text:
An electrodeposition display device is described which uses an electrolyte containing silver species and certain anion species including iodide bromide or chloride. The electrolyte also contains a substituted ammonium halide such as tetrabutyl ammonium iodide. Such display devices have high contrast, large viewing angle and rapid redissolution of the display.
1. An electrodeposition display comprising:
(a) positive and negative electrodes;
(b) electrolyte comprising organic solvent, silver-containing ionic species and ionic species containing at least one element selected from the group consisting of iodine, bromine and chlorine in which electrical activation of the positive and negative electrodes produces an electrical action which leads to electrodeposition of a partially opaque silver species thereby altering the optical contrast of the display; CHARACTERIZED IN THAT the electrolyte comprises substituted ammonium halide selected from the group consisting of substituted ammonium iodide, substituted ammonium bromide and substituted ammonium chloride.
2. The electrodeposition display device of claim 1 in which the substituted ammonium halide is a substituted ammonium iodide.
3. The electrodeposition display device of claim 2 in which at least one R group in the formula R4 N+ I- for substituted ammonium iodide has at least one carbon atom and each of the R groups have up to 20 carbon atoms.
4. The electrodeposition display device of claim 3 in which the R groups have between 3 and 8 carbon atoms.
5. The electrodeposition device of claim 1 in which the solvent has a pKa greater than 9.
6. The electrodeposition device of claim 5 in which the solvent has a pKa value greater than 12.
7. The electrodeposition device of claim 1 in which the solvent is selected from the group consisting of dimethylsulfoxide and N,N-dimethylformamide.
8. The electrodeposition display device of claim 1 in which silver-containing ionic species is a silver halide compound in which the halide is selected from the group consisting of iodide and bromide.
9. The electrodeposition display device of claim 1 in which the electrolyte comprises in mole ratios AgI, 0.05 to 0.35 moles; NH4 I, 0.015 to 0.10 moles; tetrabutyl ammonium iodide, 0.01 to 0.20 moles, solvent, 1.00 moles.
10. The electrodeposition display device of claim 9 in which the electrolyte comprises in mole ratios AgI, 0.1 to 0.22 moles; NH4 I, 0.025 to 0.06 moles; tetrabutyl-ammonium iodide, 0.02 to 0.06 moles; and solvent, 1.00 moles.
11. The electrodeposition display device of claim 10 in which the electrolyte comprises in mole ratios AgI, 0.13 to 0.18 moles; NH4 I, 0.03 to 0.05 moles; tetrabutylammonium iodide, 0.025 to 0.04; and solvent, 1.00 moles.
12. The electrodeposition display device of claim 11 in which the solvent comprises N,N-dimethylformamide.
13. The electrodeposition display device of claim 1 in which the electrolyte comprises in addition, an opacifier, comprising solid semiconducting substance.
14. The electrodeposition display device of claim 13 in which the opacifier comprises solid semiconductor substances and solid insulator substance.
15. The electrodeposition display device of claim 14 in which the semiconducting substance has a conductivity of at least 10-9 mhos/cm at room temperature.
16. The electrodeposition display device of claim 15 in which the opacifier comprises 1-90 weight percent solid semiconductor substance, remainder solid insulator substance.
17. The electrodeposition display device of claim 16 in which the opacifier comprises 20-70 weight percent solid semiconductor substance remainder solid insulator substance.
18. The electrodeposition display device of claim 17 in which the opacifier consists essentially of 30-40 weight percent solid semiconductor substance, remainder solid insulator substance.
19. The electrodeposition display device of claim 14 in which the solid semiconductor substance consists essentially of at least one suitably doped compound selected from the group consisting of uncolored, transition metal oxides in which said doping is yield a conductivity at room temperature of at least 10-9 mhos/cm.
20. The electrodeposition display device of claim 19 in which the solid semiconducting substance consists essentially of at least one suitably doped compound selected from the group consisting of TiO2, ZrO2, Nb2 O5 and Ta2 O5.
21. The electrodeposition display device of claim 19 in which the dopant concentration ranges from 0.001 to 1.0 weight percent.
22. The electrodeposition display device of claim 19 in which the semiconductor material is semiconducting TiO2.
23. The electrodeposition display device of claim 22 in which the dopant is iron in the concentration range of 0.005 to 0.025 weight percent.
24. The electrodeposition display device of claim 14 in which the insulating substance is selected from the group consisting of BeO, MgO, ZnO, Al2 O3, Ga2 O3, Sc2 O3, Y2 O3, La2 O3, Gd2 O3, SiO2, GeO2, BeAl2 O4, ZnGa2 O4, BeAl2 O4, ZnGa2 O4, MgAl2 O4, Be3 Al2 Si3 O12, GdAlO3, NaAlSi2 O6 and NaYO2.
25. The electrodeposition display device of claim 24 in which the insulator substance consists essentially of a transition metal oxide sufficiently pure to be insulating.
26. The electrodeposition device of claim 25 in which the insulating substance is selected from the group consisting of NaAlSi2 O8 and Al2 O3.
The invention is a display device which operates by electroplating material on a transparent conducting surface.
Recent interest in display systems has been extensive principally because of the development of various integrated circuit devices such as calculators, watches, microprocessors, etc. These devices and other similar devices process or store information which often requires rapid and frequent reading. Particularly desirable in such display systems are low power consumption, good visibility (high contrast and large viewing angle) and low cost. Various systems are useful in display devices including ferroelectric ceramics, liquid crystals and various electric systems, such as electrochemichromic systems. Other display systems include plasma discharge panels and light emitting diodes. Although these systems may be satisfactory for some applications, the need remains for more versatile display systems with lower power consumption, better visibility and lower cost. Display devices may also be used as light modulators as described in a reference by J. Mantel and S. Zaromb, Journal of the Electrochemical Society, 109 (1962) pages 992-993. A display system of interest has been described by J. P. Della Mussia, Mesures-Regulation-Automatisme (France), Vol. 42, No. 5, May 1977, pages 43-44. This reference describes an alternate method of making a display system using a silver plating solution.
The invention is a versatile electrodeposition display system in which the active electrolyte contains, in addition to silver and/or iodide, bromide or chloride ions (e.g., added in the form of silver iodide, bromide or chloride), a quantity of quaternary ammonium or related halide. Iodide, bromide or chloride or mixtures thereof may be used. Use of quaternary ammonium and related salts makes for a finer deposit for the display which is easier to redissolve when a suitable electric field is applied. This results in faster display devices and permits use of higher concentrations of silver species and iodide or bromide species without accumulating undesirable heavy precipitate particles which persist as dark spots. Higher concentrations of silver and iodide or bromide species lower the power requirements for the device and reduce heat dissipation problems. Also, lower power requirements increase device reliability and lifetimes because of reduced generation of free iodine and reduced electrochemical decomposition of solvent.
Mixtures of tetra-alkyl ammonium iodide and ammonium iodide (or corresponding halides) are useful where, for example, compromise is desired between dark display and fast resolution of the precipitate. Indeed, for many applications, a mixture of a quaternary ammonium salt and an ammonium salt is preferred.
The FIGURE shows a sectioned side view of an electrodeposition display device made in accordance with the invention.
In its broadest aspects, the invention is an electrodeposition display device in which the active material (generally a paste) from which the substance is electrodeposited contains an organic solvent, a silver containing substance at least partially dissolved in the organic solvent and an ammonium halide in which at least one carbon containing group is attached to the ammonium ion. Particular attention is paid to quaternary ammonium iodides, as their use leads to faster display-changing rates and finer-grain displays. Mixtures of quaternary ammonium iodide and ammonium iodide, for example, may be used to optimize display changing rates and high-contrast.
The invention employs substituted ammonium halides in the electrolyte, which are reasonably soluble in the organic solvent used. Further, the substituted ammonium halide should not give up protons easily. Considering the formula for a substituted ammonium iodide (R4 N+ I- in which each R may be different), it is required that at least one R group have at least one carbon atom and that all the R groups have twenty or less carbon atoms and that none of the substituents on the R groups give up protons easily. For example, aliphatic and aromatic substituents are useful as well as aliphatic and aromatic substituents with halide, ketone, ether, etc., functional groups. Quaternary ammonium iodide salts involving nitrogen heterocyclic compounds are also useful.
Because of high solubility, best results are obtained with 3 to 8 carbon atoms per substituent group (R group) in the formula R4 N+ I-. Within this highly preferred group, the compounds tetrabutyl ammonium iodide and tetrahexyl ammonium iodide are preferred because of easy availability and low cost. Mixtures of compounds may be used as well as mixtures of quaternary salts with ammonium iodide.
A large variety of solvents are useful in the display device. Preference is given to solvents that are highly stable to the chemical and physical conditions present in the display device. In particular, it should not decompose under the influence of the voltages used in the device nor react destructively with the other ingredients in the display device. It should provide good solubility for silver-anion complexes (i.e., Ag3 I4 -, Ag4 I5 -, Ag2 I3 -, AgI6 -5, AgBr2 -, AgCl2 -, etc.) and preferably have a large liquid range above and below room temperature (preferably melting point less than -40 C. and boiling point greater than 120 C.).
Good solubility for the complexes mentioned above is particularly advantageous because material plates out at a lower voltage. This permits faster operation, with lower power consumption and much greater contrast in the display.
The solvent should not easily give up protons (it should exhibit a very low concentration of protons) so as to prevent deterioration of contacts by reducing protons to elemental hydrogen. Proton concentrations should be in the order of magnitude less than moderately basic water. It is preferred that the pKa value should be greater than 9 and more preferably greater than 12.
Typical solvents are dimethyl and diethyl sulfoxide, N,N-dimethyl and N,N-diethyl formamide, diethyl malonate, ethyl acetoacetic ester, ketones, esters, ethers and alcohols with high pKa values. Also useful are organic carbonates such as propylene carbonate, organic lactones, organic nitriles, nitrohydrocarbons, etc.
The solvents dimethylsulfoxide and N,N-dimethyl formamide are preferred because of high solubility for the silver-anion complexes and stability. One of these solvents (dimethylsulfoxide) has the disadvantage of a high melting point, namely 18 C. but the advantage of great solubility for silver-anion complex. This solvent is preferred only when the temperature of operation does not fall below 18 C. Mixed solvents may be used (i.e., a mixture of dimethylsulfoxide and N,N-dimethyl formamide) to obtain the advantage of high solubility and extend the temperature range of operation by lowering the melting point.
In addition to solvent, the electrolyte should contain silver compound. A variety of silver compounds may be used, provided they yield solutions of silver-containing ions. Generally, it is most convenient to use silver iodide or silver bromide. Silver containing iodides such as RbAg4 I5, NH4 Ag4 I5, and similar compounds may also be used. The corresponding bromides are also useful.
Either iodide, bromide or chloride may be used as the anion. These ions may be introduced in the form of iodide, bromide or chloride salts, or as AgI, AgBr or AgCl. Ammonium iodide, ammonium bromide or ammonium chloride salts are also useful. Mixtures of chlorides, bromides and iodides also give excellent results.
Excess iodide, bromide or chloride is preferred because it accelerates resolution of the silver deposit. This results in a faster display system. Excess halide may be added as quaternary ammonium salt, ammonium halide salt or alkali-metal salt. For convenience, the silver and halide is added as AgI, AgBr or AgCl and the excess halide is added as halide salt, (i.e., LiI, RbI, LiBr, NH4 I, etc.). Mixtures of AgI, AgBr, and AgCl, as well as mixtures of halide salts (i.e., LiI, LiBr) are used.
Concentration of silver salt may range from approximately 0.001 moles per mole of solvent to saturation. Below 0.001 moles silver salt per mole solvent, the voltage necessary to electrodeposit sufficient material for good display is excessive. The ammonium halide, alkali halide and quaternary salt concentration must be adequate to bring all of the silver halide into solution.
The concentration of the various additions employed may vary broadly as indicated above and for the iodides in the table below. The ranges are expressed in terms of moles/mole of solvent.
______________________________________ Permitted Operating Best Range Range Range______________________________________AgI 0.05-0.35 0.1-0.22 0.13-0.18NH4 I 0.015-0.10 0.025-0.06 0.03-0.05NR4 I- 0.01-0.20 0.02-0.06 0.025-0.04Solvent 1.00 1.00 1.00______________________________________
Various substitutions can be made for the compounds listed above. For example, AgBr or AgCl or other silver complex compound that is soluble in the solvent (e.g., RbAg4 I5) may be substituted for AgI. The corresponding bromide or chloride may be substituted for NH4 I as well as alkali-metal iodides, bromides and chlorides. Any quaternary ammonium salt (iodide, bromide or chloride) may be used but a tetra-alkyl ammonium iodide is preferred as set forth above. Generally, chlorides are most useful where a silver back plate is used in the display device. Bromides are most useful when special color effects (for example, blue color displays) are desired. For the most part, iodides are preferred because of the low power requirements, high contrast, etc. Mixtures of iodides, bromides and chlorides are also useful.
Various solvents are useful as set forth above. The compositional limits set forth above are for a variety of solvents but particularly for N,N-dimethyl formamide. For dimethyl sulfoxide, the maximum concentrations can be increased by about 50 percent and for various esters that might be useful as solvents (e.g., diethylmalonate), the concentration range might be decreased by about 50 percent. It should be understood that the upper bound of concentration might be a saturated solution rather than the concentration set forth in the table. Also, the compositional limits refer to the liquid part of the electrolyte and various solid substances may be added to make a paste and/or to improve optical characteristics as set forth below.
Optionally, an opacifier may be added to the liquid part of the electrolyte to improve contrast ratio, lower power requirements and improve device reliability and lifetime. The opacifier may be all semiconductor particularly if particle size is small enough to keep particles dispersed. It may also be of two types of solid substances, one a semiconducting type substance and one an insulating type substance. The substances should be stable to the environment of the display device, particularly the driving voltage.
A large variety of substances may be used as the semiconducting substance including the doped counterpart of various insulating substances, such as TiO2, Ta2 O5, Nb2 O5. Either p-type or n-type may be used. Preferably, the semiconducting substances should have conductivities of at least 10-9 mhos/cm under an applied voltage at room temperature. Higher conductivities are preferred because of more rapid switching of the display and greater contrast of the display. Typical higher conductivities are at least 10-8 mhos/cm or even at least 10-7 mhos/cm. Higher conductivities up to about one mhos/cm also can be very useful. Conductivities often vary with applied voltage perhaps due to surface charge states. Upon injection of electrons during the application of voltage, the semiconductor often becomes lightly colored, increasing its conductivity. This change is not observed in the silver containing display as deposition occurs at the same time. This color disappears on voltage reversal, leaving the background clear. The semiconducting substance should also preferably be white or light colored to provide maximum contrast with the electroplated substance making up the display. The semiconducting substance should be insoluble in the electrolyte and not be irreversibly affected by the conditions (voltage, electrode action, etc.) of the display device.
The insulating substance should preferably be white or light in color in order to provide maximum contrast with the substance plating out during operation of the display device. It should also be inert to the chemical and physical conditions of the display device, as described above, and preferably be sufficiently reflective to enhance the contrast for the display.
The concentration of semiconductor and insulator substances in the opacifier may vary over large limits and still provide excellent device performance. Preferred concentrations often depend on the properties of semiconductor used, the particular semiconductor substances used, and the properties and identity of insulator substance used. Preferred concentration ranges for typical semiconductor and insulator substances are 1 to 90 weight percent semiconductor remainder insulator. Better results are obtained using a concentration range from 20 to 70 weight percent semiconductor, remainder insulator, particularly for 4A molecular sieve and Al2 O3 or mixtures of these two insulator substances. Best results are obtained using 30 to 40 weight percent semiconductor, remainder insulator substance.
Small particle size is also highly advantageous because of the increased dispersion of the deposits, its fineness and the resolution of the display. Particle sizes less than five microns are preferred. Generally, semiconductor substances and insulator substances have a range of particle sizes. For the display systems described here, it is preferred that the average particle size is less than five microns. Still smaller particle sizes are advantageous where obtainable in a suitable semiconductor or insulator substance. For example, for either semiconductor or insulator substance, average particle size less than one micron is preferred. Average particle size less than one tenth of a micron is even more preferred.
A large variety of materials may be used as the semiconducting substance including mixtures of various substances. High optical index of refraction is preferred because of greater reflecting characteristics which increase the optical contrast of the display device. Preferred are uncolored transition-metal oxides such as TiO2, ZrO2, Nb2 O5 and other compounds containing Ti, Zr, Nb and Ta. Transition metals are metals with partially filled d shells. These substances should contain impurities or dopants to make them semiconducting. The selection of impurity depends on the basic substance chosen. For example, the valence of the impurity or dopant cation should either be less than (for p-type semiconductor) or greater than (for n-type semiconductor) the cation of the basic substance. Also, the ionic radius of the impurity cation should be approximately the same as the cation of the basic substance.
Some of cations suitable for impurity doping in basic substances are given in the table below for six coordination environments:
__________________________________________________________________________Cation M2+ Be Ni Mg Zn FeRadius .45 .69 .72 .74 .78Cation M3+ Al As Ni Co Cr Fe Mn Sc Sb InRadius r .535 .58 .60 .61 .615 .645 .645 .745 .76 .80Cation M4+ Si Ti Ge Zr Sn HfRadius r .40 .605 .53 .72 .69 .71Cation M5+ P V As Nb Sb TaRadius r .38 .54 .46 .64 .60 .64Cation M6+ Mo WRadius r .59 .60Cation M7+ ReRadius r .53__________________________________________________________________________
Although the impurity concentration in the semiconductor substance may vary over large limits, particularly good results are obtained in the range of 0.001 to 1.0 weight percent. For typical semiconductors, best results are obtained in the range from 0.005 to 0.025 weight percent.
A particular good and low cost semiconductor material is reagent grade TiO2. This grade TiO2 has sufficient impurities to make it semiconducting. Various impurities may be used as described above. A particularly effective impurity for TiO2 is iron in the concentration range of 0.005 to 0.025 weight percent.
Various insulating substances may be used provided they are insoluble and inert to the conditions of the display device. Again, high reflectivity and white or light color is desirable to increase light reflection and insure good optical contrast. Typical insulating substances are BeO, MgO, ZnO, Al2 O3, Ga2 O3, Sc2 O3, Y2 O3, La2 O3, Gd2 O3, SiO2, GeO2, and mixed oxide compounds of the above such as BeAl2 O4, ZnGa2 O4, MgAl2 O4 Be3 Al2 Si3 O12, GdAlO3, etc. Also useful are insoluble mixed-oxide compounds containing alkali-metal ions. Typical examples are NaAlSi2 O6 and NaYO2. Transition-metal oxides may also be used provided they are insoluble and do not contain impurities which make them semiconducting. Typical examples are TiO2, BaTiO3, ZrO2 KTaO3, etc.
Particularly good results are obtained by the use of alkali-metal alumino silicates (zeolites commercially known as molecular sieves) because of small particle size. Such substances are readily available and inexpensive. These substances may offer other advantages such as absorption of water inadvertently entering the display device and absorption of gas products. These properties increase device lifetime. The compound NaAlSi2 O8 (commercially known as 4A molecular seive) is preferred because of extremely small particle size and easy availability. Mixtures of compounds are often useful as the insulator substance. A typical example is NaAlSi2 O8 and Al2 O3. For TiO2 as the semiconductor substance and NaAlSi2 O8 as the insulator substance, a concentration range from 30 to 70 weight percent semiconductor remainder insulating substance shows excellent results.
Useful opacifier compositions are as follows:
a. 1 gm TiO2 --2 gm 4A molecular sieve.
b. 1 gm TiO2 --1 gm 4A seive--1 gm Al2 O3.
c. 1 gm TiO2 --1 gm 4A sieve--4 gm Al2 O3.
d. 1 gm TiO2 --2 gm Al2 O3.
The reference cell may vary in structure depending on application and use. Generally, the reference cell consists of two transparent substrates (e.g., glass or plastic), which enclose a volume containing the active medium, often in the form of a paste. Electrical contact with the active medium may be provided in a variety of ways, including transparent contacts (e.g., indium-tin oxide, InO2, etc.) mounted on the inside (side facing and in contact with the active medium) of the transparent substrates. Polarity is arranged so that electrodeposition occurs on the front face. The conducting material may be put down on the transparent substrates in predetermined shapes so as to form numbers, letters, etc. Various geometric shapes for producing figures, letters, numbers, etc. may also be used. A typical example is the seven segment alpha numeric display extensively used in display devices as calculators, watches, etc.
The invention is conveniently illustrated by a description of the figure. The figure shows an electrodeposition display device, 10, made in accordance with the invention. It comprises a lower transparent glass substrate, 11, a lower transparent electrical contact, 12, made of indium-tin oxide and an electrical connection, 13, to the lower transparent electrical contact, 12. Spacers, 15, are used to offset the lower transparent glass substrate, 11, from the upper transparent glass substrate, 18, and seals, 14, and 16 are used to prevent leakage of the active material out of the cavity 20. In this particular device, the seals are made of wax paper. The inner surface of the upper transparent glass substrate, 18, also contains a transparent electrical conductor, 17, and electrical contact, 19. The cavity contains the active material with suitable organic solvent, source of silver ions, quaternary ammonium halide.
Non-Patent Citations
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Scott G Winterton, Deseret News
SALT LAKE CITY — The House approved a bill Friday that would allow the speed limit to be raised as high as 80 mph on highways and freeways throughout the state.
Rep. James Dunnigan, R-Taylorsville, the sponsor of HB80, said Utah has increased the posted speed limit to 80 mph on nearly 380 miles of freeway over the past five years.
"We're finding out changing the number on the sign has not changed people's behavior," Dunnigan said, citing Utah Department of Transportation studies that showed most drivers only upped their speed a few miles per hour.
"People have this kind of built-in comfort level, built-in speed limit," he said, noting UDOT determined that the deaths that have occurred on freeway sections with 80 mph speed limits were not related to the increase.
Dunnigan said his bill would permit UDOT to increase the speed limits on some sections of freeways in urban areas from 65 mph to 70 mph or 75 mph, and to 80 mph in less-populated areas of the state.
Higher speed limits do not have a negative impact on air quality, he said, even an increase of as much as 15 mph.
"I think we're all concerned about safety. I think we're all concerned about air quality," Dunnigan said. "It's hard to say what will happen in the future, but we have five years of data now."
The bill passed the House 63-8 and now goes to the Senate.
— Lisa Riley Roche
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Six tantalising teasers later, here we present the final film by Wes Anderson and Roman Coppola, starring Lea Seydoux: Prada Candy L'Eau.
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Armstrong's samples showed steroids in 1999: UCI
PARIS (Reuters) - Lance Armstrong returned four samples with traces of banned corticosteroids in the 1999 Tour de France, the International Cycling Union (UCI) said on Wednesday, although the governing body added it did not handle them as positive tests.
On Tuesday the Belgian newspaper Het Nieuwsblad published a copy of an alleged internal UCI memo which said a lawyer for the sport's ruling body had said the American's samples from the 1999 showed traces of corticosteroids on four occasions.
Armstrong, who has been banned for life and admitted to doping his way to seven consecutive Tour titles from 1999-2005, had already admitted to using corticosteroids for a saddle sore in 1999 although he produced a back-dated TherApeutic Use Exemption (TUE) to justify the use of a banned substance.
"During the Tour, Armstrong was tested 15 times. In the four samples indicated below traces of triamcinolone, a corticosteroid, were found. No other prohibited substances were found," the UCI said, adding that the samples in question were collected on July 4, 14, 15 and 21.
The governing body said the French Ministry of Sports also ruled that no doping offence had been committed.
"The samples taken during the 1999 Tour de France were analysed by the French National Anti-Doping Laboratory in Châtenay-Malabry," the UCI said.
"The French Ministry came to the conclusion that there had been no anti-doping rule violation. In a conversation with the UCI's Dr Schattenberg at the time, the French Ministry doctor confirmed that the presence of traces of corticosteroids found in samples taken from Armstrong was compatible with the use of a skin cream; that the use of a skin cream was accepted as proven by the French Ministry; and that there was therefore no anti-doping rule violation.
"If the corticosteroids had been used systemically (ie. injected or taken orally), the consecutive test results would have all been positive."
The UCI agreed and said that "both the French Ministry and the UCI Anti-doping Commission found that there was conclusive evidence that no anti-doping rule violation had taken place".
(Editing by John Mehaffey)
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Research in Focus - Soft Drinks: How Consumption Patterns Drive Branding and Product Development
In 2011, global soft drinks sales reached 609bn litres, up by 4% over the previous year and continuing a steady upwards trend. At the same time, global consumption continues to evolve, both in terms of what consumers are buying as well as how, where and - perhaps most importantly - why.
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text:
Look Younger with Vitamins
Youthful, glowing skin is one of the most attractive qualities in men and women. But in the hustle and bustle of our daily lives it is extremely difficult to keep skin from ageing. It is in our turbulent mid-twenties that skin tends to lose its elasticity because of depleting levels of collagen. Today, we aren't talking about make-up, hiding flaws, or expensive surgeries to get that youthful and glowing skin; we're talking about the beauty vitamins that will help you look your best. That's right - vitamins A, C and E, when incorporated into a daily skin care routine, will help you look years younger while leaving you refreshed and healthy.
Vitamin A to put a hold on premature ageing
Recommended Daily Allowance:
Men: 3,000 IU/day
Women: 2,310 IU/day
Vitamin A plays a vital role in deciding how your skin will look when you have crossed 30. If consumed in the right quantities on a daily basis, Vitamin A aids in keeping the skin's outer layer in perfect shape as well as keeping harmful free radicals at bay. It also helps in the healing process of the body. Include vitamin A enriched products in your beatuy regime, but don't forget to eat healthy meals rich in vitamin A. Foods like fish, egg yolks, greens, oranges, mangoes, apples, and pumpkins will give you adequate vitamin A. These fruits and vegetables contain plenty of beta-carotene and other carotenoids. Our body is responsible for converting these organic compounds into vitamin A. However, too much of it might get you into trouble. So, follow the daily recommended allowance.
Also Read: Vitamins and Supplements: How Much is Too Much
Vitamin C to delay the formation of wrinkles
Recommended Daily Allowance:
Men: 90 mg/day
Women: 75 mg/day
Vitamin C delays the formation of wrinkles naturally and is good for both oily and dry skin. It also helps and protects the skin from the harmful rays of the sun. Guavas, amala, limes, oranges, lemons and papayas are high in Vitamin C content. Even fish is a good source of vitamin C. Pulses left in water also provide this vitamin in abundance. Another, topical but great, way of including vitamin C in your beauty routine is through vitamin C enriched face masks.
Vitamin E to protect your skin against pollutants
Recommended Daily Allowance: 22.4 IU/day
Vitamin E occupies the number one slot in the race of beauty vitamins. And why not, after all it gives a lot in return. It delays ageing, protects your skin against harmful pollutants and is full of wonderful healing properties. The skin gets easily moisturized with its usage, thus it is suitable only for dry and mature skin. Vitamin E is found in abundance in green leafy vegetables, nuts, seeds, legumes and vegetable oil.
Image courtesy: © Thinkstock photos/ Getty Images
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text:
Sebastian Larsson's late leveller denied Alan Irvine three points on his West Brom debut as Sunderland snatched a 2-2 draw on Saturday.
A brace from Saido Berahino cancelled out Lee Cattermole's thunderbolt opener for Sunderland and appeared to have handed Irvine a dream start as the new Premier League season got under way.
However, Larsson swept home a low strike in the 85th minute to ensure Gus Poyet's men left The Hawthorns with a point.
Irvine was a surprise choice to replace Pepe Mel as head coach in June and Cattermole ensured a nervy start to the 56-year-old's West Brom bow with a rasping long-range drive after just five minutes.
But West Brom were level shortly before the break when the hosts were awarded a debateable penalty before Berahino kept his cool from 12 yards.
Steven Fletcher had a goal ruled out for offside after the break and Sunderland were further frustrated when Berahino finished from close range in the 74th minute.
However, Larsson had the last say with a composed finish after good work from Patrick van Aanholt.
Cattermole, who had previously netted just once for Sunderland, opened the scoring with an unstoppable strike in the fifth minute.
The 26-year-old collected the ball 25 yards from goal after a Sunderland set-piece and lashed his strike into the top right-hand corner, Ben Foster unable to keep it out despite getting his hands on the ball.
Despite the setback, the home side enjoyed plenty of possession, but failed to create clear-cut chances.
Sunderland should have punished West Brom for their lack of attacking prowess on the half-hour mark when the unmarked Valentin Roberge headed Larsson's teasing free-kick wide.
Chris Brunt responded for West Brom with a fizzing strike from distance that went narrowly wide, before new signing Craig Gardner - making his debut against his former club - forced Vito Mannone to tip over the bar with a dipping shot.
West Brom's pressure paid dividends three minutes before the break.
Referee Neil Swarbrick perhaps harshly adjudged that Roberge had tugged down Victor Anichebe in the area and Berahino rolled the resulting spot-kick in the bottom left-hand corner, sending Mannone the wrong way.
West Brom thought they had gone ahead shortly after the restart when Craig Dawson's header appeared to cross the line, despite Fletcher's clearance, but the referee had blown for a foul in the area.
Sunderland were also denied by the officials when Cattermole's cross was flicked by Wes Brown into Fletcher, who headed home at the back post, only to be thwarted by an offside flag.
Berahino then put West Brom ahead.
Graham Dorrans' strike was well saved by Mannone, but Gardner collected the ball on the left of the box and lofted a wonderful cross that Berahino side-footed home at the back post.
Sunderland, however, struck five minutes from time to secure a share of the spoils.
Debutant Van Aanholt found space on the left and picked out Larsson, who applied the low finish from eight yards.
0 - 1
S. Berahino (PG) 42'
1 - 1
S. Berahino 74'
(assist by C. Gardner)
2 - 1
2 - 2
85' S. Larsson
(assist by P. van Aanholt)
|B. Foster
|J. Olsson
|S. Pocognoli
|C. Dawson
|A. Wisdom
|C. Gardner
|Y. Mulumbu
|C. Brunt
|G. Dorrans
|V. Anichebe
|S. Berahino
|42' 74'
|Coach: A. Irvine
|V. Mannone
|W. Brown
|J. O'Shea
|P. van Aanholt
|V. Roberge
|A. Johnson
|L. Cattermole
|S. Larsson
|J. Rodwell
|S. Fletcher
|C. Wickham
|Coach: G. Poyet
for C. Brunt 77'
for C. Gardner 84'
for G. Dorrans 84'
for J. Rodwell 68'
for A. Johnson 73'
for W. Brown 81'
|Rafael: Chelsea are beatable
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|Paraguayan Division Profesional Review: Libertad gain ground, Cerro Porteno held
|Lovren demands better display
|´Arrogant´ Van Gaal insists United can catch Chelsea
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|Turkish Super Lig Review: Besiktas win again, Sneijder settles derby
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text:
I wish I'd n e v e r met you.
I wish I'd n e v e r met you.
I feel like the Nashville fandom is nonexistent on tumblr so if you watch Nashville on ABC reblog this
I can see your eyes staring into mine.
But it's a battlefield and you're on the other side.
You can throw your words sharper than a knife.
And leave me cold in another house on fire.
Now you only bring me black roses.
And they crumble in the dust when they're held.
Now you only bring me black roses
But I'm not under your spell,
I'm not under your spell… [x]
Hunter's new song for 'The Best of Me' Soundtrack!
"It's between me and Juliette and no one else."
(Source: whentherightonecomesalong)
Im just gunna bring this back into focus.
F. Scott Fitzgerald (via lykereally)
(Source: amortizing)—


text:
Swimming Nude - Caught the wife swimming nude one day. I dared her to post the pics on your site she said sure so enjoy I did comments at rutaboy @ rock.com
- Rocky
From the makers of DARERING comes another nugget called SELLYOURSEXTAPE. These are real people from Oregon who have never done anything like this before. They borrowed videocameras from the site owner and filmed themselves at home, in the shower, outside ... ... Click here to watch now!
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Cum with Her ||
Audio - Submit your Truth or Dare Pics and Stories! - Girls
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Kink ||
© 2004 Truth or Dare Pics


text:
Once Upon a Dead Man
TV MovieAlternate Title: McMillan and Wife
More in Television
TV Highlights
What's On This Week
A daily updated summary of the week in TV.
Program Overview
Executive Producer: Leonard B. Stern
Genre: Mystery
Genre: Mystery
Program Synopsis
A San Francisco police commissioner is dragged into a charity auction theft and a mysterious murder by his kooky wife. Rock Hudson made his TV acting debut in this pilot to his hit "McMillan and Wife" series (1971-77). Susan Saint James and John Schuck were the other holdovers from the pilot.
What's On Tonight
- A Star Who Has No Time for Vanity
- An Opera Under Fire
- Critic's Notebook: A Loving, Lingering Farewell Embrace
- Heirs Sue Bank Over Sale of Nazi-Looted Art
- Television Review: Twins, Raised in Different Worlds
- Art Review: It Was Hip to Be Square
- Indian Modernist, Artist of Mystery
- Tim Hauser, the Founder of the Manhattan Transfer, Dies at 72
- With New 'Death of Klinghoffer,' Furor Only Grows
- A Teacher Who Bridges the Eras


text:
ICE Futures U.S. will add the Port of Virginia as a delivery point for the arabica coffee futures contract, effective with the September 2016 contract, the exchange said in a notice on Tuesday.
An exchange spokeswoman declined to comment on the reason for the addition.
There are currently no exchange certified coffee warehouses in Virginia.
(Reporting by Marcy Nicholson; Editing by James Dalgleish)
The Port of Vancouver USA welcomed the Kypros Unity, commanded by Capt. Wilfredo F. Itable of Cyprus, on her maiden voyage Oct. 28.
Capt. Itable and his 20-member
Planning and execution of port and maritime safety and security in Caribbean region is all about partnerships
Maritime security and safety experts are meeting in Nassau,
Braemar (incorporating The Salvage Association) welcomed an invited group of marine insurance professionals onto its specialist port and shipyard familiarization
A government study on Thursday essentially supported the notion that easing the decades-old restriction on exporting U.S. crude was more likely to lower than raise
This week, General Dynamics Bath Iron Works celebrated two milestone events for the Arleigh Burke-class program. On October 30, Bath Iron Works held a keel laying
The latest U.K. Logistics Confidence Index commissioned by Barclays and Moore Stephens reveals that confidence in the U.K. logistics sector remains high but more
Record 2014 third quarter earnings per share of $1.34 compared with $1.21 in the 2013 third quarter, which included a $0.08 benefit due to the reduction of the United earnout liability.
Brazil's Vale posted a surprise loss of $1.44 billion on Thursday, hurt by a fall in the price of iron ore, higher production costs and a weakening Brazilian currency.


text:
15 buildings that say "San Francisco"
Visions of epic comeback spurred Harbaugh to stick with...
Jennifer Lawrence blasts Perez Hilton for posting nude photos
Lyft, Uber can operate at SFO
Gallery: Astronaut Chris Hadfield's photos from space
Monthly Archive for September, 2011
Schwarzenegger: Wasn't going to run for Guv until did so on Leno
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Herb Caen lives! Just ask Sarah Palin (VIDEO)
We always knew that deep in her heart, Sarah Palin was a longtime fan of the San Francisco Chronicle. Why else would she confuse GOP presidential candidate Herman Cain with The Chronicle's late …
Rick Perry's debate bumbling costs him in poll
(This comes from our Hearst Comrade Nolan Hicks at the San Antonio Express-News.) The first national poll conducted since last Thursday's Republican debate shows that Texas Gov. Rick Perry's bumbled …
Chris Christie, the Anti-Obama, shows off at Reagan Library
For those of you wondering why the GOP establishment is lusting after New Jersey Gov. Chris Christie, the rotund and plain-spoken fiscal conservative known as the anti-Obama, check out his speech …
Austerity for the long haul
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text:
Royal hack police worker avoids jail
A civilian police worker who hacked into force computers to steal data on a royal visit to Wales has avoided prison for crimes his lawyers claim were motivated by idle curiosity. Martin Lansley, 31, was employed by Dyfed-Powys Police when he obtained unauthorised access to classified material about a then upcoming visit by the …
"motivated by idle curiosity."
As opposed to, say, motivated by his interest in UFOs?
One law for them...
Surely "the force estimate that the hacking spree cost a total of $3bn"?
and this is different to looking for UFOs how... ? at least the UK police force weren't using default passwords... ;)
Would that work for anyone?
I wonder if I would get away with it if I did exactly the same thing (with the exception of becoming a police worker) and said I was just curious...
Oh and by the way, I'm curious about creditcard numbers too!
So ...
He didn't have Aspergers Syndrome, then?
Humble Pie?
Pains me to say it but how come this guy gets to use the 'idle curiosity' card but a certain someone else (who I will admit I despise) is off for a free 'holiday' courtesy of the United States?
But then of course there are two important factors: 1. He works for the police (albeit as a civilian) and 2. Yankee-Doodle-Dandy-Land hasn't had it's security holes exposed.
I'm off to be 'idly curious' about Semtex
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- Is your home or office internet gateway one of '1.2 MILLION' wide open to hijacking?


text:
Production Supervisor Jobs in Gauteng
Related Jobs: Production Manager Gauteng, Production Manager, Production, Supervisor, Shift Production Supervisor
Production Supervisor
Direct Employer - Gauteng
Client based in Johannesburg requires a Production Supervisor in the manufactures of products, organizing and monitoring workflow, high pressurized environment Production Supervisor Work careers Gauteng... Permanent... R1 Per Month
from: careers24.com - 5 days ago
Production Supervisor
ROC Outsourcing - Ekurhuleni (East Rand)
Duties· Accomplishes manufacturing staff results by communicating job expectations;planning, monitoring, and appraising job results; coaching, counseling, anddisciplining employees; initiating, coordinating, and enforcing systems,policies, and procedures·... Production Supervisor careers Gauteng...
from: pnet.co.za - 5 days ago
Production Supervisor
Executech - Gauteng
To apply for this position please forward your CV to . Please also include the name of the position and reference number of the position you would like to apply for. Participate within the Health, Safety and Environmental Programmes To apply for this... Production Supervisor Composite in Gauteng... Permanent...
from: careers24.com (+1 source) - 10 days ago
Production Supervisor
Capital Outsourcing Group - Isando - Walkerville
Production Supervisor Grade 122-3 years Production experience Computer Literate Production Supervisor jobs Bc... R 6000/m
from: pnet.co.za - 5 days ago
Career Direction - Johannesburg Metropolitan
Continuously seek improvement options Allocate jobs in absence of production manager Ensure machine maintenance and service ability Tube laser welding or tube making experience essential Production Supervisor jobs Gta... R25 000 + medical aid and pension (shift allowance and overtime)
from: pnet.co.za - 4 days ago
EE Workshop/Production Supervisor (GRW Commercials)
GRW Engineering - Boksburg, South Africa
Our company situated in Jetpark Boksburg is looking for a Workshop/Production Supervisor with a Technical Background. Do quality inspections of work in progress Grade 12 or equivalent qualification Requirements: Production Supervisor jobs Hamilton... Permanent...
from: careerjunction.co.za - 3 days ago
Production Supervisor
Tumaini Consulting - Gauteng
One of the top food manufacturers in South Africa is looking to employ a Production Supervisor at their plant based in Johannesburg. Requirements:National Diploma in Production Management5 -10 years' FMCG experience of which at least 3 years' are in a... Production Supervisor jobs Inc... R260k - R220k P/A
from: pnet.co.za - 9 days ago
Supervisor/Production Foreman
Boardroom Appointments - Germiston
The candidate must have the following:Must have A grade status or higher on CNC Lathes & Milling Machines Must be able to set-up machines, do off-sets & measurements, read drawings & know the basics of programming machinery. Production Supervisor jobs North West...
from: pnet.co.za - 2 days ago
Production Supervisor x2 (The Working Earth)
THE WORKING EARTH - Centurion, South Africa
Company seeks to employ Production Supervisors with strong leadership skills willing to manage 35 people. The ideal candidates needs to be driven and have the ability to work under pressure with 5 years' technical, mechanical and metal experience. The... Permanent...
from: careerjunction.co.za - 18 days ago
Discover people in your social networks who work for the listed companies.
Network contacts will not see that you've used this resource until you share or recommend the job offer after signing in.
Supervisor High Rsk( PRODUCTION)
Wozani Recruitment Agency - Gauteng
Microsoft excel and e-mail§ Ensure compliance with
from: pnet.co.za - 5 days ago


text: Bryan Stewart of Suisun City, California pays his respects to the memory of Giselle Renee Conway-Allen, 13 of Suisun City girl whose body was found in Allan WItt Park in Fairfield last Friday at a memorial set up in the park on Tuesday. Stewart said "I am a father and I just had to pray for her." Joel Rosenbaum/The Reporter, Vacaville (Joel Rosenbaum)


text:
"…Haig made Elsa's fear feel like real anxiety, which is what this character is all about. Elsa is a woman who lives in a constant state of worry that something will make her so afraid that she'll lose control again, and that's something people with anxiety can strongly relate to. It's also something Haig captured perfectly—that fear of yourself and who you are when your anxiety is at its worst. From her shaking hands and her tight fists as she struggled to control her magic just walking down the street to her struggle to control her breathing as she hid, the physical details of her anxiety were heartbreaking." (x)
Just lucky, I guess.
Lana Parrilla | BTS 4x03 [x]
Megan Fox attends the photocall of 'Teenage Mutant Ninja Turtles' on October 5, 2014 in Berlin, Germany.
Évelyne Brochu by Maxyme G Delisle
X Factor Series 11, Episode 2.
Paul Wesley - Self Assignment, September 2014 (x)
You say I'm crazy
Cause you don't think I know what you've done
But when you call me baby
I know I'm not the only one
Christina Aguilera pregnant in 2007 and 2014.


text:
occasionally I will explode into a butt of Joe Liebgott feelings; this is perfectly normal and will pass as soon as it comes.
pronouns: she/her
(Source: relative-pronoun)
{ snow day }
(Source: ohstewarts)
Pictures of Niall backstage at iHeartRadio found on a disposable camera.
Some Moonrise Kingdom fan art. Practising for a poster design exercise.
(Source: deadlybr0)
wake up.
(new collaborations between lisa & emma coming soon!)
GUYS guys guys. I know you were all there in college when I vowed to myself that I hated animation and would never do it again, but I kinda wanna do it again.
(Source: yeah-disneygeek)
(Source: thisisadulting)
Today In Solidarity (10.5.14): Voter Registration surges in Ferguson in the wake of Mike Brown's death. The ballot box is not a singular or final solution to dismantling the systems of oppression in Ferguson and beyond, but it's certainly an important area to focus on. Remember, the current city council/government is disproportionately white due in large part to voter apathy. It's not too late to get registered, but many state deadlines are coming up this week! For more info visit: VOTE MISSOURI or Rock the Vote.
There's no place where you can affect change more directly or effectively than at the local level. Don't sleep on municipal elections. #staywoke #farfromover
I just want to go home.
Fangirl Challenge → [2/5] Pilots: Gilmore Girls (October 5, 2000)
"Last Friday these two guys were tossing around a ball and one guy nailed the other right in the face. I mean, it was a mess, blood everywhere, the nurse came out, the place was in chaos, his girlfriend was all freaking out, and you just sat there and read. I mean, you never even looked up. I thought, 'I have never seen anyone read so intensely before in my entire life. I have to meet that girl.'"
If you haven't watched this show you are really missing out.
(Source: carolineforbbs)
achilles is that kid who takes gym class too seriously
#'achilles come on it's just dodgeball' 'he insulted my HONOR' (x)
#hector throws a ball directly at achilles who is momentarily distracted by agamemnon talking shit about him #and as he moves to confront agamemnon the ball shoots past him and hits patroclus right in the face #patrcolus falls to the ground in slow motion as achilles watches in horror #MMMM WHATCHA SAYYY (via)
Bryarly-Find Your Love
Album pre-order available now! It's $1 less on iTunes/Bandcamp during preorder, and you can get the track for whatever you want on Bandcamp.


text:
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Georgia Planning
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Agenda Items
The Georgia Planning Commission meets the second and fourth Tuesdays of each month at the Georgia Municipal Offices, 47 Town Common Rd. North. Agendas and minutes are available at the town's website. For more information call the Town Planner's Office at 524-9794.
Program Details
- Production Date: 12/22/2009
- Series: Georgia Planning
- Length: 01:27:07
- Town: Georgia
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