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Under an outdoor tent a few blocks from Emanuel African Methodist Episcopal Church, Sharon Simmons paused while cleaning up from the previous night's revival to ponder the idea of forgiving the white man accused of killing nine of the historic black church's members, including the pastor.
Pope Francis appealed on Friday to faithful from all Christian churches to put divisions aside and concentrate on what unites them amid the persecution and slaying of Christians in parts of the world.
Bubba Watson says he's painting over the Confederate flag on his car made popular in "The Dukes of Hazzard" television series.
Raised by firefighters from the smoking wreckage of the World Trade Center, a flag telegraphed both anguish and resolve. Planted atop a mountain on Iwo Jima, another piece of national cloth came to symbolize collective perseverance and conquest.
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Hispanic leaders are warning of harm to Republican White House hopes unless the party's presidential contenders do more to condemn Donald Trump.
Wading into presidential politics, President Barack Obama on Thursday promoted his brand of middle-class economics by drawing sharp contrasts with "mean" Republicans in a state whose GOP governor was preparing to enter the vast 2016 presidential field.
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A Montana man said Wednesday that he was inspired by last week's U.S. Supreme Court decision legalizing gay marriage to apply for a marriage license so that he can legally wed his second wife.
Loud but hardly universal catcalls from Republicans underscored the obstacles and opportunities ahead as U.S. and Cuban leaders announced an opening of embassies in Havana and Washington and a resumption of diplomatic relations severed the year President Barack Obama was born.
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On a twisty, snow-lined hill that the locals call "Devil's Backbone," a 12-ton semi-trailer came loose from its tractor and plowed into an oncoming line of pre-dawn commuters.
The superintendent at the prison where two killers broke out has been placed on leave along with his security chief and 10 other staff members amid an internal investigation into how the inmates pulled it off, a state official said Tuesday.
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A method for forming a carbon-containing layer on a polymeric substrate is disclosed. The polymeric substrate is modified physically and chemically using an inductively coupled plasma process. The carbon-containing layer can be fluorocarbon film with different physicochemical properties and structure.
1. An article comprising:
a polymeric substrate comprising a modified surface, wherein the modified surface is a physically modified surface comprising a crosslinked region;
a fluorocarbon film on the modified surface of the polymeric substrate,
wherein the fluorocarbon film is grafted to at least a portion of the polymeric substrate; and
a biocompatible layer on the fluorocarbon film.
2. The article of
exposing a polymeric substrate to an inductively coupled plasma, thereby creating a modified surface on the polymeric substrate;
depositing a fluorocarbon film on the modified surface of the polymeric substrate, wherein the fluorocarbon film is grafted to the polymeric substrate; and
forming a biocompatible layer on the fluorocarbon film.
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This invention was made with Government support under Grant (Contract) Nos. CMS-0528506 and CMS-0127754 awarded by the National Science Foundation. The Government has certain rights to this invention.
Fluorocarbon (FC) film deposition by different plasma techniques has been used in numerous electrical, mechanical, and biomedical applications mainly due to the desirable physicochemical properties (e.g., dielectric constant, surface energy, friction, and wettability) and hemocompatibility of FC films.
It would be desirable to improve the bonding between a fluorocarbon film and the substrate upon which it is formed. For example, in an article including a fluorocarbon film and a substrate, any separation between the fluorocarbon film and the substrate upon which it is disposed can result in problems, especially if the article is a medical device which resides in a patients' body.
Embodiments of the invention address the above problems, and other problems, individually and collectively.
One embodiment of the invention is directed to a method including exposing a polymeric substrate to an inductively coupled plasma, thereby creating a modified surface on the polymeric substrate. A fluorocarbon film is then deposited on the modified surface of the polymeric substrate. At least a portion of the fluorocarbon film is grafted to the polymeric substrate.
Another embodiment of the invention is directed to an article comprising a polymeric substrate comprising a modified surface. A fluorocarbon film is on the modified surface of the polymeric substrate. At least a portion of the fluorocarbon film is grafted to the polymeric substrate.
Embodiments of the invention can be used as polymeric implants and biodevices interacting with soft tissue. They can be used in biological applications requiring durable, hydrophobic, and lubricious surface coatings in particular. Embodiments of the invention relate to fluorocarbon films with desirable in vivo characteristics. The films can have strong interfacial layers that provide for enhanced adhesive strength and can have flexible surface layers for increased lubricity.
These and other embodiments of the invention are described in further detail below.
Embodiments of the invention are directed to methods for forming articles including polymeric substrates with fluorocarbon films on them. One embodiment of the invention is directed to a method. The method comprises exposing a polymeric substrate to an inductively coupled plasma, thereby creating a modified surface on the polymeric substrate. After the polymeric substrate is exposed to the inductively coupled plasma, a fluorocarbon film is deposited on the modified surface of the polymeric substrate. The inductively coupled plasma can break bonds at the surface of the polymeric substrate so that at least a portion of the fluorocarbon film is grafted (or covalently bonded) to the modified polymeric substrate. If desired, a subsequent layer such as biologically compatible layer may be formed on the fluorocarbon film.
Any suitable polymeric substrate may be used in embodiments of the invention. The substrate may be a layer on a larger surface, or may be a stand-alone substrate that may be in any suitable form. For example, the substrate may be in the form of a plate, a tube, sphere, or complex shape. In preferred embodiments, the substrate is in the form of a tube so that the formed article can be used as an artificial artery, catheter, or the like. The substrate may also have a convex shape, a concave shape, a solid of revolution shape, or any other suitable shape.
The polymeric material in the polymeric substrate may comprise any suitable polymers including homopolymers, copolymers, blends, etc. Examples of suitable polymeric materials include polyethylene, medium-density polyethylene, low-density polyethylene, polymethylmethacrylate, silicones, and polyurethanes. Low-density polymers such as low-density polyethylene are preferred. In some embodiments, high molecular weight polymers such as those that can be used in orthopedic implants or medical devices can be present in the substrate.
Once obtained, the polymeric substrate may be pretreated in any suitable manner. In some embodiments, the polymeric substrate may be exposed to an inductively coupled plasma to modify the surface of the polymeric substrate. An inductively coupled plasma is a plasma that is driven by a current oscillating in a coil, either around or adjacent to the vacuum vessel. The oscillating current gives rise to a time-varying magnetic field in the gas, which induces a local electric field, which accelerates electrons and excites the plasma.
The inductively coupled plasma may have any suitable properties and may comprise any suitable precursor gas. Suitable precursor gases may include oxygen, hydrogen, nitrogen, and noble gases. Different gases may modify the surface of the polymeric substrate in different ways. For example, an oxygen plasma can be used to produce various functional groups on LDPE surfaces and other types of surfaces. In another example, exposure to an inert plasma (e.g., Ar and He) can be used to produce polar functionalities on polymer surfaces. The modification of the surface of the polymeric substrate could also be mechanical in nature. For example, the modified surface of the polymeric substrate can be rougher than an untreated polymeric substrate.
The inductively coupled plasma process may have any suitable process parameters. For example, in some cases, the plasma chamber may be kept between about 50 and about 800 mTorr (e.g., 500 mTorr), the plasma power may be between about 75 and about 1200 Watts (e.g., 1200 W) and the treatment time may be between about 1 minute and about 30 minutes (e.g., about 15 minutes).
After exposing the polymeric substrate to an inductively coupled plasma, a fluorocarbon film may be formed on the polymeric substrate with the modified surface. The fluorocarbon film may be formed using any suitable process including a plasma process. Exemplary plasma processes include capacitively coupled and inductively coupled plasma processes.
Generally, plasma treatments of a polymeric substrate can be achieved by placing the workpiece in contact with the gas to be used in the treatment and imposing high-energy radiation, sufficient to ionize the gas to a plasma state. While not intending to be bound by any particular theory or mechanism of operation, it is believed that the plasma activates the polymer chains that are in contact with the plasma by dissociating covalent bonds in the polymer chains to form free radicals that are reactive with each other or with free radicals in the plasma gas itself. The reactions that then occur at these activated sites will vary with the type of gaseous substance used to form the plasma, or with operating conditions such as the power density, exposure time, working pressure, gas flow rate, temperature, electrode spacing, chamber dimensions, substrate bias voltage, or combinations of these conditions.
In a capacitively coupled plasma (CCP) process, electrodes are placed inside a plasma processing chamber, and they ionize precursor gases to form a plasma. An example of a capacitively coupled plasma processing apparatus is shown in
An inductively coupled plasma (ICP) may also be used to deposit the fluorocarbon film on the polymeric substrate. Inductively coupled plasma processes are described above in the pretreatment process. Similar processing conditions can be used in the deposition of the fluorocarbon film; however, the feed gas will be different in the fluorocarbon layer formation process than in the pretreatment process. Examples of suitable feed gases are provided below.
In some embodiments, a shield may be used to shield the polymeric substrate from the plasma to control the plasma process and to selectively modify the surface (either physically and/or chemically) of the polymeric substrate. The advantage of using a shielded plasma over pulsed or downstream plasma is that the treatment conditions can be varied without changing the power supply or chamber configuration. The shield may comprise inorganic materials such as Al, Pyrex�, LiF, CaF2, Al2O3, and SiO2. By using a shield, one can control the types of plasma species and/or radiation reaching the polymeric substrate. For example, Al and other radiation blocking metals may only allow uncharged particles to reach the polymer substrate. On the other hand, LiF, CaF2, Al2O3, and SiO2 may allow only uncharged particles, UV (ultraviolet) and/or VUV (vacuum ultraviolet radiation) to reach the polymer substrate.
The shield may be stationary within the chamber, or is preferably movable (e.g., coupled to a movable motor) in the chamber so that it can cover or not cover some or all of the polymeric substrate during the surface modification process step. It may also cover or not cover all or some the polymeric substrate during the deposition of the fluorocarbon film. Additionally, the shield can cover the substrate during one process, but not a subsequent process, or vice-versa.
Schematic illustrations of various processing chambers with shields are shown in
As illustrated in
The power applied to convert the gas to plasma form can be selected in accordance with the effect sought to be achieved and the desired depth to which the effect will penetrate below the surface into the bulk of the polymer. Penetration depths may be less than one millimeter, or within the range of 1-10 mm or greater in some cases. Penetration depths that are too deep may alter the properties of the underlying substrate in some cases. In some applications, suitable power intensities, expressed in terms of wattage per unit area of the surface to be treated, range from about 2 to about 100 watts per square centimeter.
Other deposition conditions are likewise variable. The exposure time for example can be selected with the considerations similar to those used for the power density. In some cases, exposure times ranging from about 2 minutes to about 60 minutes, and preferably from about 4 minutes to about 30 minutes can be used. Suitable pressures in the plasma chamber can be within the range of about 50 mtorr (6.65 pascals) to about 250 mtorr (33.2 pascals), or from about 80 mtorr (10.6 pascals) to about 230 mtorr (30.6 pascals). The flow rate of the plasma gas across the workpiece surface being treated may vary, typically from about 50 to about 2000 standard cubic centimeters per minute (measured under standard conditions of temperature and pressure, and expressed as sccm), and preferably from about 100 sccm to about 1000 sccm. The deposition process does not require elevated temperatures and can be performed at temperatures less than 50� C., preferably from about 20� C. to about 40� C.
The gas used to deposit the fluorocarbon film may comprise organic fluorides such as trifluoromethane, tetrafluoromethane, tetrafluoroethane, hexafluoroethane, difluoroethylene, and hexafluoropropylene, as well as tetrafluoroethane, hexafluoroethane, and hexafluoropropylene. These or other species can be used individually or as mixtures.
When organic fluorides are used as the treatment gas, it may also be desirable to include in the treatment gas a fluorine scavenger to control the degree of etching on the polymer surface. Examples of fluorine scavengers are hydrogen gas, sulfuric acid gas, methane or mixtures of these gases. Preferred mixtures of gases for use as the treatment gas are CF4/H2, CF4/CH4, C2H2F2/CH4, CHF3/CH4, C2H2F4/CH4, C2F6/CH4, and C2F6/CH4.
Studies dealing with FC plasmas have shown that film growth can be controlled by CxFy ions and neutrals. (Stoffels, W. W. et al., J. Vac. Sci. Technol. A, 16:87 (1998); Sasaki, K. et al., Thin Solid Films, 374:249 (2000); Cunge, G. and Booth, J. P., J. Appl. Phys., 85:3952 (1999)). For efficient FC film deposition, large monomer precursors (e.g., C3F8 and C4F8) are desirable because they produce more CxFy ions and neutrals than small monomer precursors (e.g., CF4, C2F4, and C2F6). (Stoffels, W. W. et al., J. Vac. Sci. Technol. A, 16:87 (1998); Cunge, G. and Booth, J. P., J. Appl. Phys., 85:3952 (1999); Miyata, K. et al., Jpn. J. Appl. Phys., 36:5340 (1997)). Precursor gases, for example, can include CxFy, where x and y are greater than 2, and the ratio of x to y is about 2 or more than 2. Such fluorocarbons are desirable, since they do not introduce too much fluorine into the plasma process. Too much fluorine can cause unintended etching in some cases.
The FC film properties depend on their chemical composition, which differs from that of the film precursors. FC films with different CF3, CF2, CF, and CCF concentrations can be synthesized, depending on the ion bombardment intensity and vacuum ultraviolet (VUV) and ultraviolet (UV) radiation. In addition, the presence of secondary precursors, such as H2, O2, and Ar, may also affect the chemical composition of FC films. (d'Agostino, R. et al., J. Polym. Sci.: Part A: Polym. Chem., 28:3387 (1990); Li, X. et al., J. Vac. Sci. Technol. A, 20:2052 (2002); Zheng, L. et al., J. Vac. Sci. Technol. A, 23:634 (2005); Labelle, C. B. et al., J. Vac. Sci. Technol. A, 23:190 (2005)). For example, CF2-rich FC films with uncrosslinked microstructures (
Also, as shown in
These crosslinked and uncrosslinked layers may be created by varying the processing conditions during the fluorocarbon film deposition process. For example, more intense plasma processing conditions can be used to produce the crosslinked region 12(b) and less intense plasma processing conditions can be used to produce the uncrosslinked region 12(a). In a capacitively coupled plasma processing chamber, for example, the above described shield can be used to modify the properties of the fluorocarbon film 12. For example, to create an environment where the substrate 10 is exposed to less intense plasma processing conditions to create the uncrosslinked region 12(a), the above-described shield may cover the substrate 10. During the same fluorocarbon film deposition process, the shield can then be moved so that it does not cover the substrate 10. This can result in the creation of the cross-linked region 12(b). In some cases, by simply moving the shield, one can achieve desired properties in the fluorocarbon film 12. Other plasma processing parameters such as temperature, feed gas flow rate, power, etc. need not be changed to vary the properties of the fluorocarbon film 12. In other instances, other process parameters (e.g., the power) can be adjusted to form the crosslinked and uncrosslinked regions.
Subsequently deposited layers may also have any suitable characteristics and may be formed using any suitable process. Subsequently deposited layers may include biocompatible layers including proteins, cells, etc. In some embodiments, a subsequently deposited layer may comprise proteins which can attach to CF2 or CF3 terminal groups in the fluorocarbon film. Cells, such as endothelial cells may subsequently attach to those proteins.
The articles according to embodiments of the invention may be in any suitable form. Examples of articles to be formed may include artificial arteries, implants, catheters, etc. Schematic cross-sections of suitable articles may include flat composites as shown in
The various layers 10, 12, 14 in the above described articles may have any suitable thickness. For example, the thicknesses of each of the components may be greater than about 10 nanometers in some cases, or greater than about 1 micrometer in other cases.
Smooth FC films were synthesized on surface-crosslinked, low-density polyethylene (LDPE) using a capacitively coupled octafluorocyclobutane (C4F8) plasma treatment. Differences in the nanoscale and microscale film growth mechanisms on LDPE samples with or without a plasma shield were investigated with a wide range of plasma power. Results for the film thickness, wettability, and surface chemistry are interpreted in terms of corresponding plasma conditions to elucidate the effects of plasma species, such as ions, VUV/UV radiation, and uncharged particles, on the growth, morphology, and physicochemical properties of the FC films.
Experimental Procedures
Polyethylene Specimens. Specimens of 1-cm diameter and thickness in the range of 800-900 μm were fabricated by press casting pellets of LDPE (Sigma-Aldrich, St. Louis, Mo.) onto atomic force microscope (AFM) metal disks. X-ray diffraction and differential scanning calorimetry demonstrated that the crystallinity of the LDPE specimens was equal to ˜50%. To induce surface crosslinking, the specimens were exposed to plasma generated from a radio frequency (rf) inductively coupled plasma source (Litmas Inc., Charlotte, N.C.). The plasma was produced from a high-purity (99.999%) Ar gas (Praxair, Danbury, Conn.) introduced into the vacuum chamber at a flow rate of 100 sccm under a pressure of 500 mTorr. All the specimens were treated for 15 min under plasma conditions of 1200 W rf power and sample-to-plasma source distance equal to 15 cm, producing an ion energy fluence of 1.8�105 J/m2. More details for the experimental setup and the modification of the physicochemical properties of LDPE under different Ar plasma conditions can be found elsewhere. (Tajima, S. and Komvopoulos, K., J. Phys. Chem. B, 109:17623 (2005); Tajima, S. and Komvopoulos, K., J. Phys. D: Appl. Phys., 39:1084 (2006); Tajima, S. and Komvopoulos, K., Appl. Phys. Lett., 89:124102 (2006)).
Fluorocarbon Film Deposition. FC films were grown on surface-crosslinked LDPE specimens in an rf capacitively coupled plasma reactor (RTE73 AMNS-500-E, Plasmatherm Inc., Kresson, N.J.) with a 29.4-cm plate diameter and plate-to-plate distance equal to 5 cm. The specimens were placed on the grounded (bottom) electrode, which was water-cooled to maintain a substrate temperature of 16-17� C. The reaction gas (C4F8) was introduced into the chamber at a flow rate of 50 sccm 2 min before initiating film deposition to establish a stable base pressure of 85 mTorr. Film deposition was then performed under conditions of rf power in the range of 50-450 W and working pressure between 85 and 122 mTorr (depending on the power). In all the experiments the deposition time was fixed at 2 min, except one experiment where it was 30 min. The specimens were kept under a pressure of 85 mTorr for 1 min after the film deposition to allow active plasma species to gradually reach equilibrium before turning off the power. The plasma conditions of all the FC film depositions examined in this study are given in Table 1.
In a series of plasma treatments, the specimens were shielded from the plasma by a 2.54�2.54 cm Al plate, which was placed 2 mm above the specimen surface to prevent ion bombardment and VUV/UV radiation during film growth. The distance from the specimen center to the shield edge was 7.4 mm. Hereafter, the plasma environment obtained with and without the Al shield will be referred to as shielded and unshielded plasma, respectively. The survival rate of CFx + (x=1, 2, or 3) ions of incident energy in the range of 30-150 eV after surface impingement is less than 6%. (Martin, I. T. and Fisher, E. R., J. Vac. Sci. Technol. A, 22:2168 (2004); Martin, I. T. et al., J. Vac. Sci. Technol. A, 22:227 (2004)). Hence, most ions were either absorbed or scattered as uncharged particles after impinging onto the surface of the Al shield. Therefore, only uncharged particles interacted with the crosslinked polymer surface during film growth under shielded plasma conditions.
Microanalysis Techniques. The FC film thickness, surface roughness, and changes in the wettability and chemical characteristics of Ar-treated (crosslinked) LDPE due to FC film deposition were examined with an AFM, ellipsometer, spectroscopic reflectrometer (SR), X-ray photoelectron spectroscope (XPS), and goniometer. All the film characterization studies were performed within 0.5-3 h from the film deposition to avoid any aging effects on the measurements.
Film Thickness. The thickness of the FC films grown under unshielded plasma conditions was measured with an ellipsometer (AutoEL™ II, Model A9822, Rudolph Technologies, Inc., Flanders, N.J.) with a wavelength of 633 nm and a SR (210 XP Scanning UV Nanospec/DUV Microspectrophotometer, Nanometrics Inc., Milpitas, Calif.). The films were deposited on 10-cm-diameter p-type Si(100) wafers approximately 5 min after treating the wafers with 49% HF for 10 min to remove the native oxide layer. Average and standard deviation values of each film thickness were obtained from ten measurements. Differences in the film thickness estimated with the previous techniques were on the order of the experimental scatter (standard deviation).
The FC film thickness t and refractive index were calculated from the measured ellipsometry parameters using customized software (double-layer absorbing film (DAFIBM)). The refractive index of the FC films synthesized under different plasma conditions was found to be in the range of 1.38-1.43, consistent with previous results. (Labelle, C. B. et al., J. Vac. Sci. Technol. A, 22:2500 (2004)). Film thickness measurements were obtained with an accuracy of �3 Å, assuming a film refractive index of 1.4. The same refractive index value was used to estimate the film thickness from the SR measurements.
In view of the very thin FC films grown under shielded plasma conditions, the film thickness was determined from angle-resolved XPS or ellipsometry measurements. XPS spectra were acquired with a Perkin-Elmer PHI 5400 ESCA system (without charge neutralization or monochromator) using Al—Kα (1486.6 eV) X-ray source and a 54.7� angle relative to the analyzer axis. The sampling depth h is given by
Film Surface Morphology. The morphology of the FC films at various length scales was studied with an AFM (NanoScope IV, Veeco Metrology, Santa Barbara, Calif.) operated in the contact mode. AFM scans of 1�1 and 10�10 μm2 surface areas were obtained with a resolution of 256�256 pixels, i.e., pixel-to-pixel distance (sampling length) equal to 3.9 and 39.2 nm, respectively. The sampling length indicates the scale at which the roughness parameters were determined from the AFM images. Thus, it may be presumed that the 1 μm2 and 100 μm2 area scans are indicative of the nanoscale and microscale surface topographies of the FC films. Statistical surface topography parameters, such as centerline average roughness Ra, root-mean-square roughness Rq, skewness, and kurtosis, calculated from 1 μm2 and 100 μm2 AFM surface scans were used to quantify the changes in the film surface topographies. For statistical analysis, surface roughness parameters were calculated as averages of six measurements obtained from two to three specimens of the same FC film.
Film Surface Chemical Analysis. To examine the variation of the FC film wettability with the plasma power, static contact angle measurements were performed at room temperature using a drop shape analysis system (DSA10, Krtiss GmbH, Hamburg, Germany). Average contact angles were calculated from four contact angle measurements obtained from four specimens of the same FC film (i.e., 16 contact angle measurements for each film).
Film chemical compositions were determined from XPS spectra of 1-mm-diameter sampling surface area and 5.3 nm depth using an electron take-off angle θ=45�. Survey spectra were collected with pass energy of 187 eV and resolution of 1.0 eV to identify the elements present on the surfaces. For chemical bond identification, detail scans of core level C1s, O1s, and F1s were collected with pass energy of 35.75 eV and resolution of 0.05 eV. To compensate for surface charging effects, all binding energies in the C1s core level spectra were referenced to the CF2 peak centered at 291.5 eV or the C—H/C—C peak centered at 285.0 eV. After Shirley background noise subtraction, polar functionalities were determined by curve fitting the C1s spectra with 70% Gaussian-30% Lorenzian (GL) distributions of full width at half maximum equal to 2.0 eV (AugerScan 3, RBD Enterprises, Inc., Bend, Oreg.). A goodness-of-fit parameter (corresponding to the error-mean-square parameter) of less than 3 was used in the curve fitting algorithm. Table 2 shows the peak positions of the C—F bonds used to curve fit the C1s spectra. (Clark, D. T. in Photon, Electron and Ion Probes of Polymer Structure and Properties, Eds. Dwight, D. W.; Fabish, T. J.; Thomas, H. R., American Chemical Society, Washington, D.C., 1981, pp. 247-291; Horie, M., J. Vac. Sci. Technol. A, 13:2490 (1995); Fuoco, E. R. and Hanley, L., J. Appl. Phys., 92:37 (2002)).
The FC films synthesized by capacitively coupled C4F8 plasma are hybrids of the two chemical structures shown in
The degree of crosslinking is proportional to the sum of the areas under the CF—CFn, CF, C—CFn, and C—C/C—H peaks divided by the total area under the C1s peak. This is because only these chemical bonds contribute to chain crosslinking. Thus, the percent of crosslinking X can be expressed as (Garrison, M. D. et al., Thin Solid Films, 352:13 (1999))
Since the average connectivity number m represents the average number of network-forming bonds per atom, it can be used to evaluate the rigidity of an amorphous material. (He, H. and Thorpe, M. F., Phys. Rev. Lett., 54:2107 (1985); D�her, G. H. et al., J. Non-Crystal. Solids, 42:87 (1980)). Thus, the FC film rigidity was examined by considering the number of bonds available to other carbon atoms, (Winder, E. J. and Gleason, K. K., J. Appl. Polym. Sci., 78:842 (2000)) using the relationship
Plasma Conditions. Due to the ion density dependence of C4F8 dissociation, variations in the plasma power resulted in pressure changes (Table 1). The density of uncharged particles (i.e., neutrals, radicals, metastables, and atoms) in the plasma ng, determined from the ideal gas law.
For W/FM less than a threshold value (energy deficient region), more energy is needed to form the film than the monomer and the film thickness increases with the plasma power, (Yasuda, H. and Wang, C. R., J. Polym. Sci.: Polym. Chem. Ed., 23:87 (1985); Sandrin, L. et al., Polymer, 42:3761 (2001)) while above the W/FM threshold (monomer deficient region), excessive fragmentation of the monomer molecules leads to the formation of highly reactive species (e.g., CF3 +, CF3, F) which induce film ablation and the film thickness either remains constant (Yasuda, H. and Hirotsu, T., J. Polym. Sci. Polym. Chem. Ed., 16:743 (1978)) or decreases. (Chen, R. et al., J. Appl. Polym. Sci., 56:615 (1995)). High W/FM values represent conditions of intense ion bombardment conducive to film etching. (Silverstein, M. S. et al., Polym. Eng. Sci., 36:2542 (1996); Coburn, J. W. and Winters, H. F., J. Vac. Sci. Technol., 16:391 (1979)). The threshold W/FM depends on the bonding energy of the precursor monomer and the reactor configuration (Yasuda, H. and Wang, C. R., J. Polym. Sci.: Polym. Chem. Ed., 23:87 (1985)) and can be empirically determined from film thickness and roughness measurements.
Film Growth. The thickness of the FC films grown on Si under unshielded plasma conditions versus energy/monomer mass is shown in
The thickness of the FC films synthesized under shielded plasma conditions (determined from angle-resolved XPS) is given in Table 1. The appearance of the Si2s and Si2p3 peaks in the XPS spectra corresponding to the smallest sampling depth for W/FM<15 MJ/kg indicated that these FC films were discontinuous. A steady increase in film thickness was found for W/FM>15 MJ/kg. Thus, a transition from energy-deficient region to monomer-deficient region was not observed in the absence of ion bombardment and VUV/UV radiation.
Differences in the concentration of uncharged particles below the edge and the center of the shield promoted surface diffusion of the uncharged particles. It has been argued that diffusion of uncharged particles is the dominant film deposition process under shielded plasma conditions. (Zheng, L. et al., J. Vac. Sci. Technol. A, 23:634 (2005)). According to Eq. (5), the density of the uncharged particles in the plasma is independent of plasma power. (Although increasing the power from 50 to 450 W resulted in a pressure increase from 85 to 120 mTorr, the effect of this pressure change on the density of the uncharged particles was very small, as shown in Table 1.) However, the thickness of the FC films deposited under shielded plasma conditions increased with the plasma power. This suggests that the former diffusion model, (Zheng, L. et al., J. Vac. Sci. Technol. A, 23:634 (2005)) which accounts only for uncharged particles from the plasma, cannot fully describe the film growth mechanism under shielded plasma conditions. Hence, it is desirable to include in the diffusion model the density of the uncharged particles generated from the impingement of energetic ions onto the metal shield. The number of ion-shield collisions depends on the ion density and is proportional to W/FM. Experimental evidence suggests that the CF2 concentration near the plasma-surface interface increases with the ion energy. (Martin, I. T. and Fisher, E. R., J. Vac. Sci. Technol. A, 22:2168 (2004)). Thus, uncharged particles produced from ion-shield collisions appear to play an important role in the deposition of thick films under shielded plasma conditions and high W/FM To investigate this hypothesis, a Si wafer was placed on the ground electrode with one-third of its surface covered by another Si wafer during plasma treatment at a power of 150 W. The film thickness (measured with a SR) versus distance from the shield edge is shown in
The film deposition rate under shielded plasma conditions was much less than that under unshielded plasma conditions. The results shown in
Film Surface Morphology.
Qualitative comparisons of surface topography maps provided further insight into microscale and nanoscale roughness changes.
Microscale morphologies of FC films grown under unshielded plasma conditions for relatively low and high energy/molecular mass are shown in
Particle formation at high pressures has been attributed to gas phase polymerization. (Sandrin, L. et al., Polymer, 42:3761 (2001)). In the present study, more gas phase polymerization was encountered for plasma power equal to 150 W than 50 W under a pressure of ˜85 mTorr (Table 1). Thus, gas phase polymerization occurred under conditions conducive to the development of high ion density plasma. Excess ion bombardment promoted etching of the polymerized nanoparticles. The particles produced from gas phase polymerization in this study were much smaller and less dense than those generated from C3F6 and C2F3H plasmas. (Sandrin, L. et al., Polymer, 42:3761 (2001)). In addition to particle formation by microscale gas-phase polymerization, unshielded plasma conditions and W/FM<22.1 MJ/kg yielded numerous asperities of average size and height (determined from measurements obtained from three different scans) equal to 181�27 nm and 41�7 nm, respectively. Hence, the formation of particles and asperities under unshielded plasma conditions resulted in higher Rq values than those of Ar-treated LDPE (
The nanoscale morphologies of the films grown under unshielded plasma conditions (
The grain growth mechanisms under shielded and unshielded plasma conditions observed in
Film Hydrophobicity.
The contact angle measurements could be affected by the surface roughness. Usually, rough surfaces yield higher contact angles than smooth surfaces of the same chemical composition. The surface roughness effect on the contact angle can be interpreted in terms of the roughness factor, defined as the ratio of the true surface area to the apparent area of the imaged surface. (Wenzel, R. N., Ind. Eng. Chem., 28:988 (1936); Wenzel, R. N., J. Phys. Colloid. Chem., 53:1466 (1949); Johnson, Jr. R. E. and Dettre, R. H. in Contact Angle, Wettability, and Adhesion, Ed. R. F. Gould, Adv. Chem. Ser., vol. 43, American Chemical Society, Washington, D.C., 1964, pp. 112-135; Cassie, B. D. and Baxter, S., Trans. Faraday Soc., 40:546 (1944)). The very small roughness factors (<1.6) of both microscale and nanoscale topographies indicated that the formation of particles and asperities (
Film Surface Chemistry.
Table 4 shows that the film grown in 2 min under shielded plasma conditions exhibited 46% crosslinking, suggesting that the film chemical structure might be a mixture of those shown in
In this study, FC films with significantly different chemical structures were obtained in the presence of energetic ion bombardment and VUV/UV radiation. The simultaneous effects of these plasma species resulted in the formation of crosslinked FC films, as evidenced by the increase of the CF and C—CFn peak intensities in the C1s spectrum (
The growth mechanisms of thin FC films synthesized under conditions resulting in surface interaction with uncharged particles only (shielded plasma conditions) or ion bombardment and VUV/UV radiation in conjunction with uncharged particles (unshielded plasma conditions) were analyzed in the context of results for the film thickness, morphology, wettability, and surface chemistry obtained for different values of energy/monomer mass.
The film growth rate exhibited strong dependence on the density and energy of ions as well as the density of uncharged particles generated from the plasma and ion-shield surface collisions. The later particles contributed significantly to the film growth process under shielded plasma conditions. Different film growth mechanisms were found under the effect of uncharged particles alone and under the simultaneous effects of ion bombardment, VUV/UV radiation, and uncharged particles from the plasma over a wide range of energy/monomer mass. Microscale film growth comprised the initial deposition of a layer covalently bonded to the polymer substrate, followed by the formation of islands of small asperities and large particles produced from gas phase polymerization. Nanoscale film growth was characterized by the enlargement of surface grains with the increase of plasma intensity. The FC films deposited under shielded plasma conditions and high energy/monomer mass exhibited zone 1 growth structure, while those deposited under unshielded plasma conditions exhibited either zone 3 growth structure (energy/monomer mass less than a threshold value) or grain removal by plasma etching (energy/monomer mass above a critical value).
Contact angle results demonstrated higher film hydrophobicity for shielded plasma conditions and negligible roughness effect on the contact angle measurements. XPS analysis showed that FC films grown under shielded plasma conditions exhibited less crosslinking and higher CF2 concentrations than those grown under unshielded plasma conditions. Chemical analysis revealed that thin FC films with hybrid chemical structures consisting of a crosslinked (strong) interfacial layer and a CF2-rich hydrophobic and compliant surface layer can be grown on polymer surfaces under shielded plasma conditions. The capability to tailor the FC film structure and chemical composition is intriguing and of great importance to biotechnology and various microdevice applications, where control of the surface properties is critical to reliability and performance.
Any one or more features of one or more embodiments may be combined with one or more features of any other embodiment without departing from the scope of the invention.
Any recitation of "a", "an" or "the" is intended to mean "one or more" unless specifically indicated to the contrary.
The above description is illustrative but not restrictive. Many variations of the invention will become apparent to those skilled in the art upon review of the disclosure. The scope of the invention should, therefore, be determined not with reference to the above description, but instead should be determined with reference to the pending claims along with their full scope or equivalents.
All references, applications, and patents cited above are herein incorporated by reference in their entirety for all purposes. None is admitted to be prior art.
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Balikpapan-class landing craft heavy
HMAS Balikpapan in 2011
|Class overview
|Walkers Limited at Maryborough, Queensland
| Royal Australian Navy
Papua New Guinea Defence Force
Philippine Navy (planned 2015)
|Preceded by:
|LSM-1-class landing ship medium (RAN)
|In service:
|In commission:
|General characteristics
|Landing Craft Heavy
|364 tons standard
517 tons full load
|44.5 m (146 ft)
|10.1 m (33 ft)
|2 m (6 ft 7 in)
|2 × General Motors Detroit 6–71 diesel motors (original)
2 × Caterpillar 3406E diesel engines (RAN since 2005)
|10 knots (19 km/h; 12 mph)
|3,000 nautical miles (5,600 km; 3,500 mi) unladen
1,300 nautical miles (2,400 km; 1,500 mi) with 175 tons of cargo
|180 tons of cargo
|Sensors and
processing systems:
|Racal Decca Bridgemaster I-band navigational radar
|two 7.62 mm (0.300 in) machine guns
The Balikpapan class is a ship class of eight heavy landing craft (officially Landing Craft, Heavy or LCH). All eight were originally laid down by Walkers Limited for the Australian Army in the early 1970s. A reorganisation of watercraft responsibilities in the Australian military meant the landing craft were to be operated by the Royal Australian Navy (RAN), with seven commissioned directly into RAN service during 1973 and 1974, and lead ship Balikpapan transferred from the army to the navy. Following the independence of Papua New Guinea in 1975, two of the vessels (Salamaua and Buna) were transferred to the new Papua New Guinea Defence Force (PNGDF).
During their careers, the Australian vessels have operated in support of Operation Navy Help Darwin in 1974–75, Operation Bel Isi from 1997 to 2003, INTERFET operations in 1999 and 2000, and RAMSI operations from 2003.
The six remaining RAN vessels were paid off in the 2010s: Balikpapan, Betano, and Wewak in 2012; Brunei, Labuan, and Tarakan in 2014. They are yet to be replaced in RAN service. As of 2013, the two PNGDF vessels were active, and in 2014, the former Labuan was transferred to Papua New Guinea as the training ship Lakekamu. Brunei and Tarakan are to be fitted with new safety and navigation equipment, with plans to donate them to the Philippine Navy in 2015.
Design and capabilities[edit]
Eight new heavy landing craft were ordered in 1969 as a locally-manufactured replacement for the Australian Army's four LSM-1-class landing ship medium and two ALC 50 landing craft after the Landing Ship Medium Mark II project was cancelled.[1] They are 44.5 metres (146 ft) long, with a beam of 10.1 metres (33 ft), and a draught of 2 metres (6 ft 7 in).[2] The landing craft have a standard displacement of 320 tons, with a full load displacement of 517 tons.[2] They were originally built with two General Motors Detroit 6–71 diesel motors.[3] These were replaced by Caterpillar 3406E diesel engines between 2005 and 2007 for those still in Australian service.[2] The standard ship's company is 16-strong, including two officers.[2] The sensor suite is limited to a Racel Decca Bridgemaster I-band navigational radar.[2] They are fitted with two 7.62-millimetre (0.300 in) machine guns for self-defence.[3]
The LCHs have a maximum payload of 180 tons; equivalent to three Leopard 1 or two M1A1 Abrams tanks, 13 M113 armored personnel carriers, 23 quarter-tonne trucks, or four LARC-V amphibious cargo vehicles.[3][4][5] As a troop transport, a Balikpapan class vessel can transport up to 400 soldiers between a larger amphibious ship and the shore, or embark 60 soldiers in six-berth caravans for longer voyages.[4][6] The vessel's payload affects the range: at 175 tons of cargo, each vessel has a range of 1,300 nautical miles (2,400 km; 1,500 mi), which increases to 2,280 nautical miles (4,220 km; 2,620 mi) with a 150-ton payload, and 3,000 nautical miles (5,600 km; 3,500 mi) when unladen.[3] The flat, box-like keel causes the ships to roll considerably in other-than-calm conditions, limiting their ability to make long voyages.[4] The LCHs can mate their bow ramp to the stern loading dock of the RAN's large amphibious warfare ships when operating in the ship-to-shore role.[6]
All eight Balikpapan-class vessels were constructed by Walkers Limited at their shipyard in Maryborough, Queensland.[7] All were laid down during 1971 and 1972, with lead ship Balikpapan entering service with the Australian Army Water Transport Squadron at the end of 1971.[7] After this, responsibility for seagoing Army craft was transferred to the RAN, with the other seven craft directly entering naval service during 1973 and 1974, and Balikpapan transferring over in late 1974.[7][8]
Operational history[edit]
|This section requires expansion. (January 2015)
In January 1973, the Balikpapans in RAN service were formed together as the First Australian Landing Craft Squadron, based at HMAS Moreton in Brisbane.[4] In November 1974, Salamaua and Buna were transferred to the fledgling Papua New Guinea Defence Force, along with five Attack-class patrol boats.[4][9] Five of the remaining Australian LCHs were deployed in December 1974 following Cyclone Tracy as part of Operation Navy Help Darwin; HMAS Labuan was undergoing refits at the time.[10]
HMAS Labuan was assigned to the Royal Australian Navy Reserve in June 1979, and attached to the Brisbane Port Division.[4] Three LCHs, Tarakan, Balikpapan, and Wewak were placed in reserve at NQEA in Cairns during August and September 1985.[4] They were reactivated in 1988, 1990, and 2000, respectively.[3] On entering service, Brunei and Betano initially supplemented the inshore hydrographic survey capabilities of the RAN until late 1988, when they were reassigned to the naval base HMAS Waterhen for use in diver training.[3] During May and June 1984, Balikpapan completed a 5,400-nautical-mile (10,000 km; 6,200 mi) transit from Brisbane to Penang, transporting vehicles, equipment, and personnel to RAAF Butterworth; the longest ocean voyage undertaken by a vessel of this class.[10] During 1985 and 1986, Salamaua and Buna underwent refits.[11]
Between 1997 and 2003, the LCHs were used to support the Peace Monitoring Group (PMG) in Bougainville, under Operation Bel Isi.[12] Ships deployed on this operation were involved in resupplying the PMG base in Loloho, transport of PMG personnel and humanitarian aid, and coastal patrols.[12] From 1999 onwards, the Balikpapans were also tasked with supporting INTERFET operations in East Timor, particularly those relating to the Oecussi enclave.[12] The increase in operational tempo was a major factor in the reactivation of Wewak in 2000.[12] In 2003, the landing craft began supporting RAMSI operations in the Solomon Islands.[12]
The two PNG vessels were listed in Jane's Fighting Ships as non-operational since 2011, and awaiting refits.[13] By 2013, they had been returned to service.[14] Labuan and Tarakan delivered humanitarian supplies to remote coastal settlements in the Solomon Islands in September 2014 as part of Australian support efforts in the region.[15]
Decommissioning and fates[edit]
On 11 December 2012, Wewak was decommissioned.[16] Balikpapan and Betano were both decommissioned a day later, on 12 December.[17][18][19] The other three Australian vessels were decommissioned on 20 November 2014.[20][21]
Labuan was transferred to the PNGDF for use as a training vessel, and was commissioned as HMPNGS Lakekamu on 4 December 2014.[21][22] Brunei and Tarakan are to be refurbished and fitted with new safety and navigation equipment.[23] On completion (delivery is planned for 17 May 2015),[needs update] the two vessels will be donated to the Philippine Navy.[24] According to the Australian Department of Defence, the Philippines has also expressed interest in the remaining three Australian vessels.[23]
There are plans to replace the Balikpapans in Australian service with an as-yet-unidentified class of six heavy landing craft.[16][25] The original replacement project was not due to decide on the design until between 2016 and 2018, with the new class to enter service from 2022.[5] The Department of Defence issued a request for information in early 2011, which may lead to the project being brought forward.[5]
- ^ Gillett, Australian and New Zealand Warships since 1946, pgs 79, 125
- ^ a b c d e Saunders (ed.), IHS Jane's Fighting Ships 2012–2013, p. 32
- ^ a b c d e f Wertheim (ed.), The Naval Institute Guide to Combat Fleets of the World, p. 26
- ^ a b c d e f g Gillett, Australian and New Zealand Warships since 1946, p. 79
- ^ a b c Wertheim (ed.), The Naval Institute Guide to Combat Fleets of the World, p. 25
- ^ Gillett, Australian and New Zealand Warships since 1946, p. 80
- ^ Frame, No Pleasure Cruise, p. 261
- ^ a b Swinden, Heavy Lifting for Four Decades, p. 22
- ^ Wertheim (ed.), The Naval Institute Guide to Combat Fleets of the World, p. 536
- ^ a b c d e Swinden, Heavy Lifting for Four Decades, p. 23
- ^ Saunders (ed.), IHS Jane's Fighting Ships 2012–2013, p. 602
- ^ Swinden, Heavy Lifting for Four Decades, p. 21
- ^ "Australian Navy Delivers Supplies to Solomon Islands". Naval Today. 18 September 2014. Retrieved 27 September 2014.
- ^ a b "HMAS Wewak decommissioned". Department of Defence. 11 December 2012. Retrieved 13 December 2012.
- ^ "HMA Ships Balikpapan and Betano decommissioned". Royal Australian Navy. 13 December 2012. Retrieved 19 December 2012.
- ^ "HMAS Balikpapan". Royal Australian Navy. Retrieved 19 December 2012.
- ^ "HMAS Betano". Royal Australian Navy. Retrieved 19 December 2012.
- ^ Rahmat, Ridzwan (23 July 2014). "RAN to decommission three Balikpapan-class LCHs". IHS Jane's Navy International. Retrieved 3 September 2014.
- ^ a b Staples, Natalie (20 November 2014). "Final farewell for landing craft". Navy Daily (Royal Australian Navy). Retrieved 20 November 2014.
- ^ "Defence Minister welcomes the commissioning of HMPNGS Lakekamu". Media release. Senator David Johnston. 4 December 2014. Retrieved 4 December 2014.
- ^ a b Fonbuena, Carmela (29 January 2015). "Australia's gift to PH Navy: 2 supply ships". Rapller. Retrieved 30 January 2015.
- ^ Cohen, Michael; Hardy, James (29 May 2015). "Ex-RAN heavy landing craft to arrive in Philippines by mid-May". IHS Jane's Defence Weekly. Retrieved 16 June 2015.
- ^ Berry, Paul (6 December 2012). "End of the line". Navy News (Directorate of Defence News). p. 4.
- Books
- Frame, Tom (2004). No Pleasure Cruise: the story of the Royal Australian Navy. Crows Nest: Allen & Unwin. ISBN 1-74114-233-4.
- Gillett, Ross (1988). Australian and New Zealand Warships since 1946. Brookvale, NSW: Child & Associates. ISBN 0-86777-219-0. OCLC 23470364.
- Gillett, Ross (2012). Australia's Navy: Today and Tomorrow. Part 2. Topmill.
- Saunders, Stephen, ed. (2012). IHS Jane's Fighting Ships 2012–2013. Jane's Fighting Ships. Coulsdon: IHS Jane's. ISBN 9780710630087. OCLC 793688752.
- Wertheim, Eric, ed. (2007). The Naval Institute Guide to Combat Fleets of the World: Their Ships, Aircraft, and Systems (15th ed.). Annapolis, MD: Naval Institute Press. p. 26. ISBN 978-1-59114-955-2. OCLC 140283156.
- Journal articles
- Swinden, Greg (April 2013). "Heavy Lifting for Four Decades: The Navy's Landing Craft Heavy". The Navy (Navy League of Australia) 75 (2): 20–24. ISSN 1322-6231.
External links[edit]
|Wikimedia Commons has media related to Balikpapan class landing craft heavy.


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— Science
Underwater vehicle uses a balloon to dart like an octopus
By Ben Coxworth - February 5, 2015 1 Picture
When you inflate a balloon and then release it without tying the valve shut, it certainly shoots away quickly. Octopi utilize the same basic principle, although they suck in and then rapidly expel water. An international team of scientists have now replicated that system in a soft-bodied miniature underwater vehicle, which could pave the way for very quickly-accelerating full-size submersibles. Read More


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The Cheltenham Camera Club holds two social events a year, the annual Banquet in June and the Holiday Party in December. This year's December bash will have two fun features:
1. Pot Luck Supper. All you can eat and more. In order that there is no duplication of dishes, please register to bring a particular goody. Everything from hors d'oeuvres to desserts is needed. The club will provide beverages. A sign-up sheet will be available at the December 3 meeting, and if you can't attend that meeting, please email Deb Klose at [masked] with your offering.
2. Photo sharing. We always pick a topic and invite members to submit a few photos to share with the group. This year's subjects are:
• 5 Photos I love even if the judges hate them!
• A new challenge I have taken on this year, photographic or personal.
It should be as always, a lot of fun!
I started the group because there wasn't any other type of group like this. I've met some great folks in the group who have become close friends and have also met some amazing business owners.
— Bill, started New York City Gay Craft Beer Lovers
Meetup members, Log in
By clicking "Sign up" or "Sign up using Facebook", you confirm that you accept our Terms of Service & Privacy Policy


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Photo Galleries
< MyNorthwest
Mom shares view from stands at the Little League World Series
I know many parents who can't handle watching their kids in a preseason scrimmage. I can't imagine how they would handle watching their son at the plate in front of 20,000 people on a stage like this.
1 of 6
Sammamish, Wash., pitcher Jacob Dahlstrom delivers during the first inning of a baseball game in U.S. pool play against Corpus Christi, Texas, at the Little League World Series tournament in South Williamsport, Pa., Thursday, Aug. 15, 2013. (AP Photo/Gene J. Puskar)
Photo by Gene J. Puskar
Photo by Gene J. Puskar
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Original article: Mom shares view from stands at the Little League World Series
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How the bears and orangutans keep cool at the zoo
Heran and Keema keep cool at the Woodland Park Zoo in Seattle with frozen treats.
U.S. Open at Seattle's South Lake Union
Activities at the Open for All Fan Experience at South Lake Union Park were set up to connect golf fans with the Chambers Bay tournament.
John Kerry visits Seattle
U.S. Secretary of State John Kerry greets employees at the Seattle Passport Agency on May 18. The location is one of 29 domestic passport agencies that the State Department runs. Kerry returned to the United States following a three-day trip to China and South Korea.


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Christmas Breakfast Recipes
Looking for Christmas breakfast recipes? Find Christmas breakfast recipes including breakfast menus, Christmas breakfast ideas, and more Christmas breakfast recipes.
Recipe Spotlight
To save some time during the busiest of holidays, I make and refrigerate the batter for these pancakes two hours before cooking. This way I don't have to fuss with measuring ingredients while my guests mill about the kitchen anxiously awaiting brunch. —Barbara Brittain, Santee, CaliforniaView Gingerbread Pancakes with Banana Cream Recipe


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Andrea White
March 3, 2013
WASHINGTON - The Georgetown University women's basketball squad will host the University of South Florida Bulls on Monday evening at McDonough Arena in a BIG EAST Conference matchup. Tipoff for the season finale is scheduled for 8 p.m. The Hoyas are currently 14-14 overall and 5-10 in BIG EAST Conference play.
The contest will decide BIG EAST Tournament seeding. The championship begins on Friday at XL Center in Hartford, Conn.
Tampa, Fla.
Rodgers led all scorers with 21 points and also had four boards as well as four assists and three steals. White added 12 points and nine rebounds along with three steals. The Hoyas outrebounded the Golden Eagles, 36-29, and shot 37.3 percent for the game while holding Marquette to 36.7 percent from the field.
Currently leading the way for the Hoyas is Rodgers. The shooting guard is averaging 22.3 ppg and 7.1 rpg as well as posting 99 steals and 119 assists. White is second with 11.1 ppg and 6.5 rpg, while senior center Sydney Wilson (Silver Spring, Md./St. John's College Prep) rounds out the top three with 6.8 ppg as well as 5.3 rpg.
The Bulls gave No. 3 UConn a battle early on but couldn't pull off an upset on Senior Day at the Sun Dome. Inga Orekhova posted a team-high 13 points and Andrea Smith and Alisia Jenkins added 10 points apiece as USF finished off its home slate with an 85-51 loss on Saturday afternoon. The Bulls (19-9, 8-7) shot 25 percent from the field and had a hard time stopping UConn's top scorers. Kaleena Mosqueda-Lewis finished with a career-high 32 points and Stefanie Dolson matched her career high with 25 points to help the Huskies win for the 15th time in their past 16 games.
The Hoyas are 6-4 all-time against the Bulls and 3-1 at home. Last season, Georgetown defeated USF, 66-56, in Tampa, Fla. Three players were in double figures with 12 points apiece including Rodgers, Tia Magee and Adria Crawford. Magee and Crawford both managed double-doubles with 11 and 10 boards, respectively. The last meeting in the District was during the 2010-11 season where the Hoyas won, 67-38.
Monday's game will tip at 8 p.m., at McDonough Arena. Live stats and a webcast featuring Ryan Sakamoto and Georgetown alum Monica McNutt will be available at www.GUHoyas.com.
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Fuel economy:21 cty/28 hwy
What's New for 2014 The 2014 Subaru Outback gets minor changes to its trim levels and equipment. Notably, 2.5i Premium models now have standard heated seats, while the base 3.6R trim level has been discontinued.
Fuel economy:25 cty/33 hwy
What's New for 2015 Redesigned for 2015, the Subaru Outback packs more interior space, higher fuel efficiency, a nicer interior and more intuitive controls than before.
Fuel economy:25 cty/33 hwy


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Warren Buffett says there will be another financial crisis "someday," but he'd be "surprised a lot" if global stock prices plunged soon.
Stocks stumbled after getting a one-two punch from poor China economic data and rising geopolitical tensions.
Internationally, tourism numbers are strengthening amid rises in business travel, hotel construction and airline trips.
There are lots of reasons to like the market and lots of reasons not to like it. By the end of the year they may just balance out and yield nothing.
Alibaba reportedly seeking a U.S.-listed IPO. The e-commerce site is in dispute with Hong Kong over its partnership structure.
Most industries recoil at the thought of too much regulation. Bitcoin is finding out what happens when there's not enough.
Another day, another batch of weak data from China that fell short of market expectations.
Happy Thursday. To our great relief, Bill Ackman has never accused the Morning Six-Pack of being a pyramid scheme.
Warren Buffett's Berkshire Hathaway will get a Miami television station as it breaks long-standing ties with the former Washington Post Co.
Cascading copper prices have multiple root causes that lead to one conclusion: The anticipated global economic recovery may not be all it's cracked up to be.
There is worry that the recent decline in copper and China's economic woes might be the start of a wider correction.
Obama's approval rating may have hit a new low, but he still attracted big money Democrats at a fundraiser in Manhattan.
Happy Wednesday. There's a storm coming but we promise this will be the last one of the winter ... maybe.
Hedge fund manager Bill Ackman renewed his attack on Herbalife on Tuesday.
Copper continues to crumble amid China growth worries and a weak Yuan. Strong global growth is key to keep stocks at records.
Detroit looks to emerge as at least a survivor if not a winner from its bankruptcy, with bondholders and municipal borrowers the biggest losers.
Prominent investment managers are warning of a bubble in biotechnology stocks and recommend investors avoid emerging markets in favor of Europe.
Not so long ago known as the untouchable Bond King of the investment world, the Pimco founder now finds himself the subject of intense scrutiny.
A high-frequency trader going public has its skeptics, but there are at least a few reasons why the top for that industry isn't near yet.
Happy Tuesday, which is always better than Happy Monday and certainly worthy of toasting with a Morning Six-Pack.
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Do You Have Clothing Arguments With Your Kids?
Am I alone in this? I go back to school shopping and get great stuff for my 6-year old little girl and my 8-year old son. I work hard to find a good variety, careful to make the stuff versatile so a certain shirt could go with a lot of different pants, etc., I do it within budget, and they have enough new, nice things they should feel really good about.


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Retro, retro, retro! What does it mean to you? Does it mean smelly old games with all the appeal of chewing on road kill, or a bit of a rose-tinted time when "pokes" were the only way to get one up on that three-life cap? If you find the former to be your way of thinking, stop reading right now! I'm serious, go back to your GoW and your CoD4 and those online games with "interaction" with total strangers. Go on, GO!!!
In my line of work I meet people from ALL walks of life, from the young to the old and those that speak a different launguage, and I have to get on with ALL of them! It's a hard job, but some body's gotta do it. Occasionaly I find myself talking with a fellow gamer (the conversation sure goes faster then I tell you) and find myself disscussing the pro's and con's for owning a 360 or PS3, or what the most gratuitous fun you can have in a game is (GTA wins for that mostly) and some times I meet gamers I can't understand. I'm talking about online-ers, gamers that won't (I'll stress that "WON'T") play single player offline games. Ever. And I gotta say; This really freaks me out!
The thought of NEVER taking a game at your own pace, of NEVER having a moment with just you and a game, just escapes me completly! One of my fondest memories of gaming has to be in Ocarina of Time on the N64, I'd just worked my way up the banks of the Zora River and was stopped by a large waterfall. Upon seeing the royal crest below my feet, I began to play their melody, at which point the camera panned down to show the fairys dancing in the decending sun light as the water parted and revealed a doorway, magic no? There are countless other scenarios that I could regurgitate to prove my point but I think that says enough.
For me a lot of the atmosphere that comes from a game is made by the player them self, the speed at which they proceed through a game impacts on this hugely without their knowledge and because things happen at their own pace, events have a bigger effect on them. This is some thing that just can't be derived from an onlne mutiplayer, and when I met some one who ONLY played online, well I just couldn't understand. One of the joys of gaming I discovered at a young age was the immersion certian games could bring, a lot of people said A Boy and His Blob was the dullest game they'd ever played, yet I LOVED it. I loved it for it's pace, for it's lack of a timer and for it's laid-back gameplay. When Mario 2 was released for the NES you wouldn't belive my happiness when I discovered there was no level time limit! It may sound odd but I hated having to rush through levels, I enjoyed being able to drink in nice graphics, to be able to "feel" like I had entered another world, to find some thing in a level that was fun to do and take my sweet time fannying around doing it.
Online gaming is great for short spells of tough competition, and it is loads of fun hammering another person rather than just a 'bot' to give your self an ego trip, but I can never truly feel "in" the game while playing with other people. They do odd things in games, Smack-talkers for one thing make me quit a game faster than lag on a bad day. Others who find it more fun just to disrupt a match-in-progress rather than join in, and don't get me started on the campers! What I'm saying is that I felt much happier back when games were a part of you on a personal level, y'know, like just you and "that boss" and now we're constantly being told how bad we are in respect to world wide online tables. After achieving what I felt was a good run on a game, I'm dis-heartened by being placed on the bottom end of a table and realising that if I want that top spot, I'd have to eat, sleep and shit the game for months. That's ok if you're 16 and have no job, kids or life but for us "ageing" gamers reaching the top of your game's almost an impossibility. Maybe I'm bitter cause I'm getting older and can't play for as long as I'd like or maybe my hand-eye co-ordination is going down hill with my age! What ever the reasons, I still find there's nothing better than getting a new world to potter around in and allowing yourself to become part of it, to have total control over your environment and feel the power of it. People will turn on you. AI (so far) won't, enjoy it while it lasts folks!


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Are you measuring the business value of your IT projects? It is so worth the effort!
I have referenced a number of autonomic technology projects(or proof of concepts) recently completed that have demonstrated quantifable business value. I must admit, the ability to measure business value creation did not come naturally to me (or to many of the IT groups we have worked with) and thus required a very deliberate focus.
How do we measure the impact on revenue or costs of business processes supported by IT? The majority of CIOs admit that they find it difficult to measure and communicate the business value of IT related projects to the business unit. Yet most agree that projects supported by IT consistently yield a higher return than those that are not. Given today's business climate, it is more important than ever to measure IT driven business value to insure we make the right investment decisions as we move forward.
Although the study of business value creation is largely an unfamiliar space for many technologists we can begin to build our ability to do this as a scientific approach. Here are 3 things to consider to get started:
1) Develop a set of value categories and a common taxonomy - Start by defining a small set of the most compelling measurements - you can(and will) expand these over time.
2) Measure before, during, and after - Believe it or not, for the majority of IT projects, quantification of business value is an afterthought. Start with the base case - It is critical to do the value measurement using the value categories agreed upon PRIOR to the IT project. Repeat these same measurements at agreed to project checkpoints, at project completion, and at agreed to points during the lifecycle.
3) Communicate the results (and consider your audience) - Before you go forward with your findings consider who you will be presenting to. Translate /communicate value in the terms and context meaningful to the target audience.
Measuring the business value of your IT projects
DavidBBartlett 0600017MDJ 552 Views


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It's been a long time since I've written a race report. Back in the day, I used to run like 10 races every year. I think maybe I ran one in 2014. And it was terrible. But now I can say that I've run one in 2015. Hopefully this is just the beginning. I miss racing.
In the past six months or so, Jason has gotten really into working out. His workouts put mine to shame. He's mostly been running and wanted to sign up for a 5K. We decided on the Seneca 5K, in Jason's home town of Seneca, South Carolina.
When we first decided to do the race, I was determined to train for it. But then Alexander got a stomach bug one week and then I got it the next and somehow it was the day of the race, and I wasn't trained at all. Umm, oops? That's not to say that I hadn't been running at all, but I definitely didn't train.
The weather was perfect on Saturday morning. Sunny in the upper 50s. I started off feeling good and tried to run at a pace that felt faster than normal. After about a quarter or half mile, I realized Jason was right next to me and we ran basically together. The race was an out and back. There were no mile markers which was sort of annoying, but since there was a turnaround, that helped me gauge how far we'd gone and how far the finish line was. I took some walk breaks here and there, but managed to catch back up to Jason.
We both finished in around 31:20. It was a PR for Jason!
We hung out for a while after the race and took advantage of the free beer. I mean, yeah, it was 9 am, but there's something about a race that makes it okay to have a [very small] beer.
Even though this wasn't my best time, it felt good to get back out there again. Jason and I both feel inspired to do another race soon, maybe in April. And maybe this time I'll train for it.


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Tallahassee, FL (Monroe St) 24 hour gym + tanning
1940 Monroe Street
Tallahassee, FL 32303
club information
club at a glance
24-hour access
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convenient parking
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|f7B / V8
|The block below Boyager is another jutting prow. Climb the left arete from matched on the plinth, using the eponymous pocket with your right hand.
Dave Parry Jul/2011
Ticklists: Escaping Norfolk, Compression heaven!.
Photo: Peak Bouldering Rockfax Gallery - Sam Stephenson on Monochrome (V8 7B) at Burbage North. © Rockfax


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Updated 12/18/2013
Hued in the lavenders, blues, ochers, and oranges of Aix, rooms here swim in the most gorgeous Souleiado and Rubelli fabrics: this all conjures up the swank Provence that used to be colonized by Parisian barons and dukes in the 19th century, far from the usual Provençal farmhouse idyll. Little wonder the former archbishop's palace has become the darling of shelter magazines everywhere. This hilltop garden retreat stands serenely apart from the city center on the outskirts of town (offering great views over the pink roofs of Aix), and that means the shops of Cours Mirabeau are a 15-minute walk away.
Av. de la Violette, Aix-en-Provence, 13100, France
Website: www.villagallici.com
Hotel Details:
Updated 12/18/2013
By mwgrzelak
Jul 9, 2012
I stayed twice @ Villa Gallici. In 96 and on my honeymoon in 08. A fantasy enjoyed. The rooms were upscale,the staff friendly and helpful. They arrainged for a car service to travel the area using our desires. I especially enjoyed the fragrance of lavender permeating the air and a glass of Pastis poolside in the afternoon. Walking distance to town.
No Thanks


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Updated May 24, 2013 - 8:06 am
Pat's Personal Portraits: Derrick Hall
I sat down with Derrick Hall, President and CEO of the Arizona Diamondbacks, to talk about a variety of topics about America's favorite past time. He talked about how the MLB compares to the NFL, how the new commissioner should continue Bud Selig's legacy but focus on the international part of the sport.
He brought up an interesting point on having teams play under the National League or American League rules depending on the division of the home team. I mean who wouldn't love to see Mariano Rivera hit?
Lastly, we discussed the decline in African American's, and the increase of Latino's playing in the MLB.


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Colleges >> Browse Articles
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The Difference in DegreesDo you know the difference between an AA, BA, BS, BFA or MFA? You should – especially if one is going to have your name on it in the near future! Distinguishing the different degrees can easily become alphabet soup, unless you understand what each really means. It's easy to confuse bachelor's degrees with one another, since the variations are comprised ...Published about 2 years ago |
Colleges Freeze Tuition Rates for 2013-14 School YearIt seems as though all that's ever reported is the rising cost of college tuition rates. While there is truth to that claim, many colleges are working towards making college more affordable or, at the very least, stopping rates from becoming even less affordable for students. Critics of tuition cuts or freezes question whether or not the quality of education will ...Published about 2 years ago |
The Myth of Multiple-Choice MethodologyResearch Study: Benefits of Keeping to Instincts While Test Taking are Mythical There's a new study in town that says, when it comes to multiple-choice questions, don't go with your gut. It's been pounded into our brains that our first instinct on test answers is the way to go but, according to new research data, test takers actually increased their scores ...Published about 2 years ago |
College by Dr. DreWhat if you could get a degree in disruption? Now you can at the University of Southern California, thanks to Jimmy Iovine and Andre Young (aka Dr. Dre). The music moguls donated $70 million to LA-based USC to develop an undergraduate program, dubbed The Jimmy Iovine and Andre Young Academy for Arts, Technology and the Business of Innovation. According to the ...Published about 2 years ago |
Updates to the GRE ProgramFor students looking into attending graduate or business school, updates have been made to the GRE® Program. Beginning July 1, 2013, students taking the GRE® revised General Test will be able to retake the exam as often as once every 21 days and up to five times within a continuous year. The GRE® revised General Test is available at nearly 700 ...Published about 2 years ago |
School of StyleListen up, fashion-loving Fastwebbers! There's a new school in season and it's got a big name backing it. Condé Nast, the London-based magazine publisher, has opened Condé Nast College of Fashion and Design. Like the publisher, the school is based in London, but students from all over the world are invited to apply for their available 10-week Vogue Fashion Certificate course. ...Published about 2 years ago |
Ten Questions for Parents to Ask When Considering a College Offer"If there's one mistake my students make [when choosing a college], it's not listening to their parents," says Bruce Hammond, director of college counseling at Sandia Preparatory School in Albuquerque, N.M., contributing editor to the The Fiske Guide to Colleges 2006 and author of Discounts and Deals at the Nation's 360 Best Colleges. Parents can often balance the excitement students ...Published over 2 years ago |
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Do you know when this rug will be back in stock? Thanks
This is a lovely, soft looking rug that blends well with most anything. The only complaint is that it is not actually square, but a bit off square....
Hand-tufted Coliseum Rust Traditional Border Wool Rug (6' x 9')
This elegantly crafted traditional hand-tufted wool rug is the perfect addition to any home. Made of 100 percent wool, the gorgeous geometric pattern is infused with tones of black, gold, red, and blue, allowing it to complement any decor.
ITEM#: 12348940The classic Moroccan lotus design of this multicolor Oriental-style rug brings timeless beauty to your favorite living space while cushioning your feet with a deep wool pile. The generous size is ideal for decorating large bare areas on your floor or dressing up the open space in a living room or den. The gently-worn appearance of this rug creates an heirloom effect that works well with carpet, hardwood or tile, and the fringe-free edges keep the piece looking neat and clean.
- Area rug will add a stylish touch to your home decor
- Traditional rug is hand-tufted of 100-percent wool
- Area rug is accentuated by black, gold, grey blue, and kerry blue
- Includes shades of light brown, rust red, and taupe
- Pile height is 0.625 inches thick
- Primary Color: Red
- Pattern: Floral
Tip: We recommend the use of a non-skid pad to keep the rug in place on smooth surfaces.
All rug sizes are approximate. Due to the difference of monitor colors, some rug colors may vary slightly. O.co tries to represent all rug colors accurately. Please refer to the text above for a description of the colors shown in the photo.
|Contemporary Novelty Patterned Traditional
|Border Floral Geometric
|Weave Type
|Beige Black Blue Multi Red Rust
|Rug Type
|6 ft. x 9 ft.
|100-Percent Wool
|Model Number
|Coliseum 5K
Customer Reviews
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Trial for tables
This is a lovely, soft looking rug that blends well with most anything. The only complaint is that it is not actually square, but a bit off square.Read More
Colors are great. Looks just like the photo. Yes, a lot of fuzz fills my vacuum but the rug is thick and very nice. I ended up putting it in my dining room because it didn't quite work in my family room. it looks perfect there.Read More
Very nice rug
This rug was exactly what I was looking for at a great price. It's nice and deep, the colors are as they look in the picture. My kids love lying in it!Read More
Got this last week- shipping was fast and this is a good quality rug. It's definitely a warm rusty red; nothing coral about it. The lighter cream color of the rug that you see is very warm and almost taupe. Not a lot of high contrast between the light and dark colors. All of the colors are very muted.Read More
I'm sure it was fabulous. The colors were just what I had been looking for. However, you sent the wrong rug and buy the time I received it, the one I ordered was out of stock. I am so disappointed and am unable to find anything quite like it on Overstock but I will keep looking.Read More
Beautiful, warm, nice design.
This is the 3rd wool rug I have tried to have in my living room. The 2 (other brands) were returned due to horrible shedding and off color defects. This rug is wool with a cotton backing. It shed a little on the first vacuum, which is normal, but has been nice after that. I turn the beater off on my vacuum when vacuuming wool rugs. The wool feel is a little stiffer on bare feet than the other rugs before, but still comfortable to walk on and very thick and plush. The example picture is fairly close to the real rug, but a little more muted than the photo. The Blue is a soft, and what I would call a country blue, and the rust color looks more muted and soft corral pink tones show up in bright light. Other colors are light blue, grey, cream, off white, 3 colors of brown, light to dark. The center floral design is a Dark Brown. Looks good on a wood floor with dark brown couch. One important note: Due to the thickness- (the edge of this rug measures just under 5/8" thick) I would not recommend it for a house with elderly folks, as it could be a trip hazard. . It is minor fault, but I still give it 5 stars for beauty, value and functionality. It is by far the best wool rug with a true blue combined with rust that I have found after searching for months and looking at thousands of rugs. Very hard to find.Read More
Rich colors & super thick rug.
This rug is excellent.Very thick & vivid colors..I have bought a few rugs from Overstock & all of them have been perfect....I will buy again..Read More
Beautiful Rug -- Perfect Colors
This was the second rug I ordered from Overstock this month. I needed a rug for my living room which would coordinate with my blue couch and chairs but also bring in another color for contrast. The Hand Tufted Coliseum Rust Traditional Border Wool Rug seemed like the perfect choice. I ordered it on a Friday afternoon and received it from Fed Ex on Saturday morning the next day. What fantastic service!! The rug looks superb with my decor! The colors are exactly as they appeared online. It was reasonably priced and is a very high quality rug. I am very pleased.Read More
Great rug for price
Excellent rug for the price. No problems with shedding, other than what the vacuum sucked up the first day. The colors are muted but rich. Gorgeous rust color and beautiful blues and grays, with some toffees, off whites, and dark brown in there. Feels soft and warm underfoot. Goes well with the chocolate brown suede slipcover I bought for our couch.Read More
This rug is a beautiful thick luxurious rug and I highly recommend it. As any new rug it does shed a little but with time I am sure this will stop. It is gorgeous and very well priced.Read More
Questions & Answers
Hello mkrelle, items are restocked as they become available; however, we cannot guarantee an item will be restocked. Thank you for shopping with us.
Why did you choose this product?
for the colors
size, color, design, fabric, price we liked the design. it appeared to be a good value for the price.
Right size, price and color (I hope!)
I was looking to brighten up a rather dull looking dining room. Rust seemed to be the color that I was looking for. I hope that I am pleased with my choice of this rug.
Where is this rug made?
Hello dustypparker, this rug was made in India. Thank you for shopping with us!
The color of the rug differs a lot in the pictures. This is mentioned in the reviews. Would you say it's closer to the room picture or to the darker picture of the rug alone?
Hello Findmeacarpet6, we can appreciate the fact you want a firsthand account of the product. You will receive an email notification every time you get a response. Thank you for shopping with us.
Is the border blue or black? I ordered the rug because of the blue and I don't see any black.
Thanks for your interest, the boarder is blue, there is a little bit of black throughout the rug.
Is the background color rust/orange or rust/red? Please see http://en.wikipedia.org/wiki/Rust_(color) for reference. Thanks!!
Includes shades of light brown, rust red, and taupe.
It is rust/red.
Shopping Tips & Inspiration
Dipped in Gold
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If you want to refresh your home this spring, new pendants and lamps help create a chic, brightening effect.
How to Size Your Room for an Area Rug
How to Size Your Room for an Area Rug from Overstock.com. Select the right size rug for any room using these tips. Shop with confidence for the perfect area rug size with help from this guide.
How to Choose an Area Rug for Your Bedroom
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Take the Floor
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How to Care for Wool Rugs
How to Care for Wool Rugs from Overstock.com. With a gentle approach and a little time, you can keep your wool rugs looking beautiful for many years.
How to Protect Wood Floors with Area Rugs
How to Protect Wood Floors with Area Rugs from Overstock.com. The easiest way to protect wood floors from scratches and wear is to decorate with an area rug. This guide covers what you need to know.
Best Area Rugs for Christmas
Best Area Rugs for Christmas 2014 from Overstock.com. To help get you started on your search for the perfect rug, here are this year's most popular area rug styles. Update your home for the holidays, or give a gift that's a treat for the feet.
Tips on Buying a Persian Rug
Tips on Buying a Persian Rug from Overstock.com. Add classic elegance and rich texture to your home with a Persian rug. Here's what you need to know when you're online shopping for Persian area rugs.
Sole Redemption - 5 Rugs to Make Your Feet Feel Good
Sole Redemption: 5 Rugs to Make Your Feet Feel Good from Overstock.com. Having the right area rug underfoot can activate energy zones throughout your body.
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Tips on Buying Outdoor Rugs from Overstock.com. Here's how to choose the outdoor rugs that are perfect for your home. Complete your patio or deck and save money on the outdoor area rug that's just your style.
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Rooster T. Feathers Comedy Club Tickets and Upcoming Events
Jul 9Thursday July 9, 2015 / 8:00pm
Jul 11Saturday July 11, 2015 / 8:00pm
Jul 11Saturday July 11, 2015 / 10:30pm
Jul 12Sunday July 12, 2015 / 8:00pm
Jul 18Saturday July 18, 2015 / 10:30pm
Jul 24Friday July 24, 2015 / 9:00pm
Jul 25Saturday July 25, 2015 / 8:00pm
Jul 31Friday July 31, 2015 / 9:00pm
Aug 1Saturday August 1, 2015 / 8:00pm
All patrons must be 21 years of age or older. There is a two-item minimum purchase per person.
337 Rooster T. Feathers Comedy Club Tips
The weather was a warm evening.. I wore business casual. .star this tip starred
The weather was sunny, windy, etc.. I wore jeans and t-shirt (casual, yay!).star this tip starred
I wore Jeans.star this tip starred
Very limited selection of bar food available, if you're craving something (like we were with buffalo wings), eat before!star this tip starred
Rooster's food and drinks are not very good. Low quality. I eat before I go. Sometimes the wait staff holds you to the two item minimum and sometimes not.star this tip starred
To PF Changs or something close by before the showstar this tip starred
Minimal selection of food so if you're looking for dinner headstar this tip starred
Parking Near Rooster T. Feathers Comedy Club
Click to View Interactive Map


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Town Square
Slideshow: Creatures of the night
Original post made on Sep 8, 2007
Read the full story here Web Link posted Thursday, March 8, 2007, 1:15 PM
Comments (1)
a resident of another community
on Sep 8, 2007 at 1:40 pm
question? r you still showing this on the 1st and 3rd sat or did it end in april? i wanna go and have fun! [Portion removed by Palo Alto Online staff.]
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