text:
|Publication number
|Publication type
|Publication date
|May 20, 1975
|Filing date
|Oct 16, 1973
|Priority date
|Oct 16, 1973
|Publication number
|Robert E Kolb
|Original Assignee
|Minnesota Mining & Mfg
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (3), Referenced by (38), Classifications (18)
|External Links: USPTO, USPTO Assignment, Espacenet
' United States Patent 93 Kolb [ FLUOROELASTOMER COMPOSITIONS WITH TRIORGANOPHOSPHORUS OXIDE [75] Inventor: Robert E. Kolb, St. Paul, Minn.
[73] Assignee: Minnesota Mining and I Manufacturing Company, St. Paul,
Minn. v
[22] Filed: Oct. 16, 1973 [21] Appl. No.: 406,836
[52] US. Cl 260/47 UA; 260/42.27; 260/47 UP; 260/80.77; 260/80.76; 260/87.7; 260/884 May 20, 1975 [56] References Cited UNITED STATES PATENTS 3,655,727 4/1972, Patel et al 260/47 UP 3,712,877 l/l973 Patel et al.... 260/87.7 3,752,787 8/l973 De Brunner 260/44 B Primary Examiner-Stanford M. Levin v Attorney, Agent, or Firm-Alexander, Sell, Steldt &
DeLaHunt [57] ABSTRACT 8 Claims, No Drawings FLUOROELASTOMER COMPOSITIONS WITH TRIORGANOPHOSPI-IORUS OXIDE This invention relates to a method for cross-linking fluorinated polymers and crosslinking compositions for use therein. In particular, this invention relates to compositions having improved processing characteristics and more particularly to compositions comprising adjuvant amounts of 'triorgano phosphorus oxides which cure more readily than previously known compositions, without loss of valuable physical properties.
In general, linear polymers are thermoplastic in nature and exhibit flow under the influence of heat and pressure. Such polymers can be resoftened as often as desired and are usually soluble in selected solvents. However, crosslinked or vulcanized polymers are generally thermoset, i.e., insoluble in most solvents and incapable of being resoftened without decomposition,
because they become permanently hardened. A linear polymer may, nevertheless, contain a small number of crosslinkages without completely losing its thermoplastic properties. It is generally desirable to convert thermoplastic elastomers into crosslinked elastomers in order to decrease their solubility and thermoplastic flow properties and to obtain a harder and tougher product. The crosslinking of elastomers is commonly referred to as vulcanization.
Among the most difficultly vulcanizable thermoplastic polymers are those prepared by the polymerization of halogenated monoolefins, such as, for example, the copolymers of chlorotrifluoroethylene and vinylidene fluoride, the copolymers of perfluoropropene or pentafluoropropene and vinylidene fluoride and the terpoly-v mers of perfluoropropene, vinylidene fluoride and tetrafluoroethylene. Many of these fluorinated thermoplastic polymers have unique and valuable properties. The polymers are crosslinked to retain these properties and at the same time decrease the thermoplastic flow and solubility.
In order to providea molded, cured product from a fluoroelastomer such as those above, a complex procedure must be followed, each step of which influences both the properties and the cost of the final product.
Initially, a uniform mixture of the desired formulation of gum stock and filler, curatives, processing aids, etc. must be prepared. Mixing can be done, for example, on a Banbury mixer or on a two roll mill, but, because of the toughness of the gum stock and the intensive mixing action, considerable internal heat is generated which must be controlled in order to avoid premature curing, which would effectively prevent proper forming or molding. The mixing operation is best carried out so that the temperature of the mass does not exceed 120 C. (250 F.) and preferably is maintained between 95 and 120 C. (200 and 250 F.) by appropriate cooling. The resultant formulated gum stock may then be set aside for whatever period of time may be desired, varying from hours to months, until the final forming operation is undertaken. This forming may be effected by exformulated gum stock can be placed in the cavity of the mold and the mold closed and heated. In either process, the stock must flow uniformly throughout the mold to fill all of the inner portion and must flow together and join integrally anduniformly at the interface of two or more flow streams. At the molding temperature, initial curing takes place and must continue to a sufficient stage of cure so that the molded part will maintain its integrity without distortion or tearing when it is released and removed from the molds. The higher the mold temperature, the more rapidly such a press cured state can be attained. However, sufficient time must be allowed for the mold to be filled uniformly, and hence there is a practical maximum temperature. Ideally, the viscosity should not increase significantly during the initial flow which fills the mold but should then increase very rapidly to attain a sufficiently stable state for removal.
After removal from the mold, the part is customarily post cured or oven cured. If the cure has not advanced sufficiently during the molding step, the gases released during final cure may result in bubbling, blistering and distortion.
The utility of cured fluoroelastomers depends upon solvent resistance, good compression set characteristics, and resistance to degradation of'properties at elevated temperatures. These properties, combined with the generally good elastomeric characteristics of fluoroelastomers, have resulted in the commercial use of a relatively narrow range of compositions in which the major molar component, commonly vinylidene fluoride, is combined with lesser molar amounts of one or more of perfluoropropylene, tetrafluoroethylene, trifluorochlorethylene or monohydroperfluoropropylene. A filler is generally required from a variety which have been suggested for use, although the filler usually selected is a medium reinforcing thermal carbon black.
Because the characteristics of the cured product are determined largely by the particular curing system used, most of the improvements in the characteristics of the final product have resulted from improved curing systems. The curing system dictates the conditions of mixing, forming and curing, which have a major influence on the cost of the final product as well as exerting its influence on the physical and chemical properties.
The polyamine curing systems that first enabled the achievement of satisfactory commercial products continue to be of importance. Long experience with polyamine systems has allowed safe handling and reliable processing, with the major difficulty being the tendency toward permanent deformation after extended use, that is compression set. Various additives have been described as useful as process modifiers in the polyamine curing system. For example, Dixon et al. (Industrial and Engineering Chemistry, October, 1957, page 1690) suggest the use of tricresyl phosphate, trioctyl phosphate, and dioctyl sebacate as possible plasticizers in formulations showing high compression set even at relatively low temperatures.
A curing system based on quaternary ammonium derivatives has been developed (US. Pat. No. 5,655,727) which has many of the desirable handling characteristics of the polyamine system, but produces a final prod uct with much higher resistance to compression set.
This curing system allows safe milling at l20 C. (200-250 F.) and molding temperatures in the range 3 of l60l70 C. (320-335 F.) with good flow and a short cure cycle. Cure is so rapid, in fact, at these temperatures that the stock tends to be scorchy and careful handling is required to avoid partial curing during the milling operation.
To a considerably extent these difficulties are overcome by use of quaternary phosphonium curing system based on the presence of a compound in which the phosphorus atom is covalently bonded to 4 carbon atoms and ionically bonded to an anion as described in U.S. Pat. No. 3,712,877. The covalently-bonded radicals can be straight-chain, branched or cyclic organic radicals and can be saturated, unsaturated or aromatic. Generally 4 monovalent organic radicals are present, although the phosphorus atom can be part of a heterocyclic ring. Quaternary phosphonium compounds are generally used in conjunction with a nucleophilic organic compound in which one or more hydroxyl, primary amino or secondary amino radicals are bonded through the oxygen or nitrogen atoms to an aromatic nucleus. Conventional acid acceptors, modifiers, and fillers, particularly the carbon blacks, can be used. Such systems produce a compound which is safer than the quaternary ammonium systems, provide good mold flow and satisfactory cure times over a temperature range between about 150 C. (300 F.) and 230 C. (450 F.) and particularly from about l75-190 C. (350370 F. The characteristic viscosity versus time curves for such formulations show relatively slow buildup of viscosity up to a certain point and then a very rapid increase and thus allow safe mixing on mill or Banbury, extended storage, and economical curing at press conditions.
The use of triaryl phosphoranes as curing accelerators, particularly in combination with quaternary ammonium derivatives, is described in the U.S. Pat. No.
It is an object and aim of this invention to provide curable fluoroelastomer compositions having shortfrom the disclourated fluoromonoolefin containing at least one fluoride atom substituent on each doublebonded carbon atom, each carbon atom of said fluoromonoolefin being substituted only with fluorine, chlorine, hydrogen or a lower fluoroalkyl or fluoroalkoxy radical and at least 10% of the chain carbon atoms of said copolymer being -CH groups; (2) at least one quaternary phosphonium or ammonium compound; (3) at least one triorgano phosphorus oxide. It is found that the use of triorgano phosphorus compounds frequently allows reduction in amount of Ca(OH) with both improved rate of cure and retention of desirable physical characteristics, including improved resistance to compression set, as compared to the presently known formulations.
The vulcanizable polymers which are cured according to this invention are widely known linear, saturated, fluorinated polymers which can contain unreactive substituents selected from the group consisting of hydrogen, fluorine and chlorine and which are at least half halogenated. By half halogenated is meant that at least one half of the carbon bonded hydrogen atoms of the analogous non-halogenated polymer are replaced by halogen. The preferred vulcanizable polymers are at least half fluorinated; however, it is critical that the polymer chain include Cl-l units. Homopolymers of tetrafluoroethylene and other perfluorinated comonomers require vvery high temperature toeffect crosslinking and are not within the scope of this invention. I
Linear fluorinated elastomers generally contain disordered, saturated, fluorinated carbon chains which include a substantial number of CH units, usually at least 10 percent of the chain carbon atoms- Disorder in the carbon chains is ordinarily achieved by the copolymerization of at least two monoolefmic compounds of the type hereinafter described. When one of the monoolefinic compounds contains an unsaturated chain of three or more carbon atoms, alkyl side groups, e-.g., methyl, ethyl, etc. are present in the final polymer, and these alkyl groups are preferably perhalogenat ed, most: preferably perfluorinated. Points of unbalance in the carbon chain, which are necessary for elastomeric properties, are provided by these side groups. Such side groups cause a bending of the linear carbon chain and thus provide additional degrees of freedom in space, producing an unsymmetrical chain carbon atom to which they are attached. However, unbalance is also.
provided by the presence of other unsymmetrical units in the linear carbon chain, such as -CFCl- Irrespective of the units providing such points of unbalance,
whether by two physically different substituent atoms or by a side group on a chain carbon atom, at least 10 percent of the chain carbon atoms should be unbalanced.
The linear, saturated, fluorinated carbon chaininthe elastomers may also contain chlorine substituents, provided a single chain carbon atom has no more than one chlorine attached thereto to produce instability or to influence the chemical nature of the elastomer. The presence of more than one chlorine substituent on a single chain carbon atom produces a'point of rigidity in the chain, decreasing the flexibility of the chain and the elastomeric properties accordingly.
Among the saturated polymers which may be crosslinked in accordance with this invention are the fluorinated elastomeric copolymers of chlorotrifluoroethylene, vinylidene fluoride, 2- chloroperfluoropropene, a fluorinated methyl vinyl ether, perfluoropropene, tetrafluoroethylene, 1- hydroperfluoropropene (i.e. CFH=CFCF di-' chlorodifluoroethylene, trifluoroethylene, and 1,1- chlorofluoroethylene. These monoolefins may be copolymerized with each other in groups of two or more.. They may also be copolyi'nerized with other olefiriic compounds such as ethylene. The preferred elastomers are copolymers of vinylidene fluoride with at least one,
terminally unsaturated fluoromonoolefin containing at least one fluorine atom substituent on each double bonded carbon atom, each carbon atom of said fluoromonoolefin being substituted only with fluorine, chlorine, hydrogen or a lower fluoroalkyl (e.g. perfluoroalkyl of 1-4 carbon atoms or fluoroalkoxy radical of 1-4 carbon atoms) particularly perfluoropropene, tetrafluoroethylene, chlorotrifluoroethylene and lhydroperfluoropropene. Particularly preferred are the fluorinated elastomers produced by copolymerizing perfluoropropene and vinylidene fluoride, as described in U.S. Pat. Nos/3,051,677 and-3,318,854, and those tel-polymers produced by copolymerizing perfluoropropene, vinylidene fluoride and tetrafluoroethylene as described in U.S. Pat. No. 2,968,649. The elastomeric copolymers of perfluoropropene and vinylidene fluoride having between about and 50 mole percent perfluoropropene are outstanding in this respect. Mixtures of elastomers are also suitable, for example, a mixture of 70-95 parts of an elastomeric perfluoropropenevinylidene fluoride copolymer with 30-5 parts of an elastomeric trifluorochlorethylenevinylidene fluoride copolymer.
The adjuvant triorgano phosphorus oxides employed in the present invention are compounds containing at least one phosphorus atom, one oxygen atom bonded only to each phosphorus and, additionally, three neutral organic radicals which bond through carbon or through single oxygen atoms or single trivalent nitrogen atoms to each phosphorus atom. Such compounds include triorganophosphine oxides, triorgano phosphates, triorgano amido phosphates, and the like. Such materials are described for example in Kosolopoff, Organophosphorus compounds, Chapter 9, John Wiley and Sons, New York, 1950; Kosolopoff and Meier, Organic Phosphorus Compounds, Vol. 3, Chapter 6, Wiley lnterscience 1972. I
These triorgano phosphorus oxides can be represented by the formula (org) PO where org represents a neutral organic radical. The three organic radicals may be the same or different and each radical may contain from 1 to or more carbon atoms, although one to about eight carbon atoms are preferred, with a total of not more than about thirty carbon atoms associated with each phosphorus atom. The carbon skeletal chain of the organic radical may be linear, branched, or cyclic and may be saturated, unsaturated or aromatic and may contain catenary hetero .atoms, such as oxygen, in addition to carbon. At least one org group may also contain OP( org)-2. The chain may be substituted or unsubstituted, but the substituents, if any, should preferably be neutral, i.e., neither strongly acidic nor basic radicals such as radicals derived from acids or bases having ionization constants K and K in water at C. of at least 10 or salts thereof (e.g. carboxyl, sulfonic, or phosphorus acid or salts thereof or amines, hydrazines or salts thereof) although active hydrogen in a weakly acidic form, such as aliphatic hydroxyl radical, is acceptable in small amounts, e. g. 0.5% by weight or less of the compound. Neutral substituents include but are not limited to halogen, ether, OP(org) ester, oxo, hydroxyl, nitro, CN, alkyl, aryl.
Representative triorgano phosphorus oxides include: a)a
CH3 en o l l l CH CH CH O(CHCH O) CH-CH Oi (OC H The quaternary phosphonium compounds useful in preparing curable fluoroelastomer compositions are compounds which contain at least one phosphorus atom covalently bonded through carbon-phosphorus single bonds to four organic radicals and, additionally, through an ionic bond to an anion. Such materials, their characteristics and several methods of preparation are described, for example, in Organophosphorus Compounds, G. M. Kosolapoff, (John Wiley and Sons, New York 1950), particularly Chapter five. The four organic radicals bonded to each phosphorus atom may be the same or different, and each radical may contain from one to 20 or more carbon atoms, although two to about eight carbon atoms are preferred with a.
total of not more than about 30. The carbon skeletal chain of the organic radical may be linear, branched, or cyclic and may be saturated, unsaturated, or aromatic and may contain atoms other than carbon, such as oxygen, or sulfur in addition to carbon. The chain may be substituted or unsubstituted, but the substituents, if any, should preferably not be strongly acidic radicals (i.e. radicals derived from an acid having an ionization constant in water at 25 C. of at least 10 5) or a salt thereof (e.g. carboxyl, sulfonic, or phosphonic acid or salts thereof) although active hydrogen in a weakly acidic form such as an aliphatic hydroxyl radical is acceptable in small amounts, e.g. 0.5% by weight -or less of the compound.
Quaternary ammonium compounds useful in preparing curable fluoroelastomer compositions are compounds which contain at least one nitrogen atom covalently bonded through carbon-nitrogen single bonds to four organic radicals and additionally through an ionic bond to an anion. Such material are described, for example, in U.S. Pat. No. 3,655,727, Column 4, line 65 to Column 5, line 2, and US. Pat. No. 3,752,787, at Column 6, lines 1 through 22. The four organic radicals bonded to each nitrogen atom may be the same or different, and each radical may contain from 1 to or more carbon atoms, although 2 to about 8 carbon atoms are preferred, with a total of not more than about 30. The carbon skeletal chain of the organic radical may be linear, branched or cyclic and may be satus I a) rated or unsaturated; compositions in which the nitrogen atom is bonded to one or more aromatic rings are relatively low in curing reactivity, and are generally less preferred. The radical may contain catenary oxygen, nitrogen, or sulfur atoms in addition to carbon atoms. The chain may be substituted or unsubstituted, but substituents, if any, should preferably not be strongly acidic radicals (i.e. radical derived from an acid having an ionization constant inwater at 25 C. of at least 10 or a salt thereof (c.g. carboxyl, sulfonic, or phosphonic acid or salts thereof). Although active hydrogen in a weak acidic form, such as an aliphatic hydroxyl radical is acceptable in small amounts, e.g. 0.5% by weight or less of the compound.
Represent quaternary ammonium compounds include: I
cs 2 I CH2 c N (ca;,) ca co primary amino, or secondary amino radicals are captate) not more than about 500 is preferred. The nature of the anion is not critical and is generally determined by the nature of the reactants used in synthesizing the quater-- nary compound. The anion is generally monovalent, but it may also be divalent or polyvalent. Typical anions are chloride, bromide, hydroxyl, methoxy, acetate,-
mercaptate, sulfate, bisulfate and the like. Neutral salts are preferred over acidic or basic phosphonium or ammonium compounds because of their better stability and easier handling, although it should be recognized that the compounds-may be converted to the basic form during compounding, since the vulcanizable composition contains large amounts of relatively strong base, such as magnesium oxide or calcium hydroxide.
In addition to the quaternary phosphonium or ammonium compounds, it is usually desirable to use cocuratives. Such co-curatives are well known and are described in the literature, for example, in US. Pat. Nos. 3,243,411 and 3,502,628. A particularly preferred class described in US. Pat. No. 3,655,727 comprises the aromatic hydroxy or amino compounds, that is nucleophilic compounds in which one or more hydroxyl,
bonded through the oxygen or nitrogen atom of the radical to an aromatic nucleus, such as phenyl, naphthyl, and the like. Co-curatives containing two aromatic hydroxyl groups are more particularly preferred. Such co-curatives are described and exemplified, for example in US. Pat. No. 3,752,787, as 'at Col. 3, line 33 to C01. 4, line 35 as di-, tri-, and tetrahydroxybenzenes, napthalenes, and
wherein A is a difunctional aliphatic, cycloaliphatic, or aromatic radical of 1-13 carbon atoms, or a thio, oxy, carbonyl, sulfinyl, or sulfonyl radical, A is optionally substituted with at least one chlorine or fluorineatom; x is 0 or 1; n is 1 or 2; and any aromatic ring ofthe polyhydroxylic compound is optionally substituted with at least one atom of chlorine, fluorine, or bromine. It will be understood from the above bisphenol formula that the OH groups can be attached in any position (other than number one) in either ring. Blends of two or more such compounds can also be used. One of the most useful compounds is the bisphenol known as Bisphenol AF, which is hexafluoroisopropylidene-bis(4- hydroxybenzene). I The compounds 4,4- dihydroxydiphenyl sulfone (Bisphenol S) and isopropylidene-bis(4-hydroxybenzene) or Bisphenol A are also considered as very useful bisphenols. Another very use- 9 ful compound is hydroquinone. others are illustrated by such dihydroxybenzenes as catechol, resorcinol, 2- methyl resorcinol, S-methyl resorcinol, 2- methyl hydroquinone, 2,5-dimethyl hydroquinone, and 2-t-butyl hydroquinone; also included are such compounds as 1,5-dihydroxynaphthalene and 9,10-dihydroxyanthracene. Others are illustrated as follows:
1 ,4,9 10-tetrahydroxyanthracene; 2,2',4,4'-tetrahydroxybenzophenone; 2,4-dihydroxybenzophenone; 2,4-dihydroxybenzoic acid; 4,4'-dihydroxytetraphenylmethane; 2,6-dihydroxyanthraquinone; 3,6-dihydroxyxanthone; pyromellitic-bis-(p-hydroxyphenylimide); 2,4-dihydroxyacetophenone; 4,4'-dihydroxybenzophenone; 4,4'-dihydroxydiphenyl sulfoxide; 2,4-dibenzoyl resorcinol; 2,4,5-trihydroxbutyrophenone; 2,4-dihydroxbenzaldehyde.
When changing from one co-curative to another in a given composition, one skilled in the art will be able to select a curing time and temperature that will give a suitable rate of cure for a particular application.
Referring to the bisphenol formula shown above, when A is alkylene, it can be for example, methylene, ethylene, chloroethylene, fluoroethylene, difluoroethylene, 1,3-propylene, l,2-propylene, tetramethylene,
chlorotetramethylene, fluorotetramethylene, trifluorotetramethylene 2-methyll ,3-propylene, 2-methyl-l ,2-propylene, pentamethylene, pentachloropentamethylene, pentafluoropentamethylene and hexamethylene. When A is alkylidene, it can be, for example, ethylidene, dichloroethylidene, difluoroethylidene, propylidene, isopropylidene, trifluoroisopropylidene, hexafluoroisopropylidene, butylidene, heptachlorobutylidene, heptafluorobutylidene, pentylidene, hexylidene, and 1,1-cyclohexylene. When A is a cycloalkylene radical, it can be, for example, 1,4- cyclohexylene, 2chloro-l,4-cyclohexylene, 2-fluoro- 1,4-cyclohexylene, l,3-cyclohexylene, cyclopentylene, chlorocyclopentylene, fluorocyclopentylene, and cycloheptylene. Furthermore, A can be an arylene radical such as m-phenylene, p-phenylene, 2-chloro-l,4- phenylene, 2-fluoro-l,4 phenylene, o-phenylene, methylphenylene, dimethylphenylene, trimethylphenylene, tetramethylphenylene, l,4-naphthalene, 3-fluoro- 1,4-naphthalene, 5-chloro-1,4-naphthalene, 1,5- naphthalene, and 2,6-naphthalene.
A further component which is contained in the final curing recipe is an acid acceptor, preferably an inorganic acid acceptor. Suitable acid acceptors are bases and include magnesium oxide, lead oxide (litharge, PbO), dibasic lead phosphite and zinc oxide, with magnesium oxide being preferred. The acid acceptors are used in amounts ranging from 2 to 25 parts per 100 parts of polymer. In addition, an optional base'is often desired as a cure accelerator. These optional bases are basic compounds and include inorganic oxides and hydroxides such as calcium hydroxide, barium carbonate, strontium hydroxide, and the like. The optional bases are preferably :used in amounts ranging from 0.5 to parts per 100 parts of polymer.
Triphenyl phosphine oxide is a typical 'triorgano phosphine oxide and it and other such phosphine oxides as tri-butyl phosphine oxide, phenyl diethyl phosphine oxide, diethyl octadecyl phosphine oxide and the like are employed in the present invention. Tributyl phosphate is a typical triorganic phosphate and those with skill in the art will readily perceive numerous variations which are possible within the scope of the pres ent invention. Thus, one may use triethyl phosphate, methyl dibenzyl phosphate, phenyl diethyl phosphate, methyl dioctyl phosphate and other such esters as may be conveniently available without departing from the scope of the invention as will become evident from the polymer, unless otherwise indicated, which is abbreviated pphr or alternatively parts phr. These proportions are general ranges and the particular amount for each particular cure, time and temperature will become apparent to those skilled in the art.
Formulation Ranges Component Parts phr (range) Quaternary compound 01 5 Triorgano phosphorus oxide 0.2 5 Acid Acceptor 0 25 together 3-40 Optional Base 0 25 Aromatic hydroxy or amino compound 0.2 5
Although useful elastomers are obtained within the aforementioned formulation limits, elastomeric products having particularly desirable compression set values may be obtained vy varying the relative amounts of the components within the specified ranges.
Of the acid acceptors, magnesium oxide is preferred.
At least about 2 pphr is required to provide a reasonable level of cure and rate of cure. While a satisfactorily curable composition can be obtained using only, for example, three parts of an optional base such as calcium hydroxide, it is generally preferred to use at least one part of acid acceptor such as magnesium oxide, along with the optional base to obtain improved resistance to heat aging. The maximum amount for the acid acceptor as listed above is not critical, as much as 50 to 60 pphr producing a usable but hard stock. Generally, however, no more than about 25 parts is necessary for adequate curing. Alternatively, zinc oxide, litharge or dibasic lead phosphite may be used in approximately the same proportions, and calcium oxide may sometimes be used.
In addition to the above acid acceptors, when an optional base is desired as an accelerator, it is usually present in amounts of from about 0.5 to 15 pphr. Calcium hydroxide is preferred, barium carbonate being milder and generally being used in somewhat larger amounts. At least about three parts of combined acid acceptor and optional base is generally used, for satisfactory curing. Use of eight parts or more minimizes shrinkage during. milling and preforming operations. Fillers are often added to the polymers discussed above to improvethe molding characteristics and other properties. When a filler is employed it is added to the vulcanization recipe in amounts of up to about parts phr, preferably between about 15 and about 50 parts. Examples of fillers which may be used are reinforcing thermal grade carbon blacks or nonblack pigments of relatively low reinforcement characteristics such as clay, barytes, silica, silicates, etc. Plasticizers, softeners and processing aids, preferably esters or ketones, may also be added if desired.
In accordance with this invention, the desired amount of the components of the crosslinking system is added to the unvulcanized fluorocarbon polymer (i.e., gum stock) and is intimately admixed therewith or compounded by employing any of the usual rubber mixing devices, such as Banbury mixers, roll mills, or any other convenient mixing device. It has been found that a Banbury is particularly suitable for large batches because it is more economical of time than milling. The triorganophosphorus oxides of the present invention allow adequate stability under mixing conditions even in the case of systems capable of very rapid press cure, e.g. 1 minute at 375 F. (190 C.)
The curing process typically comprises pressing the compounded mixture in or injecting the mixture into a mold and then, after demolding, i.e., removing from the mold, baking the demolded pressing in an oven. Pressing of the compounded mixture (press cure) is conducted at a temperature between about 95 C. (200 F.) and about 230 C. (450 F.) preferably between about 150 and 205 C. (300 and 400 F.) for a period of from 1 minute or less to about '15 hours, usually from 1 minute to 30 minutes. A pressure of between about 7 and about 210 kglcm preferably between about 35 and about 70 kglcm is imposed on the compounded mixture in the mold. The molds may be first coated with release agents, such as a silicone oil, and prebaked. The molded vulcanizate is then usually post cured (oven cured) at a temperature between about 150 and 315 C. (300 and 600 F.) usually at about 205 C. (400 F.) for a period of from 2 hours or less to 50 hours depending on the cross-sectional thickness of the sample. The temperature during the post cure is usually raised gradually from the lower limit of the range to the desired maximum temperature which is generally about 260 C. (500 F.) and may be held at this value for 24 hours or even longer.
A number of runs are made for comparison purposes cesses and compositions of the invention. The compositions used and the pertinent characteristics of curing and of the cured polymer are set forth in Tables 1 through 4. Tables 1 and 3 show compositions of Runs 1-1 1 and 12-21 respectively and the properties are set forth in Tables 2 and 4. In each case 100 parts of a copolymer of vinylidene fluoride and periluoropropene in molar proportions of 78:22 is used together with 30 parts phr of carbon black. As one point of comparison, material of Run 12 (Control run) requires 3 minutes press cure in commercial equipment whereas Run 13 (run according to the invention) requires 1 minute. Compounding is performed on a roll mill and curing is effected as described above.
Curing characteristics are measured in accordance with ASTM D 2084-71T, using an oscillator frequency of 100 cpm, and a 3 arc. Minimum torque and time to one pound rise are measures of the rate of initial cure, a measure of the resistance of the formulation to scorch. The torque at 12 minutes and time to pound rise indicate the rate of cure and the capability of the material to be adequately cured prior to demolding. Sheets are prepared, by by 1.8 mm. pressed at about 70 kg per square centimeter for 20 minutes at C. Physical properties are measured on samples diecut from these sheets in accordance with ASTM D 412-62T, die C.
Compression set is determined in accordance with ASTM D 395-61B using 25 mm. diameter O-rings, 3.4 mm. thick, compressed to 2.7 mm. under the indicated conditions.
Examples using hexamethylenediamine carbamate (runs 6 and 7) illustrate the polyamine cure with and without triorganophosphorus oxide, in this instance tributyl phosphate. This illustrates particularly that the use of a trialkyl or triaryl phosphate as a plasticizer as described by Dixon et al., supra, would not have provided the present results. Note that the phosphorus oxide does not significantly increase the rate of cure, nor does the resulting cured product have low compression set. Runs 9-11 inclusive and Runs 13 through 21 show compositions of the invention. Run 8 is for comparison with Run 9 and Run 12 for comparison with Runs 13 through 21.
(particularly Runs 1-11) and to demonstrate the pro- 45 TABLE 1 Run 1 2 3 4 5 6 7 8 9 10 ll Copolymer 100 100 100 100 100 100 100 100 100 100 1 Carbon black 30 3O 30 30 30 30 30 30 30 30 MgO 3 3 3 3 3 1O 10 3 3 3 3 Ca(O H) 6 6 6 6 6 6 6 6 6 2,2-bis-(p-OH-phenyl) hexafluoropropane 2 2 2 2 2 2 2 Hexamethylenediamine carbamate 1.5 1.5 Triphenylbenzylphosphonium chloride 0.6 l l 0 6 Tetrabutyl ammonium Captax 0.4 0.4 Tributyl allyl phosphonium chloride 0.4 Tributyl phosphate l l 1.5 1 1 1 Triphenyl phosphine oxide l 1 TABLE 2 Run 1 2 3 4 5 6 7 8 9 l0 l1 Rheometer C., 3 are, 100 cpm Torque, minimum (lbf. in 8 9 9 14 13 13 12 9 10 13 9 Torque, 12 minutes (lbf. in.) 94 9 10 21 21 48 53 107 104 98 94 T me to 1 lb. rise (mm 5.7 24.0 15.0 3.5 3.6 2.5 2.0 4.7 4.0 3.1 4.0 Time to 50 lb. nse (mm) 8.0 no no no no 12 12 6.9 5.6 4.5 6.0
CUTE cure TABLE 2 -Contmued Run 1 2 3 4 5 6 7 8 9 10 Postcured (22 hrs. at 260 C.)
Tensile kglcm 140 121 111 136 132 135 l Modulus lzglcm 5l 40 56 77 72 68 f Elongation at Break, 190 220 170 150 145 195 1g Hardness Shore A 75 70 71 80 82 75 I Compression Set (72 hrs. at 200 C.) 17 45 44 26 28 22 1 TABLE 3 Run 12 13 14 15 16 17 18 19 20 2 Copolymer 100 100 100 100 100 100 100 100 100 10 Carbon black 30 30 30 30 30 30 3O 3O 3 MgO 3 3 3 3 3 3 3 3 3 Ca(0l-l) 6 6 6 6 6 6 6 6 6 2,2-bis-(p-Ol-l-Phenyl)hexafluoropropane 2 2 2 2 2 2 2 2 2 Triphenylbenzylphosphonium chloride 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0. Tributyl phosphate 1 Trioctyl phosphate l Diethoxy hexylamino phosphorus oxide l Triphenyl phosphine oxide 1 Tris(2-chloroethyl) phosphate 1 Tricresyl phosphate 1 Diethyl hexylphosphate 1 Tris(N-ethyl perfluorooctanesulfonamidoethyl)phosphate 2 Tributyl phosphine oxide TABLE 4 Rheometer 175 C., 3 arc, 100 cpm Torque, Minimum (lbf. in.) 6.5 9.0 6.5 12 9.0 9.8 7.0 7.5 7.0 7.!
Torque, 12 minutes (lbf. in.) 96 93 99 90 86 89 99 97 92 9.5
Time to 1 lb. rise (min.) 5.3 4.9 4.2 2.7 3.7 3.4 4.1 4.5 4.8 2.
Time to lb. rise (min.) 8.0 5.8 5.8 4.4 5.6 5.1 6.0 6.6 7.5 3.2 Postcured 22 hrs. at 260 C.)
Tensile. (kg/cm) 128 147 152 144 146 146 137 140 135 13'.
Modulus, (kg/cm) 62 71 74 63 58 60 51 61 Elongation at Break, 195 190 207 200 170 205 Hardness, (Shore A 80 75 76 77 76 74 75 75 75 75 Compression Set (72 hrs. at 200 C.) 16.1 16.5 18.5 25.0 17.5 25.0 28.0 18.8 17.8 24
What is claimed is:
l. A curable fluoroelastomer composition comprising elastomeric copolymer of vinylidene fluoride and terminally ethylenically unsaturated fluorinated comonomer and for each hundred parts thereof:
a. 0.2 to 5 parts triorganophosphorus oxide b. 0.1 to 5 parts quaternary phosphonium or ammonium compound c. a total of 3 to 40 parts consisting of i. 0 to 25 parts acid acceptor ii. 0 to 25 parts optional base d. 0.2 to 5 parts aromatic hydroxy or amino compound.
2. A fluoroelastomer composition according to claim 1 wherein the elastomeric copolymer comprises vinylidene fluoride and perfluoropropene.
3. A fluoroelastomer composition according to claim 1 wherein the triorganophosphorus oxide is a trimganophosphine oxide.
4. A fluoroelastomer composition according to claim 3 wherein the triorganophosphine oxide is a phosphii oxide containing three like or unlike unsubstituted neutrally substituted aliphatic, cycloaliphatic or ar matic groups. 5
v 5. A fluoroelastomer composition according to clai 1 wherein the triorganophosphorus oxide is triorgan phosphate ester.
6. A fluoroelastomer composition according to clai 5 wherein the triorganophosphorus oxide is phospha ester of three like or unlike saturated or unsaturate aliphatic or cyclic unsubstituted or neutrally subsl tuted alcohols or unsubstituted or neutrally substitute phenols. 1
7. A curable fluoroelastomer composition accordir to claim 1 wherein the acid acceptor is magnesiui oxide and the optional base is calcium hydroxide.
8. A curable fluoroelastomer composition accordin to claim 1 wherein aromatic hydroxy compound is 2,1 bis-(p-hydroxyphenyl)hexafluoropropane.
|Cited Patent
|Filing date
|Publication date
|Jan 16, 1970
|Apr 11, 1972
|Minnesota Mining & Mfg
|Curing systems for vinylidine fluoride elastomers
|Jul 6, 1971
|Jan 23, 1973
|Minnesota Mining & Mfg
|Curable vinylidene fluoride elastomers containing phosphonium curing agents
|Jan 28, 1972
|Aug 14, 1973
|Du Pont
|Fluoroelastomer composition containing a triarylphosphorane vulcanization accelerator
|Citing Patent
|Filing date
|Publication date
|Jun 2, 1975
|Dec 13, 1977
|Montedison S.P.A.
|Vulcanizable compositions based on elastomeric copolymers of vinylidene fluoride, process for vulcanization thereof utilizing phosphorous metal coordination complex and vulcanized compositions obtained thereby
|Dec 27, 1977
|Dec 4, 1979
|E. I. Du Pont De Nemours And Company
|Press-curable fluoropolymer compositions and process
|Nov 25, 1981
|Dec 20, 1983
|David Hudson, Inc.
|Fluoroelastomer film compositions and solutions containing epoxy resin adducts
|Nov 25, 1981
|Dec 27, 1983
|David Hudson, Inc.
|Fluoroelastomer film compositions and solutions containing fatty polyamide curatives
|May 28, 1982
|May 8, 1984
|David Hudson, Inc.
|Novel fluoroelastomer film compositions and method for the preparation thereof
|Mar 19, 1984
|Oct 29, 1985
|E. I. Du Pont De Nemours And Company
|Peroxide-curable bromine-containing fluoroelastomers containing a sulfone
|Jul 25, 1985
|May 5, 1987
|E. I. Du Pont De Nemours And Company
|Fluoroelastomer composition containing accelerator
|Aug 27, 1986
|Jun 16, 1987
|E. I. Du Pont De Nemours And Company
|Fluoroelastomer composition containing accelerator
|Jul 22, 1986
|Mar 29, 1988
|Montedison S.P.A.
|Vulcanizable compositions of fluoroelastomers having improved self-lubricating properties and a fast cure rate
|Mar 14, 1988
|Sep 18, 1990
|E. I. Du Pont De Nemours And Company
|Fluoroelastomer composition with low tendency to foul molds
|May 26, 1992
|Dec 14, 1993
|Nippon Zeon Co., Ltd.
|Curable acrylic rubber containing dibutylaminotriazine thiol and 9,10-dihydro-9-oxa-10-phosphapenathrene-10-oxide
|Apr 4, 1997
|Feb 23, 1999
|Nippon Mektron, Limited
|Fluorine-containing elastomer composition
|Jun 12, 1998
|May 29, 2001
|Chemfab Corporation
|Fluoropolymeric composition
|Apr 6, 2001
|Jul 9, 2002
|Chemfab Corporation
|Fluoropolymeric composition
|Jun 30, 2000
|Oct 15, 2002
|Dyneon Llc
|Fluoroelastomer compositions and articles made therefrom
|Jan 26, 2004
|Apr 1, 2008
|Freudenberg-Nok General Partnership
|Dynamic vulcanization of elastomers with in-situ polymerization
|Jun 21, 2004
|Aug 19, 2008
|Freudenberg-Nok General Partnership
|Pre-molding heat treatment of dynamic vulcanizates of fluorocarbon elastomers
|Dec 27, 2004
|Nov 11, 2008
|Freudenberg-Nok General Partnership
|Fluorocarbon elastomer compositions containing wear reducing additives
|Jan 5, 2005
|Nov 11, 2008
|Freudenberg-Nok General Partnership
|Dynamic vulcanization with fluorocarbon processing aids
|Jun 27, 2005
|Feb 9, 2010
|Freudenberg-Nok General Partnership
|Reinforced elastomeric seal
|Sep 30, 2008
|Feb 16, 2010
|Freudenberg-Nok General Partnership
|Dynamic vulcanization of fluorocarbon elastomers containing peroxide cure sites
|Jun 30, 2005
|May 18, 2010
|Freudenberg-Nok General Partnership
|Base resistant FKM-TPV elastomers
|Dec 13, 2006
|Jul 16, 2013
|Freudenberg-Nok General Partnership
|Dynamic seal using vulcanization of fluorocarbon elastomers
|Jun 11, 2003
|Jan 8, 2004
|Xerox Corporation
|Chlorofluoro elastomer compositions for use in electrophotographic fusing applications
|Jan 16, 2004
|Jul 21, 2005
|Park Edward H.
|Bonding of dynamic vulcanizates of fluorocarbon elastomers
|Jan 26, 2004
|Jul 28, 2005
|Park Edward H.
|Dynamic vulcanization of elastomers with in-situ polymerization
|Feb 4, 2004
|Aug 4, 2005
|Park Edward H.
|Dynamic seal using vulcanization of fluorocarbon elastomers
|Jun 30, 2005
|Dec 8, 2005
|Freudenberg-Nok General Partnership
|Dynamic vulcanization of fluorocarbon elastomers
|Jun 21, 2004
|Dec 22, 2005
|Park Edward H
|Pre-molding heat treatment of dynamic vulcanizates of fluorocarbon elastomers
|Dec 27, 2004
|Jun 29, 2006
|Freudenberg-Nok General Partnership
|Fluorocarbon elastomer compositions containing wear reducing additives
|Dec 27, 2004
|Jun 29, 2006
|Freudenberg-Nok General Partnership
|Thermoplastic vulcanizate with high temperature processing aid
|Dec 28, 2004
|Jun 29, 2006
|Freudenberg-Nok General Partnership
|Dynamic vulcanization of non-nitrile rubbers in fluoroplastic polymers
|Jan 5, 2005
|Jul 6, 2006
|Freudenberg-Nok General Partnership
|Dynamic vulcanization with fluorocarbon processing aids
|Jun 27, 2005
|Dec 28, 2006
|Freudenberg-Nok General Partnership
|Reinforced elastomeric seal
|Jun 29, 2005
|Jan 4, 2007
|Freudenberg-Nok General Partnership
|Dynamic vulcanization of fluorocarbon elastomers containing peroxide cure sites
|Nov 14, 2006
|Mar 15, 2007
|Freudenberg-Nok General Partnership
|Dynamic vulcanization of polyurethane elastomeric material in the presence of thermoplastics
|Nov 21, 2006
|Jun 21, 2007
|Freudenberg-Nok General Partnership
|Peroxide cured fluorocarbon elastomer compositions
|Jan 13, 2006
|Jul 19, 2007
|Freudenberg-Nok General Partnership
|Fluorocarbon rubber with enhanced low temperature properties
|U.S. Classification
|525/147, 525/353, 524/139, 525/384, 525/199, 526/313, 525/340, 525/385, 526/253, 525/326.3, 525/200, 524/141, 525/374, 525/349, 524/145
|International Classification
|Cooperative Classification
|European Classification


text:
I chose the Fashion Hotel on Avenue Hassan II as a spur of the moment thing, since I needed a place relatively close to the train station in Marrakesh, for an early morning arrival. There is a Hotel Ibis right next to the station, but it was full, so I ended up here totally by chance, as it is the next closest (not including some mega-hotels, which I avoided since they are usually expensive unless booked with a package tour).
Anyway, I was pleasantly surprised when I got to the "luxury suite" since the décor was much more authentic Moroccan than I expected (it looked like it might have personality-less rooms from the outside), and the bathroom was very pretty. All of the room had lovely floor tiles, wooden furniture and paint and other decorations in good taste. I took a wonderful relaxing shower (though as usual there was nowhere to hang the shower nozzle, forcing me to juggle around without throughout the shower) and got some rest before heading to Djemaa-el-Fna, about a half-hour walk from the hotel.
Upon returning I went to bed, though I had a hard time falling asleep due to noise. Here they have this lovely suite, but the windows are like paper, so you can hear every car and motorcycle whiz by. Plus, a "mystery noise" resounds from inside the hotel, basically non-stop. It sounds like a giant rubber band being twanged over and over and over again, neverending. I suspect the elevator but can't be sure.
Then, in the middle of the night, the hotel managers knocked on the doors of the rooms adjacent to mine, from what I could hear to throw out the guests! There was a huge argument and then fight. These guests did not leave, but were infuriated by what happened, so they stayed up ALL night screaming and complaining and talking about how they were going to beat up the hotel manager and have him fired, etc. Well, this went on for hours, and despite my repeated calls to the reception desk, they did nothing to make these scandalous guests, an American man and two Moroccan girls, shut up or get out. In fact, they told ME to confront my loud, ruffian neighbors, which I refused to do since the American was talking about his martial arts skills and spewing threats. So, my lovely room at the Fashion Hotel turned into a sleepless nightmare, with zero help from the hotel to remedy the situation. I left the American a very nasty note in the morning, which I really hope he found.
Overall, a hideous hotel experience, but I'll give it 2 stars since the room really was pretty.
- Official Description (provided by the hotel):
- Fashion Hotel is situated in the centre of Marrakech, within 2 km of the Majorelle Garden and the Koutoubia Mosque. Guests are invited to enjoy the city view or swim in the pool on the rooftop terrace. The air-conditioned guest rooms at Fashion Hôtel include a seating area, a TV and a telephone. They are elegantly decorated and feature a private bathroom with a bath or a shower. A continental breakfast is served every morning at Fashion Hôtel. There is a massage room and a hammam on site and free Wi-Fi is available throughout the property. Free private parking is provided on site and Jemaâ El Fna Square is 2.4 km away. The property is 3 km from the Ben Youssef Madrasa and 4.6 km from Marrakech Menara Airport. Gueliz is a great choice for travellers interested in sunshine, sightseeing and friendly people. ... more less
- Reservation Options:
- TripAdvisor is proud to partner with Hotels.com, Booking.com, Orbitz, Expedia, Cancelon, Priceline, TripOnline SA, Travelocity, Hotwire, Agoda and Evoline ltd so you can book your Hotel Fashion reservations with confidence. We help millions of travelers each month to find the perfect hotel for both vacation and business trips, always with the best discounts and special offers.
- Also Known As:
- Fashion Hotel Marrakech

subset: commoncrawl


text:
Looking for Malta Bail Bonds? Most Malta bail bond companies can bail you (or another person) out anytime during the day or night in Malta. BailBondsNetwork.com makes it simple to find and get in touch with a licensed bail bonds company in Malta, Ohio. At your convenience, many bail bonds agents will come pick you up privately. Installment payment plans are usually available depending on case by case basis.
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text:
Melissa Steinkamp, BA
Melissa Steinkamp graduated from Transylvania University in 2014 with a BA in Psychology and a minor in Political Science. Melissa is in the 3rd year of her doctorate in clinical psychology at Spalding University. Since starting school at Spalding, Melissa has had the opportunity to work with adults, children, and adolescents. In her spare time, Melissa enjoys reading, art, and riding her horses. She is looking very much forward to her time at Groupworks!


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text:
Home » Our Work » Current Projects » Getting Men Moving
Current Projects
A Practical Problem
Across Eastern Europe there are thousands of towns and villages with no evangelical witness. We thank God for the great number of new churches planted in recent years, but the need is great and there is still much more to be done.
One of the great obstacles Christian workers face is travelling to these needy areas. Because of the economic problems in their countries many struggle to afford to buy or run a car. Public transport is unreliable or non-existent and as a result men are having to walk for hours to isolated villages in great spiritual need. The following three examples illustrate the problem and the need for help.
Leonid Turia
Leonid is a Pastor ministering in 3 villages which are all approximately 4 - 5 km apart. He has no car. There is no public transport so he is forced to either rely on lifts or make this journey on foot. Obviously this situation is far from ideal; it restricts the number of visits he can make to each village, limits the effectiveness of his ministry among the people and is a major factor in preventing more churches from being planted in an area where the spiritual need is immense.
The provision of a motor bike would be ideal for his circumstances and would undoubtedly make an enormous contribution to a more effective ministry for Christ in his region.
Yuri Didik
Yuri has just graduated from the SGA Mission School and is a Pastor in the village of Natalevka which is located about 12km from the city of Balti. He also ministers in another village called Beleutsi which is approximately 5km further. It is a district with many hills and Yuri`s only form of transport is his bicycle which limits the number of visits he can make to evangelise and encourage the Christians. He has also been attacked by dogs which seem to have a particular dislike for cyclists.
This hard-working, willing and zealous servant of the Lord would love to engage in more ministry in the villages but his lack of transport limits his opportunity to do so.
Ivan Yasilikovsky
Ivan is 67 and travels 2-3 times per week to the village of Trnova in order to pastor God's people and preach the Gospel. However the journey is difficult and time-consuming. It begins with a 3km walk to the bus station. From there Ivan makes the 40km journey and then has another 2km walk to the Church. When the services and home visits are over he begins the return journey often waiting up to 2 hours for his bus. Not surprisingly this is having an impact on Ivan's health. It is obvious that a motor bike is not the answer in this situation. The only practical solution is the purchase of a used car. We have been told we can buy a suitable vehicle for £1700.
Our aim is to purchase these motor bikes so that evangelists and church planters can reach more people with the Gospel of Christ!
The problems of transportation facing pastors and evangelists in Eastern Europe is not just an inconvenience, it is a great hindrance to effective ministry. However, with your help we can make a difference. By purchasing these motor bikes, or helping to provide other vehicles, we can give these dedicated and gifted men
more opportunities to visit
more villages so that they may plant
more churches for the glory of God!
Will you join us as we get men moving with the Gospel?
Current Projects
- Providing tools for the Task
- Ministering To Body & Soul
- Mission Without Walls
- Learning with Purpose
- Healing Broken People
- Sharing Christ Through Camps
- Training Gospel Leaders
- Emergency Relief Fund
- Gospel Partners
- Truth for our Times
- Building Hope
- Proclaiming Christ across the airwaves
- Investing in Stones That Speak
- Reaching the Republics
- Getting Men Moving
- Leadership Support
- Moldovan Camp Project
- Feeding Fertile Minds
- Bread of Life
- Equipping The Next Generation Of Christian Leaders
- Challenge 2:2:2
- Giving Hope to Children and Orphans


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Your search for "cd3g" returned 78 TaqMan® SNP Genotyping Assays
CD3g molecule
The protein encoded by this gene is the CD3-gamma polypeptide, which together with CD3-epsilon, -delta and -zeta, and the T-cell receptor alpha/beta and gamma/delta heterodimers, forms the T-cell receptor-CD3 complex. This complex plays an important role in coupling antigen recognition to several intracellular signal-transduction pathways. The genes encoding the epsilon, gamma and delta polypeptides are located in the same cluster on chromosome 11. Defects in this gene are associated with T cell immunodeficiency. [provided by RefSeq, Jul 2008]
(Mouse) P11942, (Human) P09693, (Human) Q2HIZ6, (Rat) Q64159
Please enter the information below and press OK to send your cart to Core Services for purchase.


text:
Binghamton supplement essay
Admissions Requirements; Undergraduate Admissions. Admissions Requirements Common Application and Lehigh Questions and Writing Supplement for Transfer Students. Send us your essay. With our Single Essay Review package Supplement #2: How did you learn about Vassar and what aspect of our college do you find appealing. Official website of the Office of Admissions at Syracuse University. I'm Ready to Apply! Everything you need to get started. In this Section. Admissions I'm Ready to Apply!. We no longer require a supplemental Bucknell essay. Supplemental Applications. Transfer Applicants. Freshman Applicants Binghamton University Required Online Applicants: SUNY Form. Paper Applicants: SUNY Form. Quality of the personal essay.Apply to Binghamton University, State University of New York 201 supplement to the suny application. Applicants to the following programs must submit a writing supplement via the. Your vision statement/essay should also include how you expect this.
Applying to Trinity - Tuition and Fees - Campus Visit. Suny Essay Question PDF Document 201 supplement to the suny application 2015 supplement to the suny application therefore 2017. Professional Academic Help. Starting at $7.99 per pageOrder is too expensive? Split your payment apart - Suny binghamton common app supplement essay. Your pathway to UConn Nation starts here. Freshman applicants must apply online through either the Common Application or the Coalition Application. Admission. St. Joseph's College – Long Island Campus Long Island SUNY Binghamton University Binghamton, NY 11,464 43% SUNY Buffalo State Buffalo, NY 8,811 46% . The first-year Writing Supplement essay questions and transfer Writing Supplement question are available for you to review. How do I make the Writing Supplement appear. Essay advice for Villanova University applicants. November 23, 2009 by Kevin McMullin. I'll say this about Villanova University –their admissions office has guts.
Binghamton supplement essay
Apply as a Freshman Personal essay Complete the essay component of at least 250 words on the Common Application or SUNY Supplemental Application. Important information for freshman applicants to Binghamton University. Binghamton University. Undergraduate Admissions. Academics. Apply. Visit. An essay is required for first-year applicants and must be submitted in the space provided on the online application. The essay is an important factor in admissions. Use the free College Match college search engine to find colleges that match your preferences, or look up any college by name. View detailed profiles of 2,000 U.S. Does Binghamton University require a. Does Binghamton University require a supplement if you. Boston University Common App Supplement Essay.
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Comprehensive information on admission at Binghamton University, including admission requirements and deadlines, early and regular admission rates, GPAs and test. First-year Applicant Checklist. Deadlines. Early Decision I:. Colgate University writing supplement;. Colgate requires a supplemental short-answer essay. Essay. This is a required part of the application. Take your time writing your essay. Get feedback from your parents, a favorite teacher, or your school counselor. Freshman Supplement (UCA) Writing Supplement (CA) Early Decision Agreement (optional) Professional Degree Programs essay (optional) Arts Supplement (UCA) (optional. After submitting the supplement and other required application materials, the School of Music admissions office will schedule your audition with faculty members.
With instant access to nearly 700 colleges and universities around the world, the Common App is the most seamless way to manage the application process. Apply to Tulane today using the application options below. All applications are reviewed the same way. Freshman Application. Apply for fall admission until January 15. We recommend students complete the Supplemental Essay and Activities. Recommended Application Essay & Activities Supplement: Click here. Got questions? Reach. Item ED RD; Application and Supplement Common Application with Johns Hopkins Supplement, Universal College Application with Johns Hopkins Supplement (including the. As a part of the Common Application, applicants must complete a personal essay. Additionally, Penn applicants must complete the Penn Writing Supplement.
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To apply for admission I'm working on my college application essay for Hamilton and. Does Hamilton require a Writing Supplement in addition to The Common. Heads Up! Essay Prompts From the Common App, University of California App, the Universal Application and the New Coalition App. Is there a supplement essay if one is applying with the common app? Binghamton is a little confusing regarding this topic. Information for High School Students. Admission to SUNY-ESF is competitive, but our admissions process is a personal one. Your interests, abilities and goals are. Application Materials. Apply to CWRU CWRU's member questions and optional writing supplement will then appear in the My Colleges tab;. SAT essay; SAT subject. Freshman Applicants. You will apply to BU as a freshman if you are currently in your last year of high school, have completed high school, are a GED recipient, or.


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CorGal tanks are constructed of highest-quality corrugated, galvanized steel for superior strength and durability.
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Water Containment system consists of a geotextile preliner and a flexible membrane main liner suspended inside the tank structure.
CorGal tank components are quickly assembled at the job site. Complete instructions are included.
Complete line of CorGal tanks from 6' diameter to 105' diameter.


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A team led by Johns Hopkins engineers has discovered some previously unknown properties of a common memory material, paving the way for development of new forms of memory drives, movie discs and computer systems that retain data more quickly, last longer and allow far more capacity than current data storage media.
The research focused on an inexpensive phase-change memory alloy composed of germanium, antimony and tellurium, called GST, for short. The material is already used in rewritable optical media, including CD-RW and DVD-RW discs. But by using diamond-tipped tools to apply pressure to the materials, the Johns Hopkins-led team uncovered new electrical resistance characteristics that could make GST even more useful to the computer and electronics industries. This phase-change memory is more stable than the material used in the current flash drives. It works 100 times faster and is rewritable millions of times.


text:
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Beulah speed bias removed
The Beulah Park racing surface received a facelift of sorts during the two-week break between fall and winter racing. The inside speed bias that was apparent late in the fall meet, when the four inside horses and any horse with early speed that could get to the rail had to be considered in exotic wagers, appears to be gone. Quick times - six furlongs were routinely run in the 1:09 to 1:10 range last fall - are also gone. After the first two days of the winter meet, the fastest six-furlong time has been 1:15.03. Two maiden claiming races have gone in times over 1:18.
The off-season renovation entailed the most work and required the most material of any racing surface project here since the early 1990s, according to steward and track maintenance supervisor Joe Deluca.
"We removed the old racing surface, virtually down to the base, and replaced it with eight inches of new material, so the track has been completely redone," Deluca said. "It is a very forgiving surface, and when the track compacts over time, the race times will get faster. We have had very positive feedback from the horseman."
Deluca pretty much inherited the job of track superintendent.
"The jockeys kept coming to me when they didn't think things were right with the track, so I got involved and ended up with it," Deluca said.
Maintaining the track is very time consuming and labor intensive, and it is not uncommon when the weather is bad to see Deluca on the track between races, checking the surface and directing the crew, and then rushing back to the stewards' booth.
"The main goal is to keep everybody happy," he said.


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Grant Magazine takes New York for the 3rd year in a row! We were nominated for a Silver or Gold Crown Award from the Columbia Scholastic Press Association for both online and print. This documentary represents our staff and the bonds that we form with each other as we journey through New York City.
Grant Magazine: New York Documentary 2016
About Mackie Mallison
Mackie, a second year staffer, has loved filmmaking since elementary school. When Mackie isn't making movies he enjoys playing with his brother, hanging out with friends and cooking. Since he wakes up early and gets home late from running cross-country, Mackie often takes time lapses of the sunrise and sunset. He plans on applying to film colleges so he can meet other filmmakers and collaborate on new projects.


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Ed Upton alias DMX Krew released an album on White Leather (sublabel of canadian Turbo Recordings) in 2003 under this name.
Artist descriptions on Last.fm are editable by everyone. Feel free to contribute!
All user-contributed text on this page is available under the Creative Commons Attribution-ShareAlike License; additional terms may apply.


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Discovery is a transformative learning tool to initiate a process of self-enquiry. Now available as a comprehensive and fully illustrated book in Kannada.
Following the overwhelming response for the book 'Discovery' is a transformative learning tool that aims to introduce basic human values to a person and initiate a process of self-enquiry, the translated version in Kannada language was brought out in 2010.
This compact version is an illustrated version and is presented in the form of a 'snake and ladder' game with hundred stories / parables forming the backbone of the game. Eleven theme-based charts are included to inquire into specific dimensions like Success, Leadership, Team Building, Communication and so on. The players are taken through three levels of learning at the end of each story: Explicit, Experience Sharing and Abstract Conceptualization. This leads the player towards a belief level change that is transformative in nature. This tool has been used for almost two decades now and has had a successful implementation in schools, organizations and communities, both at a self as well as group level.
Subscribe to the Arpitha Network by providing your email address below. You will periodically receive articles, updates and information about events organized by us in your city:


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titlu editat 17 Jun 2015 08:18 Lux0R^ Scripter eXtreamCS Joined: 13 Jul 2013 15:31Posts: 1206 Detinator Steam: Da Reputatie: Scripter eXtreamCSModerator ajutator Fond eXtream: 0 Re: Problema server cs FurienUltimate Wrote:Salut,imi Hi! Register now! Va dau .sma de la f_ultimate_sounds ? 0 Connect CS.TRUSTHOST.RO | SE CAUTA ADMINI ! have a peek here
Reload to refresh your session. jippo06-12-2005, 02:09Ok cool! Sign in to comment Contact GitHub API Training Shop Blog About © 2016 GitHub, Inc. Thanks!
Thanks:) The files are not on the pc though, nor a plugin that needs them.... Powered by phpBB © 2001, 2005 phpBB Group Ū└╩ą█ę▄ ąÓ±°ĶÕĒĒ¹ķ ŽÓŌĶļÓ ¶Ņ¾ņÓ ├ÓÓĒ"¹ ¶Ņ¾ņÓ ąÓńņÕ∙ÕĒĶÕ ÕĻļÓņ¹ AMX-X ĻŅņ'Ķļ "Ņ [X] ŽŅņŅ∙ĒĶĻ ŪÓŃ¾ńĻÓ. ŽŅµÓļ¾ķ±"Ó, 'ŅõŅµõĶ"Õ... čŅŅß∙ÕĒĶÕ ±Óķ"Ó (čŅŅß∙ÕĒĶÕ ńÓĻŅÕ"± Skip to content Ignore Learn more Please note that GitHub no longer supports old versions of Firefox. Username Forum Password I've forgotten my password Remember me This is not recommended for shared computers Sign in anonymously Don't add me to the active users list Privacy Policy
Back to top Report #3 ZyreX ZyreX Advanced Member Members 208 posts Locationlocalhost Posted 03 March 2011 - 05:27 PM Verifica daca sunetele se afla acolo, adica in sound/misc 0 >> Edit: please delete #2429 elmatadour commented Jun 1, 2015 Error: server failed to transmit file 'sound/misc/dohoo.wav' Error: server failed to transmit file 'sound/misc/dohnuts.wav' Error: server failed to transmit file 'sound/misc/doh2.wav' Error: Not when I join an online server. E si normal sa nu le poata downloada , daca ele nu sunt acolo. 0 >> Documentatie Krond.Org>> Tutorial sv_downloadurl>> Plugin de Securitate - Krond Functions>> Zona Clienti -> Facturi ,
Back to top Report #5 ZyreX ZyreX Advanced Member Members 208 posts Locationlocalhost Posted 03 March 2011 - 07:26 PM Pai daca nu ai, atunci trebuie sa le copiezi. Back to top Report #8 Salmus Salmus Administrator Dep. Register • FAQ • Login It is currently 23 Dec 2016 13:03 Board index » eXtream - Counter-Strike 1.6 » Probleme la servere dedicate de Counter-Strike All times are UTC Unchain My Heart by Joe Cocker on Grooveshark Back to top Report #9 alin alin Newbie Members 6 posts Posted 04 March 2011 - 11:29 PM Era la fek de simplu
I just thought it might do something funny or make the performance worse:) vBulletin v3.8.7, Copyright ©2000-2016, vBulletin Solutions, Inc. Dontask-jello06-11-2005, 23:55Then don't worry about it, if they arn't needed, just ignore it. L 03/03/2011 - 15:49:51: "StOrM<885>" say "ep cat esti om?" L 03/03/2011 - 15:49:54: "[FOCK] MoBiUs [OnE]<897><>" joined team "TERRORIST" *DEAD* KeNzO. : /top15 L 03/03/2011 - 15:49:55: "KeNzO.<876>" say "/top15" alfred-valve closed this May 13, 2013 healthycs16 commented May 13, 2013 alfred, this happens when I start a New Game...
You signed out in another tab or window. jippo06-11-2005, 17:26You must find the plugin that needs them, find the files, and put them in the correct spot. maxplayers cannot be changed while a server is running. '┐Į BUILD 5999 SERVER (0 CRC) Server # 4 Warning: Unable to open sound/misc/kenny1.wav for transfer Warning: Unable to open sound/misc/cracker1.wav for Scoring will not start until both teams have players Contributor alfred-valve commented May 13, 2013 This sounds like a mis-configured server, not a bug.
Back to top Report #6 4Fun 4Fun Advanced Member Members 87 posts Posted 03 March 2011 - 10:11 PM De unde imi fac rost de ele... ? 0 Connect CS.TRUSTHOST.RO | Reload to refresh your session. They all look like this: Warning: Unable to open sound/misc/doh.wav for transfer Does anybody know how to fix that? Check This Out Am vazut o posibila problema in consola Started by 4Fun, Mar 03 2011 03:53 PM Please log in to reply 8 replies to this topic #1 4Fun 4Fun Advanced Member Members
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Several functions may not work. Back to top Report #4 4Fun 4Fun Advanced Member Members 87 posts Posted 03 March 2011 - 07:22 PM NU am nici unul din sunetele acelea..la adresa sound/misc ..nici unul . AlliedModders > AMX Mod X > General > Warning: Unable to open sound/misc/doh.wav for transfer PDA View Full Version : Warning: Unable to open sound/misc/doh.wav for transfer jippo06-11-2005, 13:27Hi, I get http://gs.bel-net.ru...oad/sound/misc/ ą¤ąĄčĆą▓ą░čÅ čüčüčŗą╗ą║ą░ ą▓ ą│ąŠąŠą│ą╗ ąØą░ą▓ąĄčĆčģ #5 SkOcH SkOcH ąØąŠą▓ąĖč湊ą║ ą¤ąŠą╗čīąĘąŠą▓ą░č鹥ą╗čī 21 čüąŠąŠą▒čēąĄąĮąĖą╣ ą×čéą┐čĆą░ą▓ą╗ąĄąĮąŠ 28 ąÉą▓ą│čāčüčé 2014 - 17:02 ąÉ čŹč鹊 čćč鹊 ?http://gs.bel-net.ru...oad/sound/misc/ ą¤ąĄčĆą▓ą░čÅ čüčüčŗą╗ą║ą░ ą▓ ą│ąŠąŠą│ą╗ ąĪą┐ą░čüąĖą▒ąŠ =) ąØą░ą▓ąĄčĆčģ #6
Personal Open source Business Explore Sign up Sign in Pricing Blog Support Search GitHub This repository Watch 120 Star 1,038 Fork 249 ValveSoftware/halflife Code Issues 813 Pull requests 17 Projects Hosting Administrators 715 posts LocationBucuresti Posted 03 March 2011 - 11:32 PM http://forums.allied...ead.php?p=47280 http://forums.allied...ad.php?p=638940 Redenumeste wav-urile in ce ai tu acolo ... f1del1ty.oXi06-11-2005, 15:48You must find the plugin that needs them, find the files, and put them in the correct spot. this contact form Back to top Report #2 ZooMl3sS^ ZooMl3sS^ Advanced Member Members 57 posts Posted 03 March 2011 - 04:42 PM dezactiveaza-l si zi aici daca mai face la fel 0 Sunt membru


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Sports Viz – Australian Dragon Boat Championships
posted in: Dragon Boating, Example, Tableau, Visualisation | 0
How analytics leads to behavioural change
posted in: Dragon Boating, Education, Example, Tableau, Uncategorized, Visualisation | 0
Analytics is about making differences obvious in a way that enables changes in behaviour and outcomes. At the 2015 Australian Tableau Conference, I gave a presentation on the application of Sports Science using Tableau and new generation ETL tools like Lavastorm and Alteryx. Using these … Continued
Making waves with data driven performance
Tableau on Tour Presentation – Sports Science: Using Multiple Disparate Complex Data Sources to Win
Data Visualization Best Practises
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Dragon Boating Data Visualisation example
Australian Real Estate VISUALIZATION example
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Self-evaluation of essay
DESCRIPTION. One dynamic way to integrate vocabulary with reading-strategy instruction is to use student self-evaluation as a starting point for learning. By Richard Nordquist. Definition: A composition that offers value judgments about a subject according to a set of criteria. An evaluation essay or report (also called. Having drafted your essay, you have gained the perspective of hindsight. Was the subject matter more complex than you anticipated? Did your preconceived ideas … Thank you for using our education tools! The content you're looking for now exists in multiple upgraded, title-specific products. If you are a student, your valid.
Free reflective essay on a childhood memory papers, essays, and research papers. Mar 11, 2016 · College admissions officers read thousands of college application essays. These tips and strategies can help you make a strong impression.
Self-evaluation of essay
Our Professionals will present you Essay Help Online. Maybe English is not your main subject, but does not mean that there is no need look for college essay help. Essays - largest database of quality sample essays and research papers on Preschool Teacher Self Evaluation This I Believe is an international organization engaging people in writing and sharing essays describing the core values that guide their daily lives.
Self Introduction Essay For University Ajou University Self-Introduction Essay Full Name in English: Li-Ying Huang Gender: Female... Nationality: Taiwan Home. Teaching guide ( discussion guide, lesson plans, teachers' guide ) for responsibility. Produced in association with Character Counts! Classroom discussion questions. How to Write a Self-Analysis Essay. Self-analysis essays force you to think critically and honestly about yourself and your work. These essays are often assigned at.
Oct 17, 2012 · Meaningful healing threads representing a small portion of what is available on Pandora's Aquarium. We provide excellent paper writing services 24/7. Enjoy proficient essay writing and custom writing services provided by professional academic writers. Self-Evaluation Report of Educational Quality and Institutional Effectiveness - In Support of Reaffirmation of Accreditation 2015:
May 17, 2011 · UPDATE 2015 12 16 : I removed the ability to comment on this video. Insult contests and negative energy spreading will have to find another platform. Sudoku is a fun puzzle game once you get the hang of it. At the same time, learning to play Sudoku can be a bit intimidating for beginners. So, if you are a complete. Find tips, sample essays and essay critiques for each of the Common Application personal essay options. Sudoku is a fun puzzle game once you get the hang of it. At the same time, learning to play Sudoku can be a bit intimidating for beginners. So, if you are a complete.
The fifth practical assignment is more of a collection of mini-assignments. All the other Ptlls assignments are also covered, so check them out if you need. Level 3. Supreme Court of New York, Appellate Division Confirms the Commission s Revocation of Longshoreworker s Registration, and Unanimously Reverses the Prior Order and.


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Our skin is exposed to many factors which affect its appearance every day. In order to preserve the health of your skin, you need to wash it often, but doing this with water only isn't going to help. Using commercial cosmetic products has an adverse effect on our skin regardless of their marketing as they contain high levels of chemicals. Luckily, we have a solution – an ancient and safe to use remedy which will clean your skin and make it look younger than ever before.
Article Categories:Health


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The Endometriosis Family Support Group does not meet during the month of August. Please see below for information on our next meeting:
Meeting Date and Time:
Wednesday, September 20, at 7:00 p.m.
Please Note:
The September 20th meeting will be a webinar, rather than an in-person meeting. The webinar will feature Devra Densmore, Associate Director, Patient Advocacy, at Continuum Clinical. To register for the webinar, please contact Program Coordinator Megan Elder at 951-321-6514, email email@example.com or click on the image below to register online via Eventbrite (you will be sent an email with instructions on how to log in to view the webinar).
Riverside Medical Clinic Charitable Foundation's Endometriosis Family Support Group provides an opportunity for individuals who have endometriosis to share information, offer support and provide encouragement. This support group meets on the third Wednesday of most months (no meetings are held in August and December). Diagnosis, treatments, pain management, diet, exercise and lifestyle modifications are just a few of the important topics discussed. This is one of only a few endometriosis support groups that meet in Southern California, as most endometriosis groups are only offered online.
Meetings and webinars are FREE and participants are welcome from all medical groups. Spouses, partners, adult family members and close friends are welcome to attend meetings, too!
For further information about the Endometriosis Family Support Group, please contact Megan Elder, Program Coordinator, at (951) 321-6514 or email@example.com.
Click here to join our Facebook group!


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I loved this hotel and the town. It is small, quaint and centers around the church. The hotel is a two minute walk to anywhere in town.
Our room had two huge beds, closet, TV, warm showers and was clean. Each morning breakfast and coffee are made to order.
The purpose of the trip was the Festival of the Virgin of Mercedes, but I would come again as it was a nice change of pace from Panama. The town was buzzing with excitement from the parades and the hotel was right in the midst of it all.
- Official Description (provided by the hotel):
- Hotel Bali Panama, former Hotel El Prado, for more than fifty years served as the cultural and business center for the surrounding communities. The hotel has recently been refurbished to better serve its customers. Bali Panama hotel is strategically located at the heart of the banking and commercial district of Chitre. Only meters from the church, town square, shopping centers, baseball stadium, Herrera Museum, Azuero International Fair and close to the main attractions of Herrera and Los Santos. At Hotel Bali Panama, we provide a very efficient service. Our staff have the experience and knowledge necessary to professionally host our customers. For business or pleasure, we are a great choice. ... more less
- Reservation Options:
- TripAdvisor is proud to partner with Booking.com, Expedia, Hotels.com and HostelWorld so you can book your Hotel Bali Panama reservations with confidence. We help millions of travellers each month to find the perfect hotel for both holiday and business trips, always with the best discounts and special offers.


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Arts Fresco
The seventh annual Arts Fresco in Market Harborough was billed as 'an extraordinarily fun celebration of innovative street arts and spectacular entertainment,' and promised 'the best street artists from around the world.' I was interested to see whether the mental image conjured by the phrase 'street artists' – that of poorly made-up clowns juggling (I hate clowns, and hate juggling) in the midst of talent-deficient buskers with signs asking for donations of cat food – could be dispelled and replaced with something more rewarding.
When we arrived a little past midday everything was in full swing and the small market town was already buzzing with activity and atmosphere. Our route into the town centre took us past the Joules clothing store, a major sponsor of the event and host of the Traditional Seaside. A large sand pit in which a host of youngsters (and not a small number of oldsters) were hard at work with buckets and spades sat next to a man with green/blue hair and a boat on his head and a collection of deck chairs facing a stand which played host to some traditional performances by Punch and Judy, recreating a scene from a 1950s postcard.
Wandering on from surely the country's furthest inland seaside resort, we I came across some people with very strange hair, and Fairly Fresh Fish – a pair of cheeky-chappy East-ender fishmongers encouraging young and old to pet their dancing prawns and converse with a gooey eel emerging from its jelly jar.
Spying a conspicuously parked caravan a short way on, we went to investigate. It turned out to be a mobile exhibition displaying snapshots of British life with a slice of humour, a dollop of irony and a light dusting of satire. There was also somebody with an exceedingly odd hairdo.
Working our way past a small collection of craft stalls (and more people with odd hair) we came across a crowd of people. Politely squeezing our way through to a decent viewing position, we finally found out where all the strange hairstyles of the day were coming from: Osadia. These wildly dressed (and blue-skinned) Barcelonians were inviting audience members onto their stage and turning fairly normal hairstyles (in most cases) into extraordinary, one-off and, frankly, bonkers works of art.
Other artists worthy of mention include the fantastic Oxbridge undergrads Artizani punting (yes; that's the boat-and-big-stick method of travel) down the high street; fantastically charismatic and talented Goronwy Thom (who has turned my view of jugglers on its head); a pair of enormous seagulls terrorising anyone with a bag of chips; Jon Hicks, who produced a stunning pair of larger than life portraits of Freddie Mercury and Elvis Presley before our eyes; and Circus Box, the all-day circus school for children of all ages.
If you haven't been convinced by my review so far, let me add that the day's entertainment was absolutely free (apart from the pizza for lunch and the obligatory ice cream), and there wasn't a burger van or glow-in-the-dark-paraphernalia-salesperson in sight: this was all about art. All in all, it was a packed and enjoyable day out. We didn't leave until after the roads had re-opened and the street artists were packing away, yet we still hadn't seen everything. I'd encourage anyone who may be even remotely interested in this kind of event to keep an eye open for next year's Market Harborough Arts Fresco and put the date in their diary as soon as it is announced*!
More info
- Click here to see some pictures from the 2008 Arts Fresco (at the Arts Fresco website)
- Follow Arts Fresco on Twitter
- 2009 Arts Fresco Facebook event
* Sunday 13th September 2009, 12am - 5pm


text: Testing out blogsy This is Claire eating her arm. I posted it to Instagram. Posted with Blogsy Share this: Related Geoff 2 December, 2012 9:45 pm About Geoff Geoff is a 28 year old Secondary School Teacher. He spends a lot of his spare time doing stuff for Soul Survivor Melbourne, and is cursed with barracking for Richmond. His favourite number is 17 and his favourite song is Last Goodbye by Jeff Buckley The Next Big (and really little) Thing James Bond Fridays – Dr No


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Rieker women lace up boot blue 96712-14
This great lace up boot is from the current winter collection by Rieker. It is made of imitation leather and equipped with a warm lining. The autumnal colors make this shoe a real eye catcher!
|textile fleece, warm lining
|upper material:
|imitation leather
|size recommendation:
|order in usual size
|zipper, lacing


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- 第一章 套牌介绍
- 第二章 样本牌表
- 第三章 单卡分析
- 第四章 备选牌池
- 第五章 套牌变种
- 第六章 对战分析
- 第七章 其他更新
第一章 套牌介绍
奇迹控制是一套通过陀螺+抵消把战局拖入后期,再使用敦请天使或杰斯控场来赢得比赛的蓝白控制套牌。陀螺+抵消这个组合技在另一蓝白滞留控制套存在的时候已经存在,但因为人鱼的横行,蓝白控制遭到了不少抵抗。艾薇欣重临这个系列带来的奇迹机制给旧的蓝白控制注入了新的活力,于是陀螺+抵消为核心的奇迹控制得以展露头角。在2017年4月的禁牌里陀螺被禁,在随后的2个月里奇迹占meta急剧下降,直到2017年7月一套日本xxxx,让人知道去掉陀螺+抵消的奇迹原来可以这样玩,下文会用topless miracle指代没有陀螺+抵消版本的新奇迹.
第二章 样本牌表
Average Maindeck
Creature [Creature]
3 Snapcaster Mage
1 Monastery Mentor
Instant [Instant]
4 Brainstorm
4 Swords to Plowshares
4 Force of Will
2 Predict
1 Counterspell
Sorcery [Sorcery]
4 Ponder
4 Terminus
1 Entreat the Angels
1 Council's Judgment
Enchantment [Enchantment]
4 Counterbalance
Artifact [Artifact]
4 Sensei's Divining Top
1 Engineered Explosives
Planeswalker [Planeswalker]
2 Jace, the Mind Sculptor
Land [Land]
4 Flooded Strand
4 Island
3 Scalding Tarn
3 Tundra
2 Volcanic Island
2 Plains
1 Arid Mesa
1 Polluted Delta
- 数量4的牌是你想在起手就有的牌。
- 数量3的牌是你想在起手就有的牌,并且不想多于一张。
- 数量2的牌是你想在中后期抓到,并且只想抓到一张的牌。
4 Brainstorm
4 Sensei's Divining Top
4 Counterbalance
2 Jace, the Mind Sculptor
第三章 单卡分析
Snapcaster mage 讯咒法师:非常实用的多功能生物,一般用来从坟场捡brainstorm,swords to plowshare,ponder,甚至是counterspell。这张牌跟Rest in Peace有冲突。
Venser, Shaper Savant 凡瑟:随着Show and tell和掘坟类的套牌崛起,凡瑟的用量开始增多。凡瑟可以弹回靠其他牌解不了的Griselbrand,Emrakul, the aeons torn,甚至是omniscience。著名的奇迹牌手Joe Lossett非常喜欢凡瑟,并且可以跟 karakas配合弹弹弹。
Vendilion Clique 薇安留聚群: : One of the best creatures in the deck. It is almost never a dead card. Against Thresh decks it can trade with a delver of secrets or Nimble mongoose. Against combo or control you can play it at awkward times to strip the best card from their hand. The same is true against a show and tell on the stack. One of the best applications of this creature outside of Show and tell is against stoneblade. You respond to the stoneforge trigger and remove the batterskull.
Geist of Saint Traft: Efficiency at its finest. It hits like a titan for only 3 mana. It is immune to spot removal while also putting on a deadly clock. This card is usually in the sideboard and is only brought in during control mirrors or against combo decks where you cannot afford your opponent to sculpt a hand and you need a clock.
Stoneforge Mystic: Since the decks infancy people have tried mixing it with stoneblade. A few people have tried but it has not become popularized until a list topped GP Denver in 2012(list will be posted below). The addition of stoneforge greatly increases your matchup against aggro decks and speeds up the game against control mirrors. The biggest deterrent for stoneforge in the deck is the deck already has good matchups against aggro and adding in stoneforge just makes a good match better. However, Jund can be a rough matchup and they have an incredibly rough time dealing with a batterskull if they do not expect it coming.
Force of will: A necessary evil in the deck. Force doubles as the best card in the deck and the worst card in the deck. The only real reason to have this card in the deck is to not just die to combo decks. Late game you are able to "hard cast" force of will but the cost of a card early game really means you should not cast it unless you absolutely need to.
Brainstorm: I am not going to go into detail about "how to brainstorm" there have been multiple articles about how to do this, instead i will say some interactions with it in this deck specifically. Brainstorm is at its best when "digging" for a specific answer or setting up a miracle. This can also be used to find lands, or shuffle away extra counterbalances or cards not needed at this specific time in a game.
Jace, the mind sclulptor: One of the best blue cards in legacy right now. It is a good reason for playing blue. It gives you card advantage when you need it and also clears the board if need be. Late game once you have control it becomes a very good win condition. A lot of the time if you have a sensei's divining top in play it is best to +2 your self to remove cards you will not need instead of brainstorm. Mostly because assuming you have 7 cards in hand with top out. +2ing jace will increase the clock and threat level of jace while also seeing you more cards. If you brainstorm and put the two not needed cards back on top you really did not achieve anything.
Counterbalance: One of the best cards to have in play on an empty board. This is doubly true when paired with sensei's divining top. Together this can perform a soft lock on your opponent that can make it incredibly hard to deal with. By its self however, it very rarely will counter anything. You can "blind flip" if you are lucky which is one of the single most tilting things to do to an opponent. But, brainstorm will double as a single chance to counter something while also netting card selection.
Sensei's divining top: One of the best reasons to play this deck. While in play top virtually adds 3 cards to your hand. When paired with counterbalance it becomes incredibly useful. Top is also great at setting up miracles on your opponents turns. This can be anything from a terminus in a combat step while a land is animated or an Entreat the angels on your opponents turn to win the game on the spot. The only bad thing with top is if you are a slower player you can spend a lot of time topping and end up going to time a lot. Top is incredible with fetch lands as well, it can act as an instant speed ponder when in conjunction.
Some interactions with top is you can do it on your upkeep on your second turn if you need to dig for a specific card/land or if you do not have a turn 2 play at all. With multiple tops out you can use one as a cantrip and shuffle it away with a fetch land. If you were to crack a fetchland you should order your play like so: top, look at top 3, responding to that by cracking the fetch land. This is useful when playing against abrupt decay decks. They will usually wait until you are going to fetch to try to remove your top. This way ensures that if they do it you still get a chance to look at your top cards when you resolve your fetch.
Terminus/ Entreat the angels:These are being lumped together becuase i feel they should be talked about at the same time. Both are very powerful cards but are incredibly slow/clunky when not miracled. Terminus specifically was the reason this deck was able to do so well. It can be an instant speed 1 mana wrath effect. It also can remove cards that would hit the graveyard where that would help your opponent (ichorid specifically). Entreat puts in double work in this deck. It acts as one of the most threatening/efficient finishers but it is also a 3 when revealed off of a counterbalance. This is incredibly useful when playing against show and tell. The deck right now has a small amount of 3 drops to use currently.
第四章 备选牌池
第五章 套牌变种
Right now for Miracles there are 3 primary variants: UW miracles with red, miracles with Rest in peace Helm, and Esper color miracles with Thopter/Sword.
Miracles with Red
Joe Lossett 7th Place SCG Las Vegas
Pure UWMagic OnlineOCTGN2ApprenticeBuy These Cards
4 Sensei's Divining Top
4 Brainstorm
3 Jace, the Mind Sculptor
3 Swords to Plowshares
3 Terminus
1 Supreme Verdict
3 Vendilion Clique
1 Venser, Shaper Savant
1 Snapcaster Mage
2 Entreat the Angels
3 Spell Pierce
4 Counterbalance
1 Counterspell
2 Force of Will
2 Misdirection
4 Flooded Strand
1 Arid Mesa
3 Scalding Tarn
1 Polluted Delta
4 Island
2 Plains
2 Tundra
2 Volcanic Island
2 Mystic Gate
2 Karakas
2 Red Elemental Blast
1 Pyroblast
1 Force of Will
1 Misdirection
1 Venser, Shaper Savant
1 Disenchant
1 Engineered Explosives
1 Sphere of Law
3 Rest in Peace
1 Sulfur Elemental
1 Pithing Needle
1 Entreat the Angels
This is your stock UW miracles with red. The main reason people are playing red is for the addition of red elemental blast/ pyroblast. These cards work incredibly well in the mirror/combo and to a lesser extent show and tell. They act as removal for any blue card (jace, omniscience) while also being able to counter them. Its versatility is what makes it a well used addition in the deck.
Another reason to play red is the addition of blood moon. This deck plays 7-8 basics which is incredibly high for legacy deck. A resolved blood moon against the tempo/jund decks will almost always lock them out of the game.
Miracles With Rest in peace/ Helm combo
1st Place by Alex Binek at SCG Indianapolis
U/W CountertopMagic OnlineOCTGN2ApprenticeBuy These Cards
1 Vendilion Clique
1 Venser, Shaper Savant
3 Jace, the Mind Sculptor
5 Island
2 Plains
2 Arid Mesa
4 Flooded Strand
4 Scalding Tarn
3 Tundra
1 Volcanic Island
1 Karakas
1 Helm of Obedience
4 Sensei's Divining Top
1 Blood Moon
3 Counterbalance
1 Detention Sphere
2 Rest in Peace
4 Brainstorm
1 Counterspell
2 Enlightened Tutor
4 Force of Will
2 Spell Pierce
3 Swords to Plowshares
1 Entreat the Angels
1 Supreme Verdict
3 Terminus
1 Engineered Explosives
1 Ensnaring Bridge
1 Ethersworn Canonist
1 Energy Field
1 Humility
1 Counterspell
1 Disenchant
1 Enlightened Tutor
2 Red Elemental Blast
1 Swords to Plowshares
3 Geist of Saint Traft
1 Vendilion Clique
The combo with this deck is you have rest in peace in play and you then resolve helm of obedience, you then activate it for at least 1. This will mill your opponent until at least 1 cards hit the graveyard. Since Rest in peace's replacement effect removes the cards from the game this performs an infinite loop milling out the library.
This combo can greatly increase the win chance against lot of decks. Decks like Reanimator/dredge usually have a very good game 1 against us we now have silver bullets against them and not just roll over. This combo also makes the games a lot quicker. If you are usually digging for a way to kill your opponent via Jace or entreat it could be a lot quicker with helm.
RIP builds also play enlightened tutor which can help find the combo piece or even just a top if need be. Most versions will have a lot of 1 ofs in the board for increasing the virtual amount in the board usually consisting of: Moat, humility, engineered explosives, detention sphere and sphere of law.
UW/b Miracle Control with Thopter Sword
4-0 Modo Daily
Goliat2Magic OnlineOCTGN2ApprenticeBuy These Cards
1 Academy Ruins
4 Flooded Strand
5 Island
1 Karakas
2 Misty Rainforest
2 Plains
2 Polluted Delta
1 Scalding Tarn
3 Tundra
2 Underground Sea
1 Vendilion Clique
4 Brainstorm
4 Counterbalance
1 Counterspell
1 Detention Sphere
1 Engineered Explosives
2 Enlightened Tutor
1 Entreat the Angels
4 Force of Will
3 Jace, the Mind Sculptor
1 Moat
4 Sensei's Divining Top
2 Spell Pierce
1 Supreme Verdict
1 Sword of the Meek
4 Swords to Plowshares
2 Thopter Foundry
1 Disenchant
1 Elspeth, Knight-Errant
2 Lingering Souls
3 Meddling Mage
2 Perish
1 Surgical Extraction
3 Terminus
1 Tormod's Crypt
1 Vendilion Clique
This version of miracles its a bit more combo oriented. It is trying to rely on counterbalance top in the early to mid game and close the game down with the combo. The combo works like this: You have thopter foundry in play and have sword of the meek either in play or in the graveyard. You then sacrifice an artifact (not foundry) to foundry and sword will be in the graveyard. Foundry will create a 1/1 token which will trigger sword. The sword will come into play and equip on the token. You can then sacrifice the sword to keep it going. Every time you do so you will gain a life as well. The combo is extremely grindy and mana intensive but has a snowballing effect. Once it is going it is very good and tough to beat. The only issue with this version of the deck is rest in peace is a card that is gaining popularity which could really hinder your combo.
第六章 对战分析
Miracles regardless of the build has a lot of very favorable matchups. Most of these become good matchups because of the access of terminus and or counterbalance.
Against Strom/combo decks resolving counterbalance/top is back breaking. Majority of their decks revolve around 1-2 cmc cards. This is mostly true with ANT. A top against that deck it becomes incredibly hard for them to play through it.
Aggro. This deck has a very good matchup against almost every aggro deck, with the exception of goblins. This deck single handedly put maverick away. Having access to instant speed wraths and swords to plowshare makes it a nightmare for aggro decks.
Against control the late game always favor us. This puts other control decks in awkward positions, they are usually forced to play the aggressor in these matchups. They do not have the luxury of just sitting back and sculpting a perfect hand etc.
This deck does struggle against goblins. Game 1 is incredibly hard. Goblins can generate an intense amount of card advantage and put on a big clock fast. The inclusion of cavern of souls makes almost all of our counters/counterbalance useless in the matchup. Post board you can bring in more wrath effects/spot removal but the main hindrance is that we have too many dead cards.
这里有一个文档详细记录了面对不同套牌时的换备策略:Stuff Philipp said about miracles


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