therein is that amount beyond which the resulting crosslinked polymer particles are unable to swell with or further imbibe a significant portion of liquid components upon exposure thereto. In this regard, a quantity of crosslinked polymer particles would be said to swell with or imbibe a significant portion of liquid components if it swelled with or has imbibed at least 10 percent of its own weight of such liquid. Preferably, an amount of crosslinking agent is used to provide a crosslinked polymer having the capacity to imbibe from about 10 to about 500 percent of its own weight of liquid components.
It will be clear to those skilled in the art that the minimum and maximum values for the proportions of crosslinking agents suitable for inclusion in the crosslinked polymers of this invention will vary depending upon the chemical identity of the component monomers and crosslinking agents. In general, however, the crosslinking agents may comprise from as low as about 0.01 percent to as high as about 30 percent, preferably from about 0.02 percent to about 5 percent, and more preferably from about 0.05 percent to about 1.5 percent by weight of the resulting crosslinked polymer.
The production of the crosslinked polymers useful in the practice of this invention from monomers and crosslinking agents may be performed by any of the many processes known to those skilled in the art. Thus, the polymers may be formed by heating a mixture of the components to a temperature sufficient to cause polymerization, either with or without the addition of initiators. For this purpose, peroxy type initiators such as benzoyl peroxide, dicumyl peroxide, and other materials familiar to those skilled in the art may be employed, and the use of activators may be advantageous in some formulations. Alternatively, the crosslinked polymers of the invention may be formed from the constituents by photochemical or radiant initiation utilizing light or high energy radiation. For photochemical initiation, photochemical sensitizers, or energy transfer compounds may be employed to enhance the overall polymerization efficiency in manners well known to those skilled in the art.
The polymerization of the crosslinked polymers may be accomplished in a wide variety of ways, all of which are known to those skilled in the art. Thus, they may be formed by suspension polymerization as taught in U.S. Pat. No. 2,673,194 to Grim, emulsion polymerization, block polymerization, or any other useful and convenient process. Since, as will be more fully described herein, it is desirable to have the crosslinked polymer available in the form of finely particulated granules or beads, suspension polymerization is especially convenient. Blocks of bulk-formed polymer may be crushed to yield a useful product, however. The size of the particles of crosslinked polymer is of significance to the invention. As indicated, it is desirable that the crosslinked polymer be in the form of small, discrete particles or beads. The average particle size should be from about 0.001 micron to about 500 microns. It is preferred that at least 50 percent by weight of the particles have diameters below 150 microns and more preferably below 100 microns.
The multifunctional crosslinking oligomers and/or monomers useful in the practice of the invention comprise a wide variety of di- or polyfunctional moieties which are capable of addition polymerization. In general, the reactive functionalites which serve as active sites for this polymerization are ethylenic functions, e.g. acrylic, vinyl alkyl, and other reactive groups are similarly useful. The use of multifunctional oligomers and monomers in the formulation and elaboration of polymeric composites is well known to those skilled in the art, who will appreciate that it is necessary for such agents to have at least two reactive functionalities and to therefore be multifunctioned. Suitable multifunctional monomers and oligomers may be selected from numerous families of polyfunctional vinyl and/or addition polymerizable monomers such as acrylic and lower alkyl acrylic acid diesters, acrylic and lower alkyl acrylic acid esters formed from alcohols which alcohols have a second reactive function, urethane diacrylates and dimethacrylates, polyvinylic compounds, divinyl aromatic compounds, and others as will be apparent to those skilled in the art.
Preferably, the multifunctional monomers and oligomers comprise esters of unsaturated acids, e.g., acrylic, methacrylic, ethacrylic, propacrylic, butacrylic, etc., maleic, fumaric, citraconic, mesaconic, itaconic, malonic, or aconitic, etc., acids. Other unsaturated acids will be readily apparent to those skilled in the art. These acids are preferably reacted with either unsaturated or polyhydroxylic alcohols to form esters which are effective multifunctional monomers and oligomers useful in the formulation of the compositions of the invention. In general, these alcohols have one or more hydroxylic functionality and have from 2 to about 30 carbon atoms. Thus, useful alcohols include allyl, methallyl, crotyl, vinyl, butenyl, isobutenyl, and similar unsaturated alcohols as well as polyols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, glycerol, 1,3,3-trimethylol-propane, pentaerythritol, dihydroxyphenol, and alkylidene bisphenols such as bisphenol-A, 1,1-bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, dihydroxydiphenyl ether, dihydroxydiphenyl sulfoxide, resorcinol, hydroquinone, etc.
The preferred multifunctional monomers and oligomers used in the practice of the invention include the esters of a monomeric dibasic unsaturated acid with an unsaturated mono-hydroxylic alcohol such as allyl acrylate, allyl methacrylate, vinyl acrylate (methacrylate homologs), dimethallyl fumarate, N-allyl acrylamide, crotyl acrylate, allyl crotonate, allyl cinnamate, diallyl maleate, etc. Other preferred species are the di-, tri-, and higher esters of polyhydroxylic alcohols such as ethylene "glycol" diacrylate(dimethacrylate and C2 -C6 homologs), trimethylolpropane trimethacrylate, and the dimethacrylate ester of bisphenol-A as well as other acrylate and alkyl acrylate esters corresponding to Formula II, above. Alternatively, the multifunctional monomers and/or oligomers may conform to Formula III, above. In addition, the multifunctional monomers and/or oligomers for the glycidyl acrylate or allyl acrylate, divinyl (trivinyl or higher homologs) benzene, substituted divinyl benzenes, or analogous compounds. Furthermore, mixtures of crosslinking agents are useful in the practice of the invention.
Compounds such as bis-GMA and the urethane dimethacrylate formed from the reaction of hydroxyethyl acrylate, hydroxypropyl acrylate, and their methacrylate homologs with 2,2,4-trimethylhexyl-1,6-diisocyanate (hereinafter referred to as "urethane dimethacrylate" or "diacrylate") are especially useful, as are ethylene "glycol" dimethacrylate, 1,6-hexanediol dimethacrylate trimethylolpropane trimethacrylate and the dimethacrylate ester of bisphenol-A and urethane adducts thereof. The corresponding acrylates are similarly useful as is diallyl maleate.
In addition to the components described above, (i.e., crosslinked polymer, filler, and a crosslinking agent, the blend further may contain additional, optional ingredients. These may comprise initiators, activators, pigments, radiopaquing agents, adhesion modifiers, and other materials as will occur to those skilled in the art.
The blends of the invention are formulated by a mixing together of the constituent species in proper proportion, followed by aging or maturing. Several techniques are available for this and others will be apparent to those skilled in the art. Thus, it is possible to combine crosslinked polymer, filler, and a crosslinking agent in proper proportions including therewith, for example, a peroxide initiator, and a pigment. This combination is then thoroughly mixed and aged to result in a blend which has a uniform appearance.
It is understood, however, that the blends are suitable for a very wide range of dental uses, including fillings, teeth, bridges, crowns, veneers, facings, pit and fissure sealants, denture base and denture reline materials, orthodontic splint materials, and adhesives for orthodontic appliances. The materials of the invention may also be utilized for prosthetic replacement or repair of various hard body structures such as bone and may be utilized for reconstructive purposes during surgery, especially oral surgery. They are also useful for various non-dental uses as, for example, in plastic construction materials.
The nature of the chemical and physical relationships among the components of the blends of the invention is important to the practice of the invention. Chief among these relationships is the necessity that the crosslinked polymer particles be capable of swelling with or imbibing the liquid components of the invention. In accordance with the invention, the blend formed by any of the useful techniques described above is aged for a period of time sufficient to insure that the crosslinked polymer has become substantially fully swollen with, interpenetrated by or has substantially imbibed the crosslinking agent. Thus, as used herein, "aged" or "aging" refers to the maintenance of the components of the blend in association with one another in the blend for a period of time sufficient to substantially fully swell the crosslinked polymer particles with the crosslinking agent. Frequently, the aging process is manifested by a change in the consistency of the blend as equilibrium is approached. The time necessary to approach such equilibrium will vary depending upon the blending techniques, the relative proportions of materials, the particle sizes and molecular weights of the polymer, and the temperature extent in the blend. In general, aging time of from one to seven days has been found to be adequate to approach the desired equilibrium. It is to be understood that it lies well within the abilities of those skilled in the art to ascertain the optimum aging time for a formulation in view of the foregoing considerations.
Upon polymerization of the blends, a three dimensional structure is believed to be formed which may be denominated as an interpentrating polymeric network. The structure which is thought thus to form is believed to be a major contributing factor to the serendipitous combination of superior chemical and physiochemical properties which is exhibited by the articles constructed according to the practice of the invention. Interpenetrating polymeric networks are related to, but distinct from, traditional graft polymers. In general, when a second polymer is synthesized in the intimate presence of a first polymer, the resultant material has been known as a graft polymer regardless of the actual extent of chemical grafting of one polymer to the other. Interpenetrating polymer networks are thought to be formed, however, when the first polymer is substantially crosslinked into a three dimensional network prior to the formation of the second polymer, and when that second polymer is caused to form in such a fashion that it too is substantially crosslinked into a three dimensional network. Such network may also "suspend" inclusions of inorganic origin such as, for example, pigments and fillers.
Thus, an interpenetrating polymeric network may be viewed as being composed of two or more crosslinked, and hence three dimensionally arrayed, polymeric networks which co-exist in the same volume of space, but which do not necessarily have any covalent bonds in common. While the two networks may, indeed, be independent in the sense that they need posess no covalent linkages between them, they are physically trapped one "within" the other and cannot disassociate by any physical manipulation without the rupture of covalent bonds.
Central to an understanding of interpenetrating polymeric networks is the recognition that an interpentrating polymeric network is not a substance per se, but is, rather, a term descriptive of a structure. For discussions of the nature of interpenetrating polymeric network's in general, see the recent papers by L. H. Sperling et al, Macromolecules, volume 9, No. 4 (1976); Macromolecules, volume 9, No. 5 (1976); J Polymer Science, volume 12, page 141 (1977); and J. Polymer Science, volume 16, page 583 (1978); and articles cited therein. Also, see Klepner et al, J. Elastoplast, volume 5, page 196 (October 1973).
While it appears to be desirable that the crosslinking of both polymers be substantial, various degrees of crosslinking are possible in both the preformed polymer and the polymer formed in situ. In addition, it should be recognized that an interpenetrating polymeric network may be formed even when the initial and second polymers are formed from the same materials. For example, two independent networks of a polymethacrylate, suitably crosslinked, may interpenetrate each other to form an interpenetrating polymeric network. Similarly, an interpenetrating polymeric network need not be limited only to two networks, as mixtures of two or more polymers may be used as the polymer. Mixtures of two or more crosslinking agents may also be used in network formation.
It is thought that in the present invention, interpenetrating polymeric networks may be formed. Thus, when particulate crosslinked polymer is allowed to swell with or imbibe crosslinking agent, and when the imbibed crosslinking agent is subsequently caused to polymerize, an interpenetrating polymeric network may be seen to be formed within the confines of the particulate crosslinked polymer. It is believed that it is this interpenetrating polymeric network structure, which is localized in the particulate masses formed subsequent to the swelling of particulate crosslinked polymer and the polymerization of the blend, that lends the superior chemical and physicochemical properties to the articles formed according to this invention. It is believed that the aging process employed in the preparation of the precursor blends of the invention is required to accomplish substantially full swelling with interpenetration by or substantially complete imbibition of crosslinking agent by the crosslinked polymer particles, and to approach an equilibrium thereof. It is to be understood, however, that the foregoing discussion of interpenetrating polymeric networks and their application to the present invention is not to be construed as a limiting factor thereof, but, rather, is to be interpreted as a mechanism which is proposed as being applicable in the present case.
As has been indicated, the compositions of the invention exhibit superior chemical and physiochemical properties. Accordingly, the articles made from the compositions of the invention exhibit flexural fatigue, transverse strength, impact, and chemical resistance as denture bases. In addition, such articles display a unique microstructure.
The invention has, as another important feature, the inclusion of inorganic filler. Included in the inorganic fillers are the especially preferred silicious fillers. Especially preferred are the inorganic glasses. Among these are barium aluminum silicate, lithium aluminum silicate; strontium, lanthanum, tantalum, etc., alumino silicate glasses; and related materials. Glass beads, silica, especially in sub-micron sizes, quartz, borosilicates, and other fillers may also be employed. Such fillers may be silanated prior to use in the adhesives of this invention. Silanation is well known to those skilled in the art and any silanating compound known to them may be used for this purpose.
Especially preferred is silanated microfine amorphous silicone dioxide particulate. Silanated means that some of the silanol groups have been substituted or reacted with, for example, dimethyldichlorosilane to form a hydrophobic filler. The particles are typically from 50 to 95 percent silanated. Silanated inorganic fillers are considered for purposes of this invention to be inorganic fillers.
All percentages in this patent application are weight percents based on 100 percent of the final composition except where clearly indicated as precents of additive combinations.
The invention is further illustrated by the following examples:
An organic amine salt was prepared from two feedstocks as follows:
332.1 g glacial methacrylic acid (MAA) and 5.7 g BHT were added to a two liter polyethylene bottle. The mixture was agitated until the BHT dissolved into a uniform solution. The MAA solution was then placed into a -12° C. freezer for four hours. The solution froze to a solid. At substantially the same time, about 700 g of dimethylaminoneopentyl acrylate (DMANPA) was added to a one liter polyethylene bottle and placed in the freezer for four hours. The DMANPA did not freeze and remained liquid.
Both bottles were removed from the freezer and 662.2 g of DMANPA were poured onto the frozen MAA solution. the combined MAA and DMANPA were mixed on a roller mill for one hour. The resulting amine salt DMANPA-MAA was a clear, slightly viscous liquid.
A moldable denture base composition was formed that is hardenable with visible light. The denture base material was prepared according to the following formula:
______________________________________Percent by Weight of Total Composition______________________________________39.01 Urethane dimethacrylate [N,N--bis (2-methacryloyloxyethoxycarbonyl)- 1,6-diamino-2,4,4-trimethylhexane which is the reaction product of hydroxyethyl methacrylate and 2,2,4-trimethylhexyl-1, 6-diisocyanate)2.54 1,6-Hexanediol dimethacrylate (HDDMA)0.13 Camphoroquinone (CQ)0.66 DMANPA-MAA salt42.48 Poly (methyl methacrylate-co-ethylene dimethacrylate 99.8:0.2) a polymer supplied by L. D. Caulk Company*0.08 Red acetate fibers0.02 Pigments14.92 Fumed silica inorganic filler (Aerosil R972, a product of Degussa)0.16 Gamma-Methacryloxypropyltrimethoxysilane______________________________________ *The polymer was prepared according to the teaching of U. S. Pat. No. 4,396,476.
First, the CQ was dissolved in HDDMA and then mixed with the amine salt, the gamma methacryloxypropyltrimethoxysilane, and urethane dimethacrylate. The resulting liquid solution was charged to a double planetary mixer heated to 45° C. and mixed under 20 mm Hg pressure. Next, the polymer with the pigments and fibers previously blended in a V-Cone Blender was added and mixed under 20 mm pressure. The temperature was increased to 55° C. and the fumed silica was added in three increments of about equal size and mixed under 130 mm pressure each time. This produced a visible light curable (VLC) putty-paste.
The VLC putty was molded into a sheet 3.5 inches×2.5 inches×0.10 inches in a hydraulic press. The sheet was adapted as a baseplate to a stone model (coated with separator) made from an impression of the mouth. The baseplate was trimmed and then cured in two minutes on a turntable rotating under four 150 watt quartz-halogen lamps with a 400 to 500 nm band-pass filter. A preferred apparatus is shown in U.S. Ser. No. 492,284, filed May 6, 1983. The light flux varied from 100 to 130 mw/cm2 on the surface of the baseplate. Additional VLC putty was rolled into rope 0.25 inches in diameter. The rope was adapted around the ridge of the baseplate in a configuration to receive the pressed-in full arch of acrylic plastic teeth.
A bonding agent composition or adhesive tie coat was prepared by charging to a glass reactor the ingredients listed below in the proportions given and in the manner described below in a red light room.
______________________________________Percent Amount Ingredient______________________________________21.58% 1079.0 g (grams) Dicyclopentenyloxyethyl methacrylate (QM 657) Rohm and Haas Company4.32% 216.0 g Acrylic Acid7.19% 359.5 g 1,6-Hexandeiol dimethacrylate (HDDMA)0.31% 15.5 g Camphoroquinone (CQ)1.61% 80.5 g Dimethylaminoneopentyl acrylate methacrylic acid (DMANPA-MAA) salt*19.66% 983.0 g Methymethacrylate (MMA)45.33% 2266.5 g Acrylated urethane oligomer (Uvithane 782, Morton-Thiokol Corporation)______________________________________ *DMANPA-MAA salt comprising 53.21 g DMANPA, 26.73 g MAA, 0.46 g BHT prepared as described in the proceding organic amine salt preparation procedure.
The CQ was dissolved in the HDDMA and then added to the reactor. Next, the acrylic acid, DMANPA-MAA, QM657, and MAA were added with stirring. Finally, the Uvithane 782, previously heated to 60° C. for three hours, was added to the mixture with stirring. The mixture was stirred for 2.5 hours. A visually uniform solution was obtained. The solution was transferred to light proof bottles.
A set of arch form teeth was formed according to the teaching of U.S. Ser. No. 510,405, filed July 1, 1983 and assigned to the same assignee as the present application, the contents of which application are incorporated herein by reference, using the teaching of U.S. Pat. No. 4,396,377 previously referred to in this application.
The bonding agent composition formulated was applied as a visually thorough and complete covering to the ridge lap areas and about 2 mm onto the facial, lingual collar and interproximal areas of full arch upper teeth by applying with a brush. The bonding agent was bench set for two minutes and then light cured two minutes in the cure unit previously described.
The teeth coated with the bonding agent were then press-positioned in the rope of VLC putty. The teeth were then further trued in position in an articulator and then fixed in position by a two-minute light cure. Next, the facial and lingual aspects of the denture were finished with additional rope.
A liquid, oxygen barrier coating described below was applied as a top coating before curing the visible light curable denture resin. The surface after photocuring for four minutes was dry, shiny, and tack free. The denture was then removed from the stone model and the other side of the denture was coated with the liquid, oxygen barrier coating and then cured for two minutes under the light. The surface was dry, shiny, and tack free. Next, the cured denture was washed with tap water and dried with a paper towel. Both surfaces of the processed denture were shiny and tack free.
The oxygen barrier layer was prepared according to the following formulation:
______________________________________41.00% Polyvinyl pyrrolidone (Plasdone K 29/32, GAF Corporation)58.23% Water0.045 Silicone antifoam (SAG 471, Union Carbide Corporation)0.225 Surfactant (Makon 10, Stepan Chemical Corporation)0.50 Potassium sorbate______________________________________
The above ingredients were mixed together at ambient conditions and the resulting solution was a very viscous clear yellow colored liquid with a viscosity of 850 centipoises at 22° C. (Brookfield #2 spindle, 20 rpm).
The following denture base composition was prepared and formed into a denture with excellent results according to the teaching of U.S. application Ser. No. 510,404, filed July 1, 1983, which application is included by reference.
______________________________________Percent by Weight of Total Composition______________________________________39.44 Urethane dimethacrylate (Reaction product of hydroxyethyl methacrylate and 2,2,4- trimethylhexyl-1,6-diisocyanate)2.57 1,6-Hexanediol dimethacrylate (HDDMA)0.13 Camphoroquinone (CQ)0.59 Reaction product of dimethylaminoethyl methacrylate and methacrylic acid (DMAEMA-MAA)42.10 Poly (methyl methacrylate-co-ethylene dimethacrylate 99.8:0.2), a polymer supplied by L. D. Caulk Company (Polymer is in substantially spherical beads, the shape resulting from its suspension polymerization. At least 50 percent by weight of the beads have average diameters of less than 50 microns. The polymer was prepared from methyl methacrylate and ethylene dimethacrylate by suspension polymerization*).0.07 Red acetate fibers0.03 Pigments15.07 Fumed silica inorganic filler (Aerosil R972, a product of DeGussa)______________________________________ *The polymer was prepared according to the teaching of United States Serial Number 318,356, filed November 5, 1981, which was a continuation o United States Serial Number 008,507, filed February 1, 1977.
First CQ was dissolved in HDDMA and then mixed with the DMAEMA-MAA and urethane dimethacrylate. The resulting liquid solution was charged to a double planetary mixer heated to 45° C. and mixed under 20 mm Hg pressure. Next, the polymer, pigments, and fibers were blended in a V-Cone Blender. The polymer blend was added and mixed under 20 mm pressure. The temperature was increased to 55° C. and the fumed silica was added in three increments of about equal size and mixed under 130 mm pressure each time. This produced a visible light curable (VLC) putty-paste which is then further treated to remove excess entrapped air by placing the putty in a canister and subjecting it to 20 mm mercury pressure and then to high pressure in a hydraulic press. The putty was then extruded through Delrin Dies using a ram extruder into a sheet having a size of 0.1 inch×25/8 inches and a rod having a diameter of 0.375 inch. The sheet and rod were then cut into lengths of about four inches.
By putty, it is meant a viscous material that can be deformed mechanically (manually) and will at least temporarily hold the shape into which it has been deformed or molded.
A restorative composition according to the present invention was compouned in a 1 quart Readco sigma blade mixer, heated at 55° C.:
______________________________________Weight % Component______________________________________61.30% Silane treated microfine silica0.90 Aerosil R972 (DeGussa) microfine silica filler7.10 Suspension polymerized methyl methacrylate- co-ethylene dimethacrylate (99.8:0.2)27.60 Reaction product of hydroxyethyl- methacrylate and 2,2,4-tremethylhexane- 1,6-diisocyanate1.80 1,6-Hexanediol dimethacrylate0.95 3-Methacryloxypropyltrimethoxysilane0.09 Camphoroquinone0.26 Dimethylaminoethyl methacrylate0.003 PigmentsTotal 100.00%______________________________________
The silane-treated microfine silica was prepared by silaning 1000 g OX50 fumed silica (DeGussa) with 200 g 3-methacryloxypropyltrimethoxysilane in 12 liters of hexane. The silica and 10 liters of hexane were stirred together for thirty minutes in a stainless steel bucket. Next, the silane was added and stirred for one hour. An additional 2 liters of hexane were added and the mixture was allowed to settle for sixteen hours. The mixture was decanted, filtered, washed with hexane, and dried at 115° C. for twenty-four hours. The resulting cake was broken up, milled, and sieved through a #10 screen.
The camphoroquinone, dimethylaminoethylmethacrylate, urethane dimethacrylate, and 1,6-hexanediol dimethacrylate were blended together and formed into a solution and then added to the mixer. The pigment was compounded with the polymer in a ball mill. The pigmented polymer was added, mixed with the liquid, and allowed to stand for twenty hours to form a preswell. The silanated silica and R972 silica were preblended and added in increments with stirring until a homogeneous mixture was obtained. Finally, the silane was added and mixed for thirty minutes. The resulting material is suitable for a posterior filling material, will deform a matrix band, and may be cured with the Prisma-Lite visible light polymerization unit to a hard solid. The composition of Example 3 did not discolor when placed and compacted with metallic amalgam placement and compacting instruments.
All percentages in this patent application are weight percents based on 100 percent of the final composition except where clearly indicated as percents of additive combinations or of recited compositions. Where indicated as a percent of recited compositions or components, it is meant that the materials recited in the series are to be apportioned among themselves to equal 100 percent when added up. Unless another meaning is clearly intended, compound is meant to define a specific chemical compound while composition is meant to define one or more compounds having a stated characteristic either singly or in combination. A composite composition is a composition including two or more compositions differing in stated characteristic. A polymerizable composition is one that can polymerize. As a general understanding, the polymerizable compositions of the present invention harden on polymerization, turning in most preferred instances from putties or paste to solids that have firm attributes of hardness or shape retaining character, generally having some rigidity with flexing ability.
While in accordance with the patent statutes what is at present considered to be the preferred embodiment of the invention has been described, it will be obvious to those skilled in the art that numerous changes and modifications may be made therein without departing from the invention, and it is therefore aimed in the appended claims to cover all such equivalent variations as fall within the true spirit and scope of the invention.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2673194 *||Nov 9, 1951||Mar 23, 1954||Koppers Co Inc||Suspension polymerization|
|US3887652 *||May 10, 1973||Jun 3, 1975||Dart Ind Inc||Process for producing transparent graft polymer compositions|
|US4035453 *||Nov 6, 1975||Jul 12, 1977||Wacker-Chemie Gmbh||Dental impression materials|
|US4071424 *||Feb 11, 1975||Jan 31, 1978||Imperial Chemical Industries Limited||Photopolymerizable composition|
|US4125700 *||Mar 22, 1977||Nov 14, 1978||E. I. Du Pont De Nemours And Company||Preparation of methyl methacrylate polymer powders for use in plastisols|
|US4222983 *||Jul 27, 1978||Sep 16, 1980||Wacker-Chemie Gmbh||Impression compositions and process for preparing impressions|
|US4243793 *||Jul 28, 1978||Jan 6, 1981||Phillips Petroleum Company||Prepolymers for photocurable compositions|
|US4267133 *||Mar 14, 1979||May 12, 1981||Sankin Industry Co., Ltd.||Manufacture of denture base|
|US4281991 *||Jul 20, 1978||Aug 4, 1981||Perdent, Gmbh||Dental prostheses|
|US4288221 *||Jan 28, 1980||Sep 8, 1981||Minnesota Mining And Manufacturing Company||Durable, polishable direct filling material|
|US4297185 *||Sep 18, 1979||Oct 27, 1981||Techinter S.A.||Photosetting adhesive from unsaturated oligomer, photoinitiator, and betaine-forming mixture of unsaturated tert.amine and unsaturated acid|
|US4308190 *||Nov 19, 1979||Dec 29, 1981||Bayer Aktiengesellschaft||Dental materials based on organic plastics in paste form|
|US4323348 *||Jul 31, 1980||Apr 6, 1982||Bayer Aktiengesellschaft||Dental compositions|
|US4351853 *||Jan 15, 1981||Sep 28, 1982||Espe Fabrik Parmazeutischer Praparate G.m.b.H.||Method for producing prosthetic dental appliances by photopolymerizing a shapeable mass|
|US4369262 *||Jul 16, 1981||Jan 18, 1983||Bayer Aktiengesellschaft||Dental material based on crosslinked plastic and polymerizable binder|
|US4379695 *||May 27, 1981||Apr 12, 1983||Scientific Pharmaceuticals, Inc.||Dental material comprising dimethyacrylate adducts of glycidyl methacrylate with diesters of bis(hydroxymethyl) tricyclo[5.2.1.02,6 ]decane and dicarboxylic acids|
|US4383826 *||Jun 23, 1981||May 17, 1983||Blendax-Werke R.Schneider Gmbh & Co.||Adducts of diisocyanates and methacryloyl alkyl ethers, alkoxybenzenes or alkoxycycloalkanes, compositions containing such compounds, and method of use thereof|
|US4386912 *||Apr 26, 1982||Jun 7, 1983||Kuraray Company Limited||Method for filling tooth cavities employing a polymerizable urethane cement composition|
|US4389497 *||Nov 21, 1980||Jun 21, 1983||Espe Fabrik Parmazeutischer Praparate Gmbh||Use of agglomerates of silicic acid as fillers in dental materials|
|US4394465 *||Sep 5, 1980||Jul 19, 1983||Bayer Aktiengesellschaft||Dental materials based on organic plastics in paste form|
|US4396377 *||Nov 5, 1981||Aug 2, 1983||Dentsply Research & Development Corporation||Dental appliances having interpenetrating polymer networks|
|US4396476 *||Nov 5, 1981||Aug 2, 1983||Dentsply Research & Development Corporation||Blend of cross-linked polymer, swelling monomer and cross-linking agent and curing process|
|US4442240 *||Jul 14, 1983||Apr 10, 1984||Bisco, Inc.||Dental filling materials|
|EP0059525A2 *||Jan 12, 1982||Sep 8, 1982||Dentsply International, Inc.||Dental compositions|
|EP0070634A2 *||Jun 28, 1982||Jan 26, 1983||Dentsply International Inc.||Visible light curable sealants|
|GB2074590A *||Title not available|
|1||*||J. Elastoplast by Klempner et al., vol. 5, p. 196 (Oct. 1973).|
|2||*||J. Polymer Science by L. H. Sperling et al., vol. 12, p. 141 (1977), and vol. 16, p. 583 (1978).|
|3||*||Macromolecules by L. H. Sperling et al., vol. 9, Nos. 4&5 (1976).|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4761136 *||Aug 6, 1987||Aug 2, 1988||Kerr Manufacturing Company||Visible light cured impression material|
|US4813876 *||May 8, 1987||Mar 21, 1989||Dentsply Research & Development Corp.||Method of treating living pulp tissue|
|US4863977 *||Nov 10, 1987||Sep 5, 1989||Dentsply Research & Development Corp.||Process for preparing interpenetrating polymer network objects employing rubber-modified polymers|
|US4892478 *||Mar 21, 1988||Jan 9, 1990||Dentsply Research & Development Corp.||Method of preparing dental appliances|
|US4940676 *||Jun 16, 1988||Jul 10, 1990||Board Of Regents, The University Of Texas System||Ceramic compositions and methods employing same|
|US5210109 *||Sep 21, 1992||May 11, 1993||Dentsply Research & Development Corp.||Interpenetrating polymer network compositions employing rubber-modified polymers|
|US5266402 *||Dec 18, 1990||Nov 30, 1993||Minnesota Mining And Manufacturing Company||Interpenetrating pressure-sensitive adhesive polymer networks|
|US5298758 *||Dec 7, 1992||Mar 29, 1994||Dentsply Research & Development Corp.||Denture curing apparatus and method|
|US5304586 *||Aug 2, 1991||Apr 19, 1994||Dentsply Research & Development Corp.||Radiopaque fluoride releasing VLC dental composites and the use of specific fillers therein|
|US5326346 *||Jul 27, 1992||Jul 5, 1994||Board Of Regents, The University Of Texas System||Light-cured urethane dimethacrylate ocular prosthesis|
|US5362486 *||Apr 10, 1992||Nov 8, 1994||Helene Curtis, Inc.||In-situ polymerization of oligomers onto hair|
|US5477054 *||Mar 25, 1994||Dec 19, 1995||Dentsply Research & Development Corp.||Denture curing apparatus and method|
|US5502087 *||May 16, 1994||Mar 26, 1996||Dentsply Research & Development Corp.||Dental composition, prosthesis, and method for making dental prosthesis|
|US5736619 *||Apr 21, 1995||Apr 7, 1998||Ameron International Corporation||Phenolic resin compositions with improved impact resistance|
|US6121344 *||Mar 17, 1999||Sep 19, 2000||Kerr Corporation||Optimum particle sized hybrid composite|
|US6300390||May 6, 1999||Oct 9, 2001||Kerr Corporation||Dental restorative composite|
|US6976997 *||Jun 18, 2003||Dec 20, 2005||The Board Of Trustees Of The Leland Stanford Junior University||Artificial cornea|
|US8765836||Jan 26, 2010||Jul 1, 2014||Dentsply International Inc.||Hybrid polymer network compositions for use in dental applications|
|US20040049268 *||Jun 18, 2003||Mar 11, 2004||Jaan Noolandi||Artificial cornea|
|US20040224283 *||Nov 26, 2003||Nov 11, 2004||Sun Benjamin J.||Method of forming a dental product|
|US20090030109 *||Apr 9, 2008||Jan 29, 2009||Hare Robert V||Dental composite restorative material|
|US20100044895 *||May 12, 2009||Feb 25, 2010||Sun Benjamin J||Method of forming a dental product|
|EP0630640A1 *||Jun 23, 1994||Dec 28, 1994||Dentsply International Inc.||Dental composition, prostheses and method for making dental prostheses|
|WO2017055629A1 *||Oct 3, 2016||Apr 6, 2017||Dsm Ip Assets B.V.||Particle-based multi-network polymers|
|U.S. Classification||523/212, 522/83, 522/92, 522/95, 523/115, 522/77, 522/28, 523/116, 525/903|
|International Classification||C08L51/00, C08F265/04, C08F2/00, C08F291/00, C08F289/00, C08L23/00, A61K6/08, C08L21/00, C08L101/00, C08L7/00, C08L51/02, A61K6/083, C08L33/00, C08F291/02, C08F2/48, C08L33/02, C08F2/44|
|Cooperative Classification||Y10S525/903, C08F291/00, C08F265/04, A61K6/08|
|European Classification||C08F291/00, A61K6/08, C08F265/04|
|Aug 21, 1985||AS||Assignment|
Owner name: DENTSPLY RESEARCH AND DEVELOPMENT CORP. MILFORD,
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:TATEOSIAN, LOUIS H.;WILSON, W. DONALD;REEL/FRAME:004442/0936
Effective date: 19840106
|Jun 6, 1989||REMI||Maintenance fee reminder mailed|
|Aug 14, 1989||FPAY||Fee payment|
Year of fee payment: 4
|Aug 14, 1989||SULP||Surcharge for late payment|
|May 5, 1993||FPAY||Fee payment|
Year of fee payment: 8
|Jun 10, 1997||REMI||Maintenance fee reminder mailed|
|Nov 2, 1997||LAPS||Lapse for failure to pay maintenance fees|
|Nov 4, 1997||SULP||Surcharge for late payment|
|Nov 4, 1997||FPAY||Fee payment|
Year of fee payment: 12
|Jan 13, 1998||FP||Expired due to failure to pay maintenance fee|
Effective date: 19971105


- Prince Charles and his wife, Duchess Camilla, are no longer in self-isolation after Charles tested positive for COVID-19 last month.
- BAZAAR.com understands that both the Prince of Wales and the Duchess of Cornwall are in good health, and following government and medical guidelines.
- Both royals are currently residing at the Birkhall estate in Scotland amid the ongoing global health crisis.
Camilla, Duchess of Cornwall, is officially out of self-isolation.
Sources confirm to BAZAAR.com that Camilla and her husband, Prince Charles, have reunited since the two separated and went into self-isolation due to Charles's COVID-19 diagnosis last month. Charles exited self-isolation last week following a period of quarantine after displaying mild symptoms of the novel virus, but the duchess remained sequestered within their home as a precaution.
Both royals are in "good health" and will continue to isolate together at their Birkhall estate in Scotland.
More From Harper's BAZAAR
Original Post 3/30/20:
Prince Charles is embarking on a thorough recovery after testing positive for the novel coronavirus last week.
The Prince of Wales has been in self-isolation in Scotland with his wife, Camilla, Duchess of Cornwall. But according to a statement from a Clarence House spokesperson, Charles is on the mend. "Clarence House has confirmed today that, having consulted with his doctor, The Prince of Wales is now out of self-isolation," the statement read.
The heir to the throne displayed "mild symptoms" on March 22, took the test on March 23, and received the positive results on March 24. It's unclear exactly when or how he contracted the disease.
BAZAAR.com understands that Charles is in good health and operating under the current standard government and medical restrictions that apply nationwide in the United Kingdom. The BBC reports that, per government guidelines, anyone showing symptoms should isolate for seven days, while everyone living with that person should isolate for two weeks. Duchess Camilla will remain in self-isolation until the end of the week to ensure she does not showcase any coronavirus symptoms.
As the country continues to combat the global pandemic, other members of the royal family have also continued to follow government advice to help slow the spread of the novel virus. Queen Elizabeth II and Prince Philip are currently self-quarantining at Windsor Castle, the Cambridges are doing the same at Anmer Hall in Sandringham, and the Sussexes have recently hunkered down in Los Angeles, California.
Bianca Betancourt is the culture editor at HarpersBAZAAR.com, where she covers all things film, TV, music, and more. When she's not writing, she loves impulsively baking a batch of cookies, re-listening to the same early-2000s pop playlist, and stalking Mariah Carey's Twitter feed.


text:
Contemporary Creole blues with an African flair.
Pascal Danae-Guitar and vocals
Baptiste Brondy- Drums and vocals
Previously on Delgres …
In 1802, only 8 years after it was abolished by French Revolution, Napoleon Bonaparte restored slavery in the French colonies. In Guadeloupe the mixed blood commander, Louis Delgrès gave his life to prevent the return of the abomination. In vain.
After Delgres and his supporters’ deaths, fierce repression fell upon Guadeloupe .
Thousands were forced into exile or fled, some to Louisiana, birthplace of the Blues. And the air still vibrates from the remaining fragrance of a secret blues, whispered solely at nightfall.
Long forgotten heroes that only the heart remembers; father, mother, cousin, brother or friend that no one will ever mention in books or papers but who gave everything, silently.
Such as Louise Danae ( Pascal’s ancestor) freed from slavery in 1841 along with her three children. She was 27.
Delgres is retrieved memories of blended songs, dances and tears of the long lost drifting souls of New-Orleans, where the blues get loud with the sound of rust, struggle and hope.
Like a broken barrel of guadeloupean rum flooding the Mississipi delta, Delgres gets everyone drunk with music. So drunk with music that Africans, Indians, poor whites and all the others don’t really know where to stand anymore. So they dance! They dance to that ragged blues!
And here we are, prestigious clandestins, aboard this ship,freely sailing from Pointe a Pitre to Congo square, from Lafayette to Basse Terre, under carribean stars, all together, yet alone with Delgres.
US TOUR DATES
10/4 @ Joshua Tree Lake RV & Campground – Joshua Tree, CA
10/5 @ Theatre Raymond Kabbaz – Los Angeles, CA
10/7 @ Joshua Tree Music Festival – Joshua Tree, CA

domain: artistic


text:
Baking Simulator 2014 is an exciting Cooking Game and published on May 29th, 2014 and has been played 23,804 times and has a rating of 77% after 398 votes.
Baking simulator 2014 delivers to you an awesome experience of baking and cooking. With first person view and lots of options to do with your mouse you are handed over with a unique cooking simulator of all times. Enjoy backing.
Baking Simulator 2015 - Baking Simulator 2016 - Baking Simulator 2017 - Baking Simulator 2018 - Baking Simulator 2019
Just Online Games is a great place to play best online games. We add more and more exciting & super games to our top online games collection everyday. Have fun playing over 33.000 online games.
Copyright © 2011-2017 Free Online Games, trademarks and logos are the property of their respective owners. All Rights Reserved.

domain: entertainment


Skyline GT-R BNR34
65100-RSR45 → 65100-RSR45-01
660101111 → 660102040
There is also a rain visor attached to the air cut-out duct to prevent water from seeping into the engine bay.
Item is carbon.
There may be scratches caused by the manufacturing process.
*This item has minor rubbed scratches from the production process since made of carbon. This is the unpainted product. Please send a body shop to apply the clear coating. We are not liable for the damage ( rubbed scratches ) from the production process.


text:
This preview has intentionally blurred sections. Sign up to view the full version.View Full Document
Unformatted text preview: 1. Fill in the box with the appropriate starting material(s), product(s) or
reagents. For products draw only the major organic products (unless
otherwise speciﬁed). Note: H30+ = dilute aqueous acid. D
1. LiAlD4 OH
2. H20 0
1. EtMgBr m
2. H3O+ 2. In the box below, provide a detailed electron-pushing mechanism of the
reaction. Be sure to include any intermediates and relevant resonances
structures. 0—0» H 4‘- HI (2 equiv) f VI 3. Provide a detailed electron-pushing mechanism of the reaction shown
below. Be sure to include any intermediates and relevant resonances
structures. HO \ st04 OH mm .qsvzﬁwv ...
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This note was uploaded on 03/03/2010 for the course CHEM 237 taught by Professor Andersen during the Spring '08 term at University of Washington.
- Spring '08

domain: chemistry


text:
Protests Also Erupt Across South Carolina in Wake of George Floyd’s Death
Protests over the death of George Floyd also erupted across South Carolina this weekend. Curfews were enacted and ignored in multiple counties and cities including Columbia, Charleston, Myrtle Beach and more. Following peaceful protests on Saturday, downtown Charleston was vandalized, burned and looted. The rioters were met with tear gas, armored cars and 35 people ended up being arrested. Mayor Brenda Bethune declared a civil emergency for the city of Myrtle Beach yesterday and a curfew was put in place from 6 PM to 6 AM. At least 23 people have been arrested, many for disorderly conduct, over the demonstrations held yesterday.

domain: sociology


text:
All News Releases By Date
U.S. EPA ANNOUNCES CHANGES IN CLEANUP AT KOPPERS SUPERFUND SITE
Release Date: 9/5/1996
Contact Information: Paula Bruin, U.S. EPA, (415) 744-1587
(San Francisco)--The U.S. Environmental Protection Agency (U.S. EPA) announced it has decided on an amendment to the plan for cleaning up contaminated soils at the Koppers Superfund site, Oroville, Calif.
The amendment affects both the soil cleanup standards and the cleanup technologies selected in the 1989 record of decision. The state of California concurs with the amended remedy.
The amended plan will base the soil cleanup levels on continued industrial, rather than future residential, use of the site. The revised plan was first proposed after several discussions with local land use planning authorities, local officials and the community. The cleanup will protect workers at the site, and deed restrictions will prevent future residential development of the Koppers property.
U.S. EPA reevaluated soil cleanup standards and technologies that were selected in 1989 when the original cleanup decisions for the Koppers site were made. Further analysis and studies found that the chosen cleanup technologies were not successful in reducing contaminant levels to the residential cleanup standards.
The revised soil cleanup plan calls for contaminated soils to be excavated and placed in an on-site landfill. The excavated areas will then be filled with clean soil. Beazer East Inc., the company responsible for financing the cleanup, has already begun construction of the landfill cell. Excavation of contaminated soil will begin later this year and should be completed within 12 - 18 months. After all the soil is placed in the landfill, a final cap consisting of a heavy duty liner and protective soil layer will be placed over the top of the landfill cell.
As part of U.S. EPA's overall cleanup plan, two groundwater treatment plants have been built to clean up contaminated groundwater and prevent any further migration of contaminants from the Koppers property.
The Koppers site is located just south of Oroville near State Route 70. Wood treating operations have been used at the site since 1948. Chemical handling procedures, wood treatment and storage operations resulted in soil and groundwater contamination. The groundwater, surface water and soils have been contaminated with pentachlorophenol (PCP), dioxins, polynuclear aromatic hydrocarbons, chromium and arsenic.
In 1984, the Koppers site was added to the National Priorities List (NPL). The NPL is the list of uncontrolled hazardous waste sites nationwide which pose the greatest threat to human health and the environment. Sites on the NPL qualify for federal long-term cleanup efforts.
# # #

domain: news


text:
The government has approved draft changes to the Money Laundering and Terrorist Financing Prevention Act, which will significantly improve the scope of preventing money laundering.
The planned changes would create protection for whistleblowers and a legal basis for creating a database of bank accounts based on the electronic arresting system. The Financial Intelligence Unit will be granted access to the register to be created. The changes in legislation will create a legal mechanism for improving the quality of data on beneficial owners of companies and other legal entities.
According to the Minister of Finance Martin Helme, the draft legislation is very important for improving Estonia’s scope for countering money laundering. “Estonia is not a place for money laundering. The government will do everything to keep our economic environment to be honest and transparent. The parliament last week passed legislation imposing stricter regulations on granting licences for activities involving virtual currencies. The government has also presented the parliament with draft legislation designed to increase maximum fines in the financial sector. These laws give Estonia a stronger legal basis to counter money laundering much more efficiently,” said Finance Minister Martin Helme.
The draft approved by the government will also create a basis for establishing a list of politically exposed persons in Estonia, for whom higher requirements will be applied for the prevention of money laundering. Such persons include ministers, members of parliament, heads of constitutional institutions and state authorities as well as board members of political parties. The draft also increases protection of whistleblowers and widens the circle of obliged entities who must take into consideration stricter money laundering prevention measures in their activities. The planned changes are important step from Estonia in transposing rules established with the fifth European Union directive on the prevention of money laundering (AMLD V).
The adoption of the draft legislation is important in anticipation of the Moneyval assessment in the autumn of 2021. This time Moneyval will assess how Estonia has implemented different laws and regulations in practice and consider the capability of the country’s institutions to tackle money laundering. “We must exert effort as a state in order to pass the assessment successfully," said Finance Minister Martin Helme.
Moneyval or Committee of Experts on the Evaluation of Anti-Money Laundering Measures and the Financing of Terrorism is the Council of Europe expert committee that evaluates countries' measures for preventing money laundering prevention.
The draft legislation approved by the government and the explanatory memorandum are available for review on the website of the Ministry of Finance:
· Explanatory memorandum https://www.rahandusministeerium.ee/sites/default/files/news-related-files/rahapts-191218seletuskiri.pdf (PDF)

domain: finance


text:
A petition which has attracted more than 19,000 signatures against the possible closure of a rural village school has been handed in to 10 Downing Street.
Branton Community First School could shut its doors for the last time in summer 2017, as part of proposals for the reorganisation of schools under the Alnwick Partnership. Consultation on the plans runs until October 22.
Last week, Branton pupils Charlie and Immy Wood, along with mum Claire – who launched the petition – and grandmother Anne, went down to London to hand in the document.
Signatures have come from around the world and Anne said that it showed the strength of feeling against the proposal to shut the schoool, which recently marked the 90th anniversary of being in its current building. Last Friday, Berwick MP Anne-Marie Trevelyan went to the school to chat to parents and pupils.
The petition can still be signed online. Signatures have also been added to paper copies of the petition.


text:
Why Suffer? Gulf Coast Eye Institute is Here for You
Dry eye is more common today than ever before! More than 100 million people worldwide suffer from dry eye, which can be caused by many factors. This condition is often painful and certainly annoying.
Why so much dry eye?
Near work – computers, smart phones, video games, certain occupations – all of these things are likely to blame for the increase in dry eye symptoms. All of these activities interfere with quality and quantity of blinks. Not enough quality blinks means not enough natural tears, which means dry eye symptoms.
Common symptoms of dry eye include dryness, burning, grittiness, soreness, irritation and eye fatigue.
Dry eye can affect your life – at work and at home – including making it difficult to work comfortably at a computer monitor. At Gulf Coast Eye Institute, we offer a variety of treatments for dry eye depending on its source and severity.
- Addresses root cause of the most common form of dry eye
- LipiFlow is an exciting breakthrough in the treatment of dry eye.
- LipiFlow treatment addresses the root cause of evaporative dry eye, the most common form, by unblocking the meibomian glands that secrete oily lipids.
In controlled clinical studies of patients who received a single LipiFlow treatment, the average meibomian gland score at 4 weeks increased by 2-3 times over the baseline condition! In other words, LipiFlow uses heat and gentle movement to unclog the glands on the rim of your eyelid that help keep your tears from evaporating. When they’re free and clear, they’re able to function properly to keep more tears on your eye’s surface.
The LipiFlow System is a non-invasive, in-office treatment that takes only minutes to complete for each eye. Many patients report a noticeable improvement in the days following the LipiFlow treatment, with relief continuing to improve 3-4 weeks following the procedure. This treatment can be repeated as needed.
Schedule Your Dry Eye Consultation | Or Call To Talk to a Gulf Coast Eye Institute Patient Care Coordinator 956-320-7510.
In the Event There Is Trauma or Injury To The Eye
PROKERA® is a therapeutic device used by Gulf Coast Eye Institute eye doctors to protect, repair and heal damaged eye surfaces. PROKERA is best described as a biologic corneal bandage. It is made by clipping a piece of amniotic membrane tissue in between two rings made out of a clear, flexible material.
For Patients With Irregular Shaped Corneas or Keratoconus, We Feature SynergEyes Hybrid Contact Lenses.
For those who have been diagnosed with keratoconus, Gulf Coast Eye Institute is pleased to offer patients SynergEyes lenses. SynergEyes makes hybrid contact lenses for patients with astigmatism, presbyopia and irregular corneal conditions. Patients can now see life with crystal clear vision, clarity and comfort all day long. This is the only hybrid lens that is highly breathable made from healthy materials and is an advanced lens designed specifically for people with irregular corneas.

domain: medical


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The Northern Lights are one of the most spectacular natural phenomena. They are also known as aurora borealis and occur when electrically charged particles from the sun collide with particles in our atmosphere. The energy released by this collision produces an array of colours that we can see when it is dark outside.
The northern lights season in Lapland lasts for several months, but there are some things to know before visiting Lapland during this period to see the northern lights. So here are 6 interesting facts about the northern lights in the village of Levi (Lapland) and beyond:
1. About the Northern Lights Village in Levi
The Northern Lights Village in Levi (Lapland) is a resort that offers accommodation in traditional Finnish log cabins, as well as activities such as dog sledging, snowmobiling, and reindeer safaris. It is located in a prime location for viewing the Aurora Borealis, or Northern Lights.
The village is also near the Levi Ski Resort, making it a popular spot for winter sports enthusiasts. Overall it is a popular tourist destination for experiencing the natural beauty of Lapland and the Northern Lights.
2. The Aurora Cabins
Experience a unique way to stay and sleep under the Northern Lights. The Aurora Cabins at the Northern Lights Village are a magical way to experience the wintry star-filled sky and the Northern Lights from your bed. The laser-heated glass roof opens up into the northern sky, directly above the bed. These magical glass cabins are heated with laser-heated glass, offering you a warm restful sleep while lying comfortably beneath the starry sky and aurora borealis.
The Aurora Cabins are a unique way to experience the wintry star-filled sky while lying comfortably in bed. The laser-heated glass roof opens up into the northern sky, directly above the bed. When it's time to sleep under the stars again, you can close it back down! Each cabin is equipped with all amenities including a fireplace and hot tub, so you can enjoy it all year round.
This is the perfect getaway for couples or solo travellers who want to experience nature and the Northern Lights. It's the only place in Finland where you can see the magical lights without having to ski out into the wilderness. You'll get a warm welcome, cosy accommodation and an unforgettable experience.
3. Northern Lights or Aurora Borealis
Aurora Borealis, also known as the Northern Lights, is a natural phenomenon that occurs in the night sky above the polar regions. The lights are created when solar winds collide with Earth's magnetic field and cause the gases in our atmosphere to glow.
The Northern Lights can be seen from many places around the world but it is most common to see them at higher latitudes during autumn and winter. When you visit Levi village (Finland), you are in an ideal location for viewing these magnificent lights!
4. Aurora Season in Lapland | Northern Lights season
When can you see the northern lights? You'll have to wait until September or October to see the Northern Lights, but it's worth it. The best time of year is from September to March.
Winter is a popular time of year for people who want to experience this phenomenon, as temperatures are colder and there's less light pollution. The Northern Lights are at their most vivid during the months of December to February when the sun barely sets. You can see them on any night of the year, though their visibility is best between these months.
To get a good view of them, you should head up north and take in one of the many tours that provide blankets and hot drinks – or even a glass of champagne – while you wait for them to appear. Aurora Borealis are most visible when there's no light pollution from nearby cities or towns. They are often seen as greenish streaks across the night sky.
5. How can you hunt for Aurora in Lapland?
The Northern Lights are one of the most spectacular phenomena in nature and can be seen from time to time in Lapland. For those who do not have much experience or knowledge about the Aurora Borealis, it may seem impossible to find them yourself. However, finding your own northern lights is not nearly as difficult as you may think!
To start out with, you need to know when and where these northern lights appear most frequently. There are several factors that influence how often they appear:
Time of year: In general, they can be seen between September and March (although this varies depending on where you live). The best months are generally November through February; however, there are exceptions! Keep in mind that weather conditions also play an important role here: so keep reading if that's something important for your trip planning purposes too...
Time of day: If we're talking about daytime sightings only, then this simply comes down again mostly just because during these hours there will usually be less light pollution around due to fewer people being awake yet — meaning less interference from artificial sources such as street lamps etcetera).
One of the most exclusive locations is near the resort of Levi, away from the hustle and bustle of tourism, where you'll have an unobstructed view of the northern horizon and an almost 360° view of the sky.
Fancy a trip to this place?
Then book one of Scandinavian Travel Group's unique tours in advance here to hunt for the northern lights in comfort and enjoy your stay at Levi Resort:
POLARMAN'S CAMP 1
POLARMAN'S CAMP 2
The programs can offer you the following pleasant extras:
Warm-up area in the Aurora Dome
Outdoor campfire area, grilled marshmallows and sausages
Warm drink (non-alcoholic berry juice or our special magic drink) with gingerbread.
Visit Aurora hunters’ Snow Igloo Park
Photo and video session
6. The best way to photograph the northern lights
The best way to photograph the northern lights is with a tripod. Tripods allow you to keep the camera steady and ensure that your shots are in focus. It's also important to use a wide-angle lens so you can capture more of the sky and make sure that there is room for movement.
When photographing aurora borealis, it's important to choose a shutter release method that will help reduce blurriness caused by camera shake or subject motion (for example, moving clouds). A cable release should work well for this purpose if you're using an SLR camera—but if not, try setting up your smartphone so it can act as an external shutter button without needing any cables at all!
An aperture setting around f/4 works well for aurora photography because it allows enough light in but blurs out some of those distracting stars around the edges of what we see with our eyes (which makes them seem brighter).
Try setting your ISO low too; this will let us get longer exposures without getting too much noise pollution onto our images when they're displayed later on computer screens or printed out onto paper prints themselves!
7. There are plenty of ways to see the Northern Lights, but staying at a lightproof village might be the best way
To see the Northern Lights, you have to be in the right place at the right time. While you could certainly take a chance on your own and hope for the best, it's much easier to join one of these tours that will guarantee you see the lights.
Stay at a lightproof village like Northern Lights village Levi in Lapland
These villages are specially designed so that light from street lamps, traffic and other sources of illumination does not enter into them (instead being directed away from them). This means guests can enjoy an authentic Lapland experience without any artificial light pollution!
Stay at a hotel with blackout blinds
Many hotels in Finland provide complete darkness by closing their blinds during bedtime hours so guests can sleep without disruption from any nearby street lamps or other forms of artificial illumination.
Stay in a cabin or yurt near Finland's dark national parks
There are many spots throughout Lapland where no artificial lighting exists, including inside some parks which were created specifically for this purpose! Just make sure to bring warm clothes; these areas tend towards very cold temperatures even during summer months due to high elevation levels above sea level (the average elevation level is around 1000 m).
8. Where else can the northern lights be seen except for Lapland
If you want to see the northern lights, you have to go north. The aurora borealis can be seen in northern parts of Europe, northern parts of the USA and Canada, northern parts of Norway and Iceland, and northern parts of Russia. The aurora australis can be seen in southern parts of Australia.
The Northern Lights can be seen from many places around the world but it is most common to see them at higher latitudes during autumn and winter. When you visit Levi, you are in an ideal location for viewing these magnificent lights!
All in all, you're hunt for the Northern Lights in Lapland should be an exciting adventure. The lights are elusive and can be difficult to find, but with some patience, perseverance and luck (and maybe even a few tips from this blog post), you’ll have no problem spotting them!
This article contains photos used with permission from @ScandinavianTravelGroup.

domain: geography


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Survey respondents admitted to taking their pet’s health and wellbeing seriously. At the same time only 61 percent said their dogs are vaccinated for Lyme and less than half (47%) are vaccinated against lepto. What’s more, 33 percent and 69 percent, respectively, are unsure about the prevalence of Lyme or lepto in their area, highlighting the urgent need for broader awareness of risk exposure and proper prevention.
A report from the ASPCA (The American Society for the Prevention of Cruelty to Animals) found that more than 23 million American households – or about one in five – welcomed a pet into their home during the pandemic. As COVID-19 restrictions lift around the country, owners and pets who spend more time outdoors, traveling and socializing with other pets will find themselves vulnerable to Lyme and lepto.
Lyme disease in dogs can cause a number of serious symptoms, including joint swelling, depression and loss of appetite. Dogs that are at risk for Lyme disease are also at risk for leptospirosis – a serious and potentially fatal infection that carries symptoms such as vomiting, anorexia and lethargy. Dogs are at risk when they lap water out of a puddle or are exposed to contaminated mud and soil that infected animals have urinated in.
“Whether you live in rural areas, the suburbs or in the city, your dog could be exposed to diseases simply by engaging in their regular daily activities,” said Dr. Casey Locklear, Elanco’s U.S. medical lead for infectious disease prevention. “At Elanco, we believe vaccinated pets are the happiest pets. Pets and parents share a unique and loving bond and our goal is to make sure pets live longer, healthier lives.”
Vaccines are the best preventative measure for protecting pets against infections and the long-term, negative impacts of disease. Elanco offers innovative products to advance the health of animals, including a robust portfolio of pure, safe and effective vaccines.
The nationwide survey, conducted by Savanta, January 2022, consisted of 3,002 American adult respondents.
Additional highlights include:
- 79 percent say our pet’s well-being is high on our to-do list
- 85 percent agree that vaccinations for dogs are valuable
- 52 percent let our pets sleep in the bed
- 21 percent kiss our pets on the lips
- 36 percent share food with our pets
- 77 percent describe our pets as “loving”
- 83 percent consider their pet their “ride or die”
These new findings support a study published by Elanco in January 2022 that analyzed variability in non-core vaccination rates of over 3.5 million pets across the United States. That report found wide variation in lifestyle vaccination rates, highlighting a need for veterinary practices to address gaps in patient protection.
Pet owners should seek out information about pet disease and lifestyle vaccines from reputable and trusted veterinarians. The full Wag Stats survey results and more information about Lyme and lepto can be found here.


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Awesome Tanks 3 Game elevates the thrilling experience of tank warfare to new heights with its latest release.
This top-down 2D tank shooter captivates players with its visually stunning graphics, innovative physics engine, and streamlined twin thumb controls, ensuring a seamless gaming experience. As war erupts across the digital battlefield, players are tasked with annihilating monstrous foes, demolishing enemy tanks, and exploring uncharted territories within the game's expansive levels.
What sets Awesome Tanks 3 Game apart is its deep customization system. Players can fine-tune their combat vehicles using the in-game currency, upgrading to more powerful weaponry and enhancing their tank's performance to suit their battle style. Whether engaging in solo missions or diving into the strategic depth of 2-player tank shooter games online, there is a wealth of content to explore.
For those who revel in creativity, the Level Editor is a standout feature, allowing you to design and share custom levels with the gaming community, adding a unique personal touch to the warzone. From the intensity of 3d tank games to the strategic gameplay of war tank games and the adrenaline rush of zombie tank game encounters, Awesome Tanks 3 Game delivers a diverse and immersive experience.
Whether you're a fan of offline tank games for PC, seeking lightweight shooting games under one GB, or craving the competitive edge of 1v1 shooter games online, tankroyale.io promises endless entertainment and challenge.
Release date: 14 March 2024 , Platform: Web browser
204 played times

domain: game


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An FIR has been filed against the Vishva Hindu Parishad (VHP) and the other organisers of an event in Delhi, where certain speakers allegedly delivered hate speeches, police said on Monday.
The VHP dismissed the claim that permission for the event was not taken from the city police as "laughable" and said police personnel were deployed at the venue of the event in Dilshad Garden.
Delhi BJP MP Parvesh Verma courted controversy on Sunday after he allegedly called for a total boycott of a community at the event held to protest against the killing of a 19-year-old Hindu man in northeast Delhi.
Verma, however, said he did not refer to any particular community in his address.
"An FIR has been registered against the organisers under section 188 (disobedience to order duly promulgated by public servant) of the Indian Penal Code (IPC) for not taking permission from police," Deputy Commissioner of Police (Shahdara) R Sathiyasundaram said.
The event was organised by several right-wing outfits, including the VHP.
VHP spokesperson Vinod Bansal said it is laughable that the police is saying no permission was taken for the programme, during which thousands of people, including police personnel, were present.
"Let alone permission, we fixed the venue at the Ramlila Ground in Dilshad Garden after suggestions and recommendations from senior police officers. We had earlier planned to organise the gathering near Manish's (the man killed in northeast Delhi) house but on the request of the police, changed the venue to the Ramlila Maidan," he claimed.
In a video purportedly of the event, Verma is heard saying, "Wherever you find them, there is only one way to straighten them -- total boycott. Do you agree with me?"
The Bharatiya Janata Party (BJP) MP told PTI, "I did not name any community. I just said those involved in the killing of Hindus need to be boycotted."
Manish was stabbed to death in Delhi's Sundar Nagri earlier this month.
The Delhi Police has arrested all the accused in the case -- Aalam, Bilal and Faizan -- and said they killed Manish due to an old rivalry.
The police had on Sunday said it was obtaining the details of the event held in east Delhi's Dilshad Garden and added that no permission was taken for organising it.
Verma is heard in the video seeking a response from the crowd to his call for a "total boycott" of the community and asking them to raise their hands if they agreed with him.
"We will not buy anything from their shops or pay them any wages. This is the only treatment for them," he is heard saying in the video.
Manish's killing was captured on a CCTV camera. In the footage, three men are seen walking down a lane and accosting the victim.
The footage shows one of the three men grabbing Manish by his collar and slapping him. The other two also join in and start stabbing the victim with knives.


At each of our ten-year anniversary milestones, Coast Guard Foundation leadership paused to reflect on the organization's accomplishments and recognize those who contributed to its success, and honor the men and women of the United States Coast Guard who serve with honor, respect and devotion to duty.
This year- our fiftieth-anniversary-mark- is no different, and we proudly produced a video that highlights our beginnings in 1969 as the Coast Guard Academy Foundation. How Do You Say Thank You? recognizes those who founded the organization, and those who later expanded our mission, and features our pillar areas of support for the Coast Guard. The production acknowledges the generosity of our donors over the last fifty years who have helped us stand shoulder-to-shoulder with those who serve.
Here's how we acknowledged our anniversary in other milestone years:
1979- Plaque dedicated at the Coast Guard Academy in recognition of 10 years of support.
1989- Special feature in the Coast Guard Foundation Annual Report highlighting 20 years of excellence and the Foundation’s newly expanded mission
1999- Timeline and support highlights in the Annual Report reflecting 30 years of programs and projects
2009- Commemorative book published detailing the Foundation’s history and reflecting on core support and event program. The book, Legacy, was dedicated to G. William Miller, one of the organization’s founding board members and key supporters. The book was released at the Coast Guard Foundation’s Salute to the Coast Guard in October 2009 in New York City.


U.S. gas pipeline industry regulations now require additional compliance from pipeline operators. The first rule went into effect on July 1, 2020 with some enforcement discretion due to COVID-19. Whether you have fully implemented the rule or are just starting to implement the rule, this paper is a good overview.
In hopes of preventing future loss of life and property, Congress mandated the “Pipeline Safety, Regulatory Certainty, and Job Creation Act of 2011,” which requires that the Pipeline and Hazardous Materials Safety Administration (PHMSA) develop stronger regulations.
These updated regulations can pose significant challenges to pipeline operators. Lake Superior Consulting, a Shawcor company, has put together eight steps for you to follow to ultimately help you meet current regulations, improve safety, and your overall operation.


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The theme that I am exploring is Healing.
a little explanation on the conceptual drawing:
Since the artist uses beautiful crochet and lace to pursue this theme, I am going go back to the beginning step/material for making a crochet: thread. Having the idea of healing in mind, at this stage, I am using a messy bun of thread. At first, it does not even look like a beautiful crochet, but the fact is the crochet cannot be made if the thread is not there. So the thread is the initial step toward a beautiful (healed) end, however, like so many of us, the thread in here is not flawless, ready to start becoming a crochet. In here we see a messy potential bun of thread (a scared figure/symbol – which has the potentials of getting healed). I printed the crochet patterns on the background paper, by placing a candle in the center of this messy bun, it creates the effects of the potential beautiful shadow of this messy bun: getting healed/becoming a crochet.Then, I cut out a corner of this piece of paper in the shape of crochet; again more encouragement toward the strong belief that even that messy bun had the potential healing if it has the motivative light withing it which makes it see the final picture: a beautifully finished crochet.
The bay that I am assigned to is near University center, so it is basically a rather crowded passageway for students.
By identifying this very characteristic of this particular sight, I am going to continue this idea (passageway), but I want people to get out of their everyday life thoughts while they are walking toward UC and notice this structure in a rather joyful, pleasant way that brings a smile on their face. Smile even for a moment is a beautiful, powerful sign than body shows a state of happiness. their smile while passing under this passageway shows that they are torn away from the stress they are dealing with as a result of anything throughout the day which can be considered as a scar that they get used to. But by being drawn out of their state of mind into a beautiful, bright, ordered, harmonic passageway, is short but heals the scar (the stress, the every day thinking).
I would like to be able to have this messy bun as a passageway on the pavement, but once you pass through inside this installation, you notice that it looks nothing like outside of it. the inside it very much ordered knitting patterns with are all covered in a white color to even shines it more once the sun hits it from outside.
the goal is to remind people, no matter how messy the life, the situations, the people themselves look like the healing can rise from withing at any moment one wishes and puts an effort toward it.
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domain: hobby


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Since last year, I shared my experience of “senile plaque” on my face. Some people have been concerned about how it is after treatment, and whether there is “black back”.
nearly 10 months since the last treatment, I feel that the effect is still good. There are still some imprints, but they are still too weak than before treatment. You can compare the appearance before treatment in the original article with the current appearance in the figure below.
after treatment, I paid more attention to sunscreen than before, which should have some protective effect. Moreover, I also experienced a photon therapy after laser treatment. The photon itself has a certain effect on the pigmentation of the skin, and may also produce some superimposed effects.


HDB resale prices dipped 0.1 per cent in October compared to September, driven by a 0.9 per cent fall in the resale prices of five-room flats.
By contrast, the resale prices of HDB three-room flats and executive flats rose 0.6 per cent and 0.8 per cent respectively, while resale prices of four-room flats stayed flat.
This was according to the SRX Property Price Index for HDB Resale released on Thursday.
Year on year, prices have decreased by 0.5 per cent from October 2015 and fallen 11.5 per cent since the peak in April 2013.
On the transactions side, resale volume rose 0.4 per cent to 1,673 resale flats sold in October, from 1,666 transacted units in September.
Year on year, resale volume fell 4.2 per cent compared to 1,746 units resold in October 2015. Resale volume was also down by 54.2 per cent compared to its peak of 3,649 units in May 2010.