text:
Process of forming multilayered structures
The present invention provides for a method of producing an integral multilayered porous membrane by simultaneously co-casting a plurality of polymer solutions onto a support to form a multilayered liquid sheet and immersing the sheet into a liquid coagulation bath to effect phase separation and form a porous membrane. The support can be a temporary support or form an integrated support for the membrane. The plurality of layers may be of the same polymer or different, same concentration or viscosity or different and may be subjected to the same processing conditions or different ones to form unique structures.
[0001] This invention relates to a process for forming multilayer porous membranes having improved layer to layer junction structure, and to the membrane so formed. More particularly, this invention relates to a process for making a multilayer porous membrane from a multilayered liquid sheet produced by a co-casting method, and to the membranes so formed.BACKGROUND OF THE INVENTION
[0002] Polymeric microporous membranes have been prepared previously. Most of the commercialized membranes are symmetric in nature. Symmetric membranes have an approximately uniform pore size distribution throughout the membrane. The production of skinless symmetric microporous membranes are described, for example in U.S. Pat. No. 4,203,848 for polyvinylidene fluoride (PDVF) and in U.S. Pat. No. 4,340,479 for polyamide membranes. These preparations are generally described to consist of the following steps: a) preparation of a specific and well controlled preparation of a polymer solution, b) casting the polymer solution in the form of a thin film onto a temporary substrate, c) coagulating the resulting film of the polymer solution in a nonsolvent and d) removing the temporary substrate and e) drying the microporous membrane.
[0003] Membrane manufacturers produce membranes that are robust and reliable for sterile filtration using such methods. Such membranes are primarily single layer symmetric membranes, although other structures have been investigated and used for such membranes.
[0004] Another single layered structure is the asymmetric membrane, where the pore size of the membrane varies as a function of location within the thickness of the membrane. The most common asymmetric membrane has a gradient structure, in which pore size increases from one surface to the other. Asymmetric membranes are more prone to damage, since their retention characteristic is concentrated in- a thick, dense surface region or skin see U.S. Pat. No. 4,629,563. It has been found, however, that increased productivity results from having the feed stream to be filtered contact the larger pore surface, which acts to prefilter the stream and reduce membrane plugging, see U.S. Pat. No. 4,261,834. Additionally, others have been successful in making asymmetric non-skinned or skinless microporous membranes. One such product is sold as Express™ membranes made by Millipore Corporation of Bedford, Mass.
[0005] Practitioners in the art of making microporous membranes, particularly asymmetric membranes, have found that membranes which contain large (relative to membrane pore size) hollow caverous structures have inferior properties compared to membranes made without such hollow structures. These hollow structures are sometimes called "macrovoids", although other terms are used in the art. Practitioners striving for membranes of very high retention efficiency prefer to make membranes without such hollow structures.
[0006] Perhaps the most direct variation of the single layer structure is a multilayered unbonded laminate. While laminates can be made from layers of the same or different membranes, they have drawbacks. Each layer has to be made in a separate manufacturing process, increasing cost and reducing manufacturing efficiency. It is difficult to manufacture and handle very thin membranes, less than say 20 microns, because they deform and wrinkle easily. This adds the inefficiency of producing a final product with thin layers. Unbonded laminates can also come apart during fabrication into a final filter device, such as a pleated filter, which will cause flow and concentration non-uniformities.
[0007] Other methods of forming multilayered microporous membrane structures are known. U.S. Pat. No. 5,228,994 describes a method for coating a microporous substrate with a second microporous layer thereby forming a two layer composite microporous membrane. This process requires two separate membrane forming steps and is restricted by the viscosities of the polymer solutions that can be used in the process to prevent penetration of casting solution into the pores of the substrate.
[0008] Attempts have been made to produce multilayer microfiltration membranes. U.S. Pat. No. 4,770,777, describes a process with the following steps: casting a first membrane layer, b) embedding a fabric support into this first membrane and c) casting a second membrane layer on top of the embedded fabric to form a kind of membrane/fabric/membrane sandwich. The presence of a nonwoven could however lead to defects and imperfections, which are undesirable. U.S. Pat. No. 5,500,167 describes a method of preparing a supported microporous filtration membrane. This method consists of applying a first casting solution onto the first side of a porous nonwoven support material to form a first casting solution layer having a substantially smooth surface, then applying a second casting solution onto the substantially smooth surface of the first casting solution layer to form a second casting solution layer prior to the complete formation of a microporous membrane from the first casting layer, and forming a continuous microporous membrane having first and second zones from the first and second casting solutions such that the first side of the support material is integral with the first zone while not protruding into the second zone, and the first zone has a pore size at least about 50% greater than the pore size of the second zone. This product requires a nonwoven support which could lead to defects or imperfections. In U.S. Pat. No. 5,620,790, a membrane is described made by pouring out a first layer on a support of polymeric material onto a substrate and subsequently pouring out one or more further layers of a solution of polymeric material onto the first layer prior to the occurrence of turbidity in each immediately successive preceding layer, the viscosity of each immediately successive layer of a solution of polymeric material having been the same or less than that of the preceding layer. In U.S. Pat. No. 5,620,790, improved throughput is achieved by making fairly thick membranes which will tend to lower overall permeability.
[0009] In all three multilayer casting processes described above, however, a significant interval of time or a setting time between the separate coating steps is essential to the process of forming a multilayer membrane. Such sequential casting can cause the formation of a dense layer at the interface between the two layers in the membrane. This makes these methods undesirable in terms of robustness, since variability of the process during this setting time can lead to non-uniformity. While U.S. Pat. No. 5,620,790 discusses that a minimum setting time of several seconds to 2 minutes are advantageous, the prior art processes cannot reduce the interval between coating applications to essentially no time.
[0010] In the present invention, the inventor has surprisingly found that at essentially no time between the coating applications, one forms membranes in which there is a continuous change of membrane structure without a discontinuity through the junction between layers.
[0011] Furthermore, in the prior art a well-defined demarcation line is found between the two layers. This demarcation line signifies a drastic change in pore size going from a more open to a more tight structure. It can also signify a region of dense, skin-like structure. Either of these structural regions can lead to a lower permeability and an undesirably fast accumulation of particles at the interface and consequently a drastic flux decline. A more subtle change in pore size between two adjacent would reduce this effect and be beneficial for the retentive behavior of the overall structure of the membrane.
[0012] In a brief study as part of the Doctoral thesis of the inventor ("Membrane Formation by Phase Separation in Multicomponent Polymer Systems"; University of Twente, NL 1998), hereby included as reference, the effect of a second polymer solution layer covering a first polymer solution layer on the demixing or phase separation of each layer was studied. The purpose of this work was to qualitatively determine if a dense (non-porous) separation layer of reduced thickness could be formed by covering a first polymer solution layer with a second polymer solution layer of a different composition and then forming a membrane by immersion methods in the usual way. The polymer content and solvents were chosen to produce dense surface layer membranes, such as pervaporation membranes. The author compared the modes of phase separation for single and two layer membranes by comparing overall membrane structure with scanning electron microscopy photomicrographs. No membrane properties were measured. It was inferred from the photomicrographs that the dense layer thickness could be varied by this procedure.
[0013] The inventor found in the development of the present invention that in order to produce microporous membranes of improved properties, it was critical that the structure of the interfacial region between the layers be controlled. Initial work showed that if a dense region formed at the interface, membrane properties suffered. In particular, membrane permeability was reduced and filtration throughput was low for membranes having a distinct dense region at the interface. There was no motivation in the prior art to optimize this region in conjunction with overall membrane structure.
[0014] Moreover, it was found during the development of the present invention that throughput is controlled by the structure of the layer with the larger average pore size in combination with the structure of the interface. Whereas the prior art had concentrated on optimizing the structure of the retentive layer, particularly for membranes with a dense retentive layer, (e.g., reverse osmosis and pervaporation), in the present invention, the inventor was faced with the problem of controlling the retentive properties of all layers and the interfacial regions as well.
[0015] U.S. Pat. No. 5,620,790 teaches that for sequentially cast membranes, a viscosity restraint is imposed in that the viscosity of the lower layer should be higher than the viscosity of the upper layers.
[0016] Accordingly, it would be desirable to provide a process for forming a integral multilayer microporous membrane that is macrovoid free. In addition, it would be desirable to provide a simplified process wherein the layers are cast simultaneously in order to form in a controlled manner regions of intermediate pore size at the junctions of adjoining layers.BRIEF DESCRIPTION OF THE INVENTION
[0017] In accordance with the present invention, a process is provided for producing multilayer microporous membranes including the steps of a) preparing a plurality of lacquers, b) co-casting these lacquers to form a multilayer liquid sheet and c) immersion of the co-cast multilayer liquid sheet into a liquid bath/coagulation bath to effect phase separation in a continuously layer sequence. An optional extraction step after coagulation can be provided to extract all the residual solvent within the microporous structure. The microporous membrane then is dried under restraint.
[0018] The multilayer microporous membrane of this invention is free of a dense interfacial layer between layers. In addition, adjacent layers are inseparable and integral with one another, and are free of macrovoids. Each of the layers of the multilayer membrane of this invention can be a retentive layer in that they retain a retentate component while permitting through passage of a filtrate.BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a side view of an apparatus useful in effecting the process of this invention.
[0020] FIG. 2 is a graph of a flux of the membrane of this invention as a function of air membrane bubble point.
[0021] FIG. 3 is a photomicrograph of a multilayer membrane according to prior art.
[0022] FIG. 4 is a photomicrograph of an asymmetric microporous membrane of the prior art.
[0023] FIG. 5 is a photomicrograph of an asymmetric membrane of this invention.
[0024] FIG. 6 is a photomicrograph of the bottom surface of the membrane of FIG. 5.
[0025] FIG. 7 is a photomicrograph of the top surface of the membrane of FIG. 5.
[0026] FIG. 8 is a photomicrograph of a cross-section of a membrane of this invention.
[0027] FIG. 9 is a photomicrograph of the top surface of the membrane of FIG. 8.
[0028] FIG. 10 is a photomicrograph of the bottom surface of the membrane of FIG. 8.
[0029] FIG. 11 is a photomicrograph of the top surface of an air cast membrane of this invention.
[0030] FIG. 12 is a photomicrograph of the bottom surface of an air cast membrane of this invention.
[0031] FIG. 13 is a photomicrograph of the top surface of an air cast membrane of this invention.
[0032] FIG. 14 is a photomicrograph of the bottom surface of an air cast membrane of this invention.
[0033] FIG. 15 shows a cross-sectional microphotograph of a multilayered structure of the present invention wherein both layers are asymmetrical.
[0034] FIG. 16 shows a cross-sectional microphotograph of a multilayered structure of the present invention wherein one layer, in this instance the top layer is symmetrical and the bottom layer is asymmetrical.DESCRIPTION OF SPECIFIC EMBODIMENTS
[0035] The present invention provides for a method of producing an integral multilayered porous membrane by co-casting a plurality of polymer solutions onto a support to form a multilayered liquid sheet and immersing the sheet into a liquid coagulation bath to effect phase separation and form a porous membrane. The support can be a temporary support which is removed subsequent to membrane formation. Alternatively, it be incorporated into the final structure if desired After formation, the porous membrane is washed free of solvent and other soluble materials. It can then be further extracted to reduce fugitive materials to a low level and then be dried.
[0036] In the present invention, "co-casting" means that the individual layers are cast essentially simultaneously with each other with substantially no time interval between one cast layer and the next cast layer. Co-casting is an important aspect of the invention because it allows for formation of controlled pore size regions at the junctions of layers. In the prior art, a well-defined demarcation line is formed between the sequentially cast layers. A drastic change in pore size going from a more open to a more tight structure can lead to undesirable fast accumulation of particles at the interface and/or the formation of a skin layer at the demarcation point and consequently a drastic flux decline. Possibly due to partial mixing of adjacent co-cast lacquers or due to high shear forces at the interface between two adjacent co-cast lacquers, a sharp interface can be replaced by a more subtle change in pore size between two adjacent layers. Such an interfacial zone is beneficial for the retentive behavior of the overall structure of the membrane. At the same time, it allows the formation of microporous structure with no discernable demarcation line in the structure.
[0037] Likewise, the term "integral" means a structure, that although formed of multiple layers and often different polymeric materials, that is bonded together so that behaves it as one structure and does not delaminate or separate in normal use.
[0038] FIG. 1 illustrates a multiple layer forming apparatus 10 for casting multilayered membranes. As shown, the apparatus is designed to produce a two-layered liquid film and has two chambers 50 and 60 containing the solutions 14 and 16, one for each layer, to be cast. If desired, additional chambers may be added to form additional co-cast layers. The apparatus comprises a front wall 20 and a back wall 40 with a separating wall 30 between the front and back walls. The separating wall defines the volumes of the two chambers. Two side walls, not shown, complete the apparatus. In operation, the apparatus is fastened onto a typical membrane casting machine, and a support web 18 is moved or passed under the stationary apparatus and the two solutions are dispensed through gaps or outlets 80 and 90. The thickness of the two layers is controlled by the distance (gap) set between the moving web and the outlet, illustrated by gap settings 80 and 90. The final liquid layer thickness is a function of gap distance, solution viscosities, and web speed. The back wall of the apparatus usually is held a small distance above the support to prevent wrinkling or marring the support. Back wall gap, support speed and solution viscosity are adjusted in practice to prevent solution from leaking out through the back wall gap. The apparatus can be fitted with heating or cooling means for each chamber separately, or for the apparatus as a whole, if necessitated by the solution characteristics, or to further control final membrane properties.
[0039] As illustrated the process relies on gravity driven flow. However, the chambers can be covered and sealed if needed, and fitted with an inlet for a pressurized fluid, usually an inert gas such as dry nitrogen or argon. The chambers can then be pressurized separately as required by the solution viscosity and process requirements. In another embodiment, the solutions are pumped.
[0040] The temporary support 18, such as a non-porous plastic or metal sheet, with the co-cast multilayer liquid sheet is then immersed in a coagulant bath (not shown) as is well-known in the art for a period to effect phase separation of the polymer solutions in a continuously layered sequence and form an integral multilayer microporous polymeric membrane. After formation, the membrane is usually washed to remove residual solvent and other low molecular weight components of the casting solution and wound onto a core. The temporary support 18 is wound onto a separate wind up drum (not shown).
[0041] If the support is not temporary but is intended to be a permanent portion of the finished product, one may use a nonporous film for uses such as diagnostic strips or a porous, nonwoven fabric such as TYVEK® sheets, a stretched porous PTFE sheet such as is available from W.L. Gore & Associates of Timonium, Md., or a microporous membrane made of cellulosic material or plastic or other such materials commonly used in the art as support layers for these types of membranes.
[0042] In a continuously layered sequence of coagulation, coagulation occurs from the liquid film surface that first contacts the coagulation bath and then through the subsequent layers of the multilayered liquid sheet. Each layer dilutes and changes the coagulant as the coagulant diffuses through the layers. Such changes to the nature of the coagulant affect the membrane formation of each layer and of the final multilayer membrane. Layer thickness, composition and location of each layer relative to the other layers will affect membrane structure and properties. This is obviously different from a single layer membrane and from membranes made from laminates of single layers.
[0043] The process is adaptable to complementary membrane formation steps. For example, in our co-pending application, No. 60/206,622 filed May 24, 2000, a process of producing symmetric and/or asymmetric membranes is disclosed in which a single layer liquid film of a membrane forming composition containing a semi-crystalline polymer is briefly heated before phase separation. Such heating controls the final membrane pore size and cross-sectional structure. In an embodiment of the present invention, one or several layers would be formed from such compositions utilizing the thermal process of the co-pending application to give additional methods of forming desired pore size and membrane architecture.
[0044] In another embodiment of the present invention, the teachings of U.S. Pat. No. 5,444,097 are used in which a membrane is made from a polymeric solution exhibiting a lower critical solution temperature (LCST). Heating the solution above the LCST causes phase separation. This step is incorporated in the process of the present invention after the multilayered liquid film is formed to further vary and control the structures of the resulting membranes. One or several of the solutions of the present invention would be LCST solution. Similarly, solutions with an upper critical solution temperature (UCST) which phase separate when cooled below the UCST, would be formed into a multilayered liquid film in a heated state and cooled to obtain phase separation. In both the LCST and UCST embodiments, further phase separation can be provided by immersion into a coagulant, as described previously.
[0045] Air casting, sometimes called vapor induced phase separation, in which phase separation occurs during an evaporation step, can be adapted to this process by forming a multilayered liquid layer from solutions containing an evaporative solvent and less evaporative non-solvents, and subjecting the liquid film to an evaporative environment, such as a heated air stream, optionally containing water vapor.
[0046] The process of this invention provides for separate control of the individual regions of the membrane, a region being comprised of membrane formed by each solution and a possible interfacial region and the controlled pore size regions at the junctions of layers. This process allows a wider range of useful viscosities of the individual layers, a better control of the thickness of the two or more individual layers and avoids possible skinning effects or dense regions at the interface between the two or more layers, usually between 2 and 4 layers. In one embodiment, a nonwoven support can be used to increase mechanical stability, although unsupported composite membranes have sufficient mechanical strength (depending on pore size). This combination therefore allows the formation of better controlled, higher integrity, multilayer microporous membranes with improved fluxes.
[0047] The process of this invention also allows for independent casting of very thin layers. Layer thickness depends not only on the casting device geometry but also on flow and viscosity of both lacquers. In the process of this invention, the well-defined demarcation line seen in prior art between the two layers can be significantly reduced or avoided. A drastic change in pore size going from a more open to a more tight structure can lead to undesirable fast accumulation of particles at the interface and consequently a drastic flux decline. Possibly due to partial mixing of adjacent co-cast lacquers or due to high shear forces at the interface between two adjacent co-cast lacquers, a sharp interface can be replaced by a more subtle change in pore size between two adjacent layers. Such an interfacial zone is beneficial for the retentive behavior of the overall structure of the membrane. At the same time, it allows the formation of microporous structure with no discernable demarcation line in the structure. In addition, in some cases, shrinkage of the formed membranes can be prevented in a co-cast mode while a considerable shrinkage occurs in single films. This also allows the use of membrane structures, which would otherwise be difficult or impossible to make from a particular lacquer, especially for membranes with a very small pore size, shrinkage is found to be substantial as single films.
[0048] As discussed above, this process can be used with any of the known methods for forming microporous membranes such as liquid casting or air casting. Additionally, the polymers and solvents/nonsolvents used for making such microporous membranes can also be used.
[0049] Preferred polymers include but are not limited to PVDF, nylons such as Nylon 66, polyamides, polyimides, polyethersulphones, polysulphones, polyarylsulphones, PVC, PET, polycarbonates, cellulose, regenerated cellulose, cellulose esters such as cellulose acetate or cellulose nitrate, polystyrenes, polyetherimides, acrylic polymers, methacrylic polymers, copolymers of acrylic or methacrylic polymers, or blends of any of the above and the like.
[0050] The polymer solutions of the present invention typically consist of at least one polymer and at least one solvent for the polymer or polymers. The solution may contain one or more components that are poor solvents or non-solvents for the polymer or polymers. Such components are sometimes called "porogens" in the art. The solutions are preferably homogeneous. They can optionally contain one or more components, which are non-solvents for the polymer. The polymer solution can either be stable in time (good solvent quality) or be meta-stable in time. This solution also can potentially have a lower critical solution temperature or an upper critical solution temperature. Example components of such solutions are well known in the art, and it is not necessary to exhaustively list all possible variations. Solvents that are used included such examples as dimethyl formamide, N,N-dimethylacetamide, N-methyl pyrrolidone, tetramethylurea, acetone, dimethylsulfoxide. A myriad of porogens have been used in the art, including such examples as formamide, various alcohols and polyhydric compounds, water, various polyethylene glycols, and various salts, such as calcium chloride and lithium chloride.
[0051] One can form the layers of the same polymer and solvent, varying the viscosity, additives and treatment (before, during or after formation) or one can different polymers for the different layers. When using different polymers one must select polymers that are compatible with each other. Additionally, the solvents and phase separation materials should be the same if possible or at least compatible so that they do not adversely affect the other layer(s).
[0052] The microporous structures of the present invention may have an average pore size of from about 0.01 microns to about 10 microns, preferably from about 0.01 to about 2 microns.
[0053] As discussed above, the use of various formulations and processing steps, such as the thermal assisted formation process of No. 60/206,622 filed May 24, 2000 can create some unique multilayered products. One can form multilayered products with all layers being either symmetrical or asymmetrical, with at least one layer being symmetrical and the others being asymmetrical, with at least one layer being asymmetrical and the others being symmetrical, with both inversely asymmetrical such that the pores form an hourglass like structure with the smallest pore size being within the depth of the cross section of the structure, etc. Symmetric membranes have a porous structure with a pore size distribution characterized by an average pore size that is substantially the same through the membrane. In asymmetric membranes, the average pore size varies through the membrane, in general, increasing in size from one surface to the other. Other types of asymmetry are known. For example, those in which the pore size goes through a minimum pore size at a position within the thickness of the membrane. Asymmetric membranes tend to have higher fluxes compared to symmetric membranes of the same rated pore size and thickness. This invention allows one to form unique structures to handle specific applications and needs.
[0054] Asymmetrical membranes may have a pore size gradient of from about 2:1 to about 1000:1, preferably from about 2:1 to about 100:1. This asymmetry is measured by comparing the average pore size on one major surface of the layer with the average pore size of the other major surface of that layer. In this invention, one can create two or more asymmetrical layers, each having a different or if desired, similar asymmetry.
[0055] Additionally, as mentioned above, one vary the thickness of each layer within a wide range and still obtain a self-supporting, integral multilayered structure. Typically, one desires to have the thickness of the membrane structure to be between 50 and 200 microns in thickness as this provides good filtration characteristics and self support. With the present invention one can still achieve the same overall thickness but can control the relative thickness fo one layer to the other to create unique and desirable membrane structures. Typically, one can make one layer as thin as 10 microns and it will result in an integral multilayered structure so long as the remaining structure is a suitable thickness. Thus for example in a 150 micron thick membrane, one can have a first layer that is from about 10 to about 140 microns thick while the other is correspondingly from about 140 microns to about 10 microns in thickness.
[0056] FIG. 15 shows a cross-sectional microphotograph of a multilayered structure of the present invention wherein both layers are asymmetrical.
[0057] FIG. 16 shows a cross-sectional microphotograph of a multilayered structure of the present invention wherein one layer, in this instance the top layer is symmetrical and the bottom layer is asymmetrical.EXAMPLE I
[0058] Solutions were made consisting of 17 to 24 w % polyvinylidenefluoride (PVDF) and 83 to 76% N-methylpyrrolidone (NMP). Each solution was divided into several smaller quantities, which each underwent a different thermal treatment, as shown in Table 1. Each thermal treatment consisted of heating the polymer solution to a predetermined temperature and holding the solution at that temperature for 2 hours. Temperatures ranged from 38 to 50° C. During treatment the solutions were gently agitated using a roller mill. Thereafter the solutions were cooled to room temperature.
[0059] Multilayers of two polymer solutions were co-cast using an apparatus such as illustrated in FIG. 1. Lacquer reservoirs 50 and 60 were filled with the two different polymer solutions. By moving the belt relative to the casting apparatus, a multilayer structure was cast without any setting time between the two lacquers. The volumetric flow of the two polymer solutions and the thickness of each layer was controlled by the gap settings 80 and 90 of FIG. 1. The formed multilayer was immersed in a methanol bath having a methanol concentration as high as 95% for approximately two minutes. The bath was kept at room temperature. The flow of the methanol was counter current to the direction of introduction of the multilayer to allow good extraction of NMP from the multilayer membrane. After immersion in the methanol bath for about 2 minutes, the multilayer membrane was removed from the support belt and extracted in a water bath for about 4 minutes. Thereafter the multilayer membrane was taken up onto a core. The membrane was then extracted further in water, immersed in isopropyl alcohol (IPA) and dried under restraint in air. In the Table below the various conditions for co-casting are summarized.
[0060] This rendered membranes which exhibited higher fluxes compared to commercial, symmetric, hydrophobic PVDF membranes (Durapore® membranes, available from Millipore Corporation of Bedford, Mass.) of a similar thickness. In FIG. 2, a flux vs. bubble point map is displayed illustrating the flux improvement of the membranes made by the present invention. FIG. 2 shows that the membranes of the present invention have higher flux properties at similar bubble points. 1 Top-layer Thickness [PVDF] Tmax- [PVDF] Tmax bath Top-layer Mean Corrected belt side belt side bath side side thickness BP Air flow Air flow [w %] [C] [w %] [C] [um] [psi] [scfm/psi] [scfm/psi*] 1a 20 32.5 20 50 46.4 44 0.0489 2.2 1b 20 40 20 50 32.2 32 0.0674 2.2 1c 20 45 20 50 7.1 0.1648 1d 20 32.5 20 60 10 40 0.012 0.12 1e 20 45 20 60 39 12 1f 17 42.5 17 20 11 1g 20 42.5 20 50 162 10.5 0.1059 17.3 1h 24 42.5 24 20 1I 17 45 17 20 32 0.0352 1j 20 37.5 20 50 41 51.7 0.0399 1.7 1k 20 40 20 50 65 31.2 0.0636 4.1 1l 20 42.5 20 50 58 29 0.0629 3.6 1m 17 37.5 17 50 80 24.5 0.0659 5.2 1n 24 42.5 24 50 38 1o 17 37.5 17 50 73 6.8 0.0659 4.8 1p 17 37.5 17 50 69 1q 24 37.5 24 50 50 5.2 0.2535 12.6 1r 24 45 24 50 90 1s 20 37.5 24 50 21.8 0.045 1t 20 42.5 24 50 57 30.4 0.0459 3.2 1u 20 40 24 50 68 27.5 0.0542 3.6 1v 17 37.5 24 50 60 14.7 0.0573 3.4 1w 17 37.5 20 50 27 22.6 0.0663 1.7 1x 24 37.5 20 50 151 18 0.0849 12.8 1y 20 40 17 50 14.5 0.1012 1z 17 37.5 20 50 45 52 0.0386 1.7 1aa 17 37.5 20 50 45 37 0.0371 1.6 1ab 20 40 20 50 1ac 20 40 20 50 1ad 20 42.5 20 50 59 15 0.0875 5.1 1ae 20 42.5 20 50 38 12.5 0.139 5.3 1af 20 45 20 50 47 6 0.18 8.5 1ag 20 45 20 50 52 5.5 0.17 8.84 1ah 20 40 20 50 29.8 30 0.0494 4.8 1ai 20 40 20 50 10 0.1608 Reference: hydrophobic Durapore ® membrane identified by pore size rating 0.45 15 0.045 5.5 0.22 27 0.028 3.5EXAMPLE II
[0061] In a comparative test of drying formed and washed membranes, it was demonstrated that multilayer membranes have the potential to shrink less as compared to a symmetric membrane cast from a single polymer solution.
[0062] In this experiment a PVDF solution was made from 16 w % Solef 1015 (Solvay, Belgium) in NMP and a solution of Kynar 741 (Elf Atochem, USA) in NMP. The Solef solution was cast as a single layer and as a co-cast film with the Kynar solution. Both films were immersed in a methanol bath under exactly the same conditions of casting speed (2 minutes immersion), temperature (room temperature) of the coagulation and lacquer. After immersion, the membranes were extracted in water and dried on an impingement dryer under the same reduced pressure, the same drying time and the same temperature. This drying occurred under the same web speed, which set the unidirectional tension on the membrane. The composite membrane did not shrink at all, while the single film cast from the Solef solution lead to a width reduction to 65% of its original width. Reduction of membrane shrinkage will provide for improved yields in membrane production, and will allow for more efficient processing of the produced membranes.EXAMPLE III
[0063] In this experiment, a membrane made with a short "setting time" is compared to a membrane made by the present invention. FIG. 4 shows a dense interface between the two polymer solutions. This membrane was made by sequentially casting a second polymer solution onto a first film of PVDF lacquer. In all of the experiments where lacquers were simultaneously cast, no such interface was observed.
[0064] Two polymer solutions are made using 20% PVDF and 80% NMP. A multilayer film was produced by casting a first layer of the PVDF solution on a glass plate. The first layer was exposed to the atmosphere before a second layer was cast on the first layer. Atmospheric exposure was accomplished by having a short space, approximately two centimeters between sequential casting steps. The formed multilayer was immersed into methanol until a membrane was completely formed and then extracted in water. The membrane was dried under restraint in air.
[0065] The membrane was fractured in nitrogen and a scanning electron microscope image was taken of the cross-section. This image is given in FIG. 4. A distinct dense region is clearly apparent at the interface of the adjoining layers.
[0066] FIG. 5 shows a typical cross-section of a membrane of the present invention with completely different pore sizes in both layers. This membrane was prepared by simultaneously cocasting of two solutions having the same composition (20 w % Kynar 741) and a similar viscosity but a different thermal history. Two regions can be seen, but there is no dense interface.EXAMPLE IV
[0067] In this example, a cocast multilayer membrane is produced by casting a solution of higher viscosity for the top layer on a solution of lower viscosity. Using a polymer concentration of 24 w % PVDF for the upper layer solution and a polymer concentration of 20 w % PVDF for the lower solution, a structure was formed which has a very small pore size at the top part, a larger pore size at the other surface and a zone in the membrane where pore size changes gradually. (See FIG. 6). No interface is discernable.
[0068] A 24% and a 20 w % PVDF solution were made in NMP. Viscosities of a 24 w % and a 20 w % PVDF solution are in the range of 12,000 cP and 3,500 cP respectively. A multilayer was cast as explained in example 1, with the 24 w % solution being cast so it faces the methanol bath, the 20 w % solution facing the support belt. SEM images were taken of the multilayer as given in example 3. Surprisingly, no interface was observed between the two layers. FIG. 6 is a cross-sectional view of the membrane; FIG. 7 is a view of the surface of the membrane at the bath side, showing a skinless tight pore structure; FIG. 8 shows a view of the surface of the membrane at the belt side, showing a skinless open pore structure.EXAMPLE V
[0069] In this example two solutions of the same polymer type and concentration, but different viscosities and temperature treatments are co-cast. The viscosity of the top layer solution was increased by having 5% lithium chloride in the polymer solution. Furthermore, the temperature to which this higher viscosity solution was raised and held was 47.5° C., compared to 44° C. for the lower layer solution. A higher temperature treatment is known to result in a larger membrane pore size for this type of polymer solution.
[0070] The solutions were made with the following compositions: 2 Treatment [PVDF] [NMP] [LiCl] temperature [C.] PS1 20 75 5 47.5 PS2 20 80 0 44
[0071] When a higher viscosity solution (PS1) was used on top of layer of a lower viscosity solution (PS2), structures as displayed in FIGS. 9, 10 and 11 are obtained. Here a more open layer can be observed at the top layer (bath side) (see FIG. 9) compared to the bottom layer (belt side) (see FIG. 10). The difference in pore size is not surprising since the membrane was formed from two individual lacquers with the upper lacquer (PS1) treated to a higher temperature, which will produce a solution giving a larger pore size compared to the lower lacquer (PS2). Viscosity of the upper solution was changed by adding 5% LiCl. Both solutions contained 20 w % PVDF. However these membranes also had no discernable interface between the two layers, which as stated above can be beneficial for membrane performance (see FIG. 11).EXAMPLE VI
[0072] To demonstrate that with the disclosed method, no setting time is required as prior art indicated and that the method is not too dependent on the precise method of diffusion induced phase separation, two membranes were cast using the air-cast method, disclosed by Zeman (in Journal of Membrane Science, Vol. 84, p. 93-106 (1993)). Two polymer solutions of relatively low viscosity solutions were made by dissolving two molecular weights of cellulose acetate in a mixture of acetone and methyl-2,4 pentanediol (MPD). The two different cellulose diacetate polymers are CA-398-60 with a average Mw of about 240 kDa and CA-398-30 with a Mw of about 174k Da from Eastman Chemical Products. The first polymer solution (PS3) had the following composition: 9% CA-398-30, 40% MPD and 51% acetone. The second polymer solution (PS4) had the following composition: 9% CA-398-60, 40% MPD and 51% acetone.
[0073] Similar solutions were used by Zeman et al. to show the influence of the molecular weight on surface morphology during air casting. By using the co-casting method as explained above, multilayered membranes were made. Since co-casting was used no setting time was allowed between the application of the two layers. Membranes were cast with gap settings of about 30 mil and 16 mil. These membranes were exposed to humid air +/−55 % RH at 25 C for 30 minutes. Thereafter the membranes were washed in water overnight to remove the remaining MPD and finally the membranes were air dried.
[0074] The first membrane was made by applying solution PS3 on top of PS4, while in the second experiment solution PS4 was on top of solution PS3. FIGS. 12 and 13 show the two surfaces of the first membrane, while FIGS. 14 and 15 those of the second membrane. In both cases, isolated pores are observed in the surface of the membrane that was exposed to air. It is clear that co-casting enables the deposition of two layers of low viscous materials without an intermediate "setting" step. This clearly demonstrates that the proposed process does not need any control over the setting step and is a clear advantage for process controls.
[0075] The inventor has found that co-casting two solutions allows one to control the surface pore size and pore morphology combination for both surfaces. For example, the membrane shown in FIGS. 12 and 13 has a top surface corresponding to the air side surface of a membrane cast from only the solution used for the top surface and a bottom surface formed at the support that corresponds to the bottom surface of a membrane cast only from the polymer solution used to make the bottom layer. Furthermore, the example demonstrates that the surface properties of the multilayer membrane can be designed by choosing the formulation properties of the two solutions: i.e. in this example the molecular weight of the polymer.EXAMPLE VII
[0076] The following two examples VII and VIII demonstrate that different structures can be generated using the cocast method and that this method can be used with other polymers as well.
[0077] Two polymer solutions were made with the following concentrations: 15 w % polyethersulphone, 29.7w % N-methylpyrrolidone and 55.3 w % triethyleneglycol and 11w % polyethersulphone, 32.0 w % N-methylpyrrolidone and 57.0 w % triethyleneglycol. These solutions were cocast according to the present invention. The first solution was used as the bottom solution, while the latter for the top solution. The cocast film was exposed to air for 3.5 secs at a temperature of 69° F. and a dew point of 20° F. and subsequently immersed in a water bath at 61° C. for about 75 seconds.
[0078] The membranes showed a peak IPA bubble point of 27 psi and a water permeability of 2200 lmh/psi. FIG. 15 shows a cross-sectional microphotograph of a multilayered structure of the present invention wherein both layers are asymmetrical.EXAMPLE VIII
[0079] Two polymer solutions were made with the following concentrations: 15 w % polyethersulphone, 29.7 w % N-methylpyrrolidone and 55.3 w % triethyleneglycol and 13 w % polyethersulphone, 14.4 w % N-methylpyrrolidone and 72.6 w % triethyleneglycol. These solutions were cocast according to the present invention. The first solution was used as the bottom solution, while the latter for the top solution. The cocast film was exposed to air for 3.5 secs at a temperature of 68° F. and a dew point of 20° F. and subsequently immersed in a water bath at 55° C. for about 75 seconds.
[0080] The membranes showed a peak IPA bubble point of 29 psi and a water permeability of 1700 lmh/psi.
[0081] FIG. 16 shows a cross-sectional microphotograph of a multilayered structure of the present invention wherein one layer, in this instance the top layer is symmetrical and the bottom layer is asymmetrical.
[0082] A practitioner skilled in the art of developing and producing microporous membranes will be able to discern the advantages of the present invention. It is not the intent of the discussion of the present invention to exhaustively present all combinations, substitutions or modifications that are possible, but to present representative methods for the edification of the skilled practitioner. Representative examples have been given to demonstrate reduction to practice and are not to be taken as limiting the scope of the present invention. The inventor seeks to cover the broadest aspects of the invention in the broadest manner known at the time the claims were made.
1) A process of forming multilayered microporous structures comprising the steps of:
- a. preparing two or more solutions of a polymer and a solvent for said polymer,
- b. cocasting the two or more solutions onto a support,
- c. effecting a phase separation of the two or more solutions and,
- d. recovering the microporous multilayered structure.
2) The process of claim 1 further comprising after the cocasting step of (b) but for effecting a phase separation of step (c), subjecting at least one of the solutions to heating to attain a predetermined temperature in said solution.
3) The process of claim 1 further comprising extracting the remaining components of the solvent system from the recovered microporous structure.
4) The process of claim 1 further comprising drying the recovered microporous polymer structure.
5) The process of claim 1 wherein each polymer solution is a homogenous solution.
6) The process of claim wherein at least one of the two or more polymer solutions is a homogeneous solution.
7) The process of claim 1 further comprising at least of the two or solutions contains one or more components that are non-solvents for said polymer solutions.
8) A multilayered membrane formed of two or more layers, the membrane being microporous, integral and having been formed by a process of cocasting.
9) A multilayered membrane formed of two or more layers, the membrane being integral and said membrane being made by the process of claim 1.
10) The multilayered membrane of claim 9 wherein at least one layer is asymmetrical.
11) The multilayered membrane of claim 9 wherein at least one layer is symmetrical.
12) The multilayered membrane of claim 9 wherein at least one layer is asymmetrical and the remaining layers are symmetrical.
13) The multilayered membrane of claim 9 wherein all of the layers are asymmetrical.
14) The multilayered membrane of claim 9 wherein all of the layers are symmetrical.
15) The multilayered membrane of claim 9 wherein there are a first and a second layer and the first layer has a thickness of from about 10 microns to 140 microns.
16) The multilayered membrane of claim 9 wherein at least one layer is asymmetrical and the asymmetry of pore sizes from a first major surface to a second major surface is from about 2:1 to about 1000:1.
17) The multilayered membrane of claim 9 wherein the average pore sizes range from about 0.01 to about 10 microns.
18) The multilayered membrane of claim 9 wherein the average pore sizes range from about 0.01 to about 2 microns.
19) A multilayered, microporous membrane formed of two or more layers, the membrane being integral and said membrane being made by the process of:
- a. preparing two or more solutions of a polymer and a solvent for said polymer,
- b. cocasting the two or more solutions onto a support,
- c. effecting a phase separation of the two or more solutions and,
- d. recovering the multilayered structure.
20) A microporous, polymeric structure comprised of a first layer and a second layer, wherein at least the first layer is symmetrical.
21) A microporous, polymeric structure comprised of a first layer and a second layer, wherein at least the first layer is asymmetrical.
22) The structure of claim 20 wherein the second layer is asymmetrical.
23) The structure of claim 20 wherein the second layer is symmetrical.
24) The structure of claim 20 wherein the first layer has a thickness of from about 10 microns to about 140 microns.
25) The structure of claim 21 wherein the second layer is asymmetrical.
26) The structure of claim 21 wherein the second layer is symmetrical.
27) The structure of claim 21 wherein the first layer has a thickness of from about 10 microns to about 140 microns.
Type: Application
Filed: Nov 1, 2002
Publication Date: Nov 13, 2003
Patent Grant number: 7229665
Inventor: Willem Kools (Winchester, MA)
Application Number: 10275210
International Classification: B01D063/08;


text:
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subset: commoncrawl


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Speaker: Dolley Madison created role of first lady
Dolley Madison wasn't the first first lady of American politics, but her charm, her support of her husband and her ability to bring people together in an era of acrimony and upheaval in Washington came to exemplify the role for more than a century and made her a merchandising icon, according to Holly Shulman, director of the Dolley Madison Digital Edition at the University of Virginia.
Shulman's lecture, "Dolley Madison and the Creation of the First Lady," drew more than 100 people Tuesday night as part of James Madison University's weeklong presidential inauguration festivities.
"She certainly held [Washington] society in her hand," Shulman said.
A widow who stole the heart of a reticent Virginia statesman named James Madison and followed him to the nation's capital for his tenure as secretary of state and later as the country's fourth president, Dolley Madison is perhaps best known as "the hostess who served ice cream and saved George Washington's portrait" during British troops' burning of the White House in 1814, Shulman said.
Indeed, while her husband was busy developing into the role of a wartime president, Dolley Madison played the part of the ceremonial hostess to perfection, Shulman said. Unlike Philadelphia, the cosmopolitan former seat of American government, Washington, D.C. — still a largely undeveloped and impoverished city in the early years of the republic — offered Dolley "a blank slate" on which to leave her mark, one free of the pressure of having to compete with high society, Shulman said. In the new capital city, she said, the Madisons could "easily outrank, out-dress and out-party any American."
Dolley made a point to dress for social events in a republican, rather than monarchical, style — velvet dresses and pearls as opposed to the European women's fashion of satin and diamonds — and with the help of the architect Benjamin Latrobe, she decorated the public spaces of the White House in a manner "fine enough for European dignitaries, but plain enough for a good American harvest table," Shulman said.
Her parties — known as "Wednesday night squeezes" — were welcome diversions from the tedium of public service, and she used the events to help ease the political tensions of the day, Shulman said. This was particularly important during the Madison administration, she said, as two emerging factions — Republicans and Federalists — wrestled for control of the new government.
Despite her many charms, Dolley Madison was not universally loved during her husband's tenure as president, Shulman said, and she faced many of the same societal limitations as other women of her day.
"All first ladies become lightning rods for criticism of their husbands," she said. "Dolley was criticized, but she did manage to hold this society together and, in doing so, probably helped James Madison as a leader."
In her lifetime, Dolley became the symbol of the American hostess, and her likeness, which grew along with the development of commercial packaging and advertising, graced an array of products, from ice cream to jewelry, well into the mid-20th century. Even long after her death, Shulman said, she has remained "an icon of hospitality and of women's leadership by virtue of her tact, her generosity, her wisdom and her charm."
Dr. Anthony Eksterowicz, professor emeritus of political science at JMU and co-editor of the 2003 book "The Presidential Companion: Readings On the First Ladies," said Dolley Madison had a penchant for what scholars have termed "parlor politics." "She took politics out of the street, where it was practiced vitriolically, and brought it into the parlor, where it gained a measure of sensibility," he said.
JMU's own "first lady," Mary Ann Alger, who was in attendance Tuesday, said she is currently reading several books on Dolley Madison and has drawn inspiration from her legacy.
"She was very cutting edge for her day," Alger said. "Getting people together and connecting people was a real strength of hers. I think I would have liked her."
# # #
By Jim Heffernan ('96)
March 13, 2013
Published: Wednesday, March 13, 2013
Last Updated: Thursday, November 10, 2016


text:
Sweet Gifts
We carry Indian mithai and Persian sweets for all occasions.
Indian Sweets For Diwali Festival:
Shop for diwali sweet gifts made in USA in this section. Special homemade Indian
mithai packed in upscale diwali gift boxes and traditional mithai dubba. Diwali is a time
for delicious, traditional sweets such mouthwatering barfi, laddoos and katlis. On this
day, people wear new clothes and share gifts and sweets with their friends and relatives.
Exchanging sweets has become a part of the tradition.
Some of the popular diwali Mithai are-
Barfi: This special sweet is made of milk and sugar, garnished with cardamom and
Jalebi: Another well renowned Indian mithai ,Jalebis are made of sugar and besan
(gram four).
Kaju Katli: A soft diamond shaped sweet made from freshly ground cashews.
Peda: A delicious milk fudge.
Moti Choor Ladoo: The most famous of all Indian sweets. Round in shape, made of
besan and consisting of cardamom, pistaschio, and a touch of saffron.
Badam Barfi: Square shaped Barfi made from Almonds and topped with cardamom seeds
and pistachio nuts.
Persian Sweets For Nowruz Festival:
Noruz or Persian New Year falls on spring equinox around March 21st. Noruz lasts for 13
days. It is a special day for Iranians. They believe on this day, earth is recreated and
new crops grow. Persians share gifts and sweets with their friends and relatives. The
gifts given usually include confectioneries, especially gaz made in Isfahan or sowhan.
Other types of sweets, pistachio nuts, dried nuts are also appropriate gifts for the
Payment methods:
Shipping Methods:


text:
So hey, over the next couple of weeks, there will be a "virtual book tour" for Yes Means Yes: Visions of Female Sexual Power and a World Without Rape, in which Jaclyn, Jessica, and various contributors will be dropping by various other contributors' and friends' blogs.
It kicks off today at Feministing, with a live chat at 3 p.m. EST, featuring Jessica, Jaclyn, Samhita Mukhopadhyay, Miriam Perez, and Cara Kulwicki.
On February 12, I'll be posting a Q&A with Kimberly Springer, author of the essay "Queering Black Female Sexuality."
And on February 20, Jill Filipovic at Feministe will host the "grand finale conversation" with Rachel Kramer Bussel, Toni Amato, Javacia Harris, Stacey May Fowles, Hanne Blank, Heather Corinna, and yours truly.
Other stops on the tour will include:
The F-Word – 2/3
Q&A with Leah Lakshmi Piepzna-Samarasinha
RH Reality Check – 2/4
Live chat with Julia Serano & Latoya Peterson
Our Bodies Our Blog – 2/5
Q&A with Brad Perry & Lisa Jervis
Shakesville – 2/9
Live chat with Jaclyn
Scarleteen – 2/10
Heather Corinna
Angry Black Bitch – 2/11
Q&A with Tiloma Jayasinghe
Bitch Ph.D. – 2/16
Guest blogging with Jaclyn & Jessica
Shameless – 2/17
Q&A with Jill Filipovic
Q&A with Anastasia Higginbotham
Radical Doula – 2/19
Q&A with Hazel/Cedar Troost
Please check it all out! And of course, buy the book!


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Clinics and Hospitals
The Pet Memorial Program at the University of Florida College of Veterinary Medicine provides a way to make a difference. A gift to the Pet Memorial Program in memory of someone's beloved pet relays the message that you truly care about this significant loss in their lives, and in a way that benefits all animals by supporting Florida's only College of Veterinary Medicine. Many people are touched that someone has taken the time to let them know how much they sympathize by remembering their pet in this special way. A contribution to the Pet Memorial Program can aid in the healing process when a pet passes away, and offers an opportunity to acknowledge pain and loss in a meaningful way.
Thank you for your support of the Pet Memorial Program, at the University of Florida. Many students, faculty and animal friends benefit from gifts like yours to the University of Florida, College of Veterinary Medicine.
Be sure to complete the 2-step process below:
Step 1:
Complete the form below. Once this information is collected and processed we will then mail a sympathy card to the recipient named in the form.
Step 2:
Please submit your donation on the UF Foundation secure site
OR you may mail your donations to the following address:
Mail to:
Pet Memorial Program
University of Florida
College of Veterinary Medicine
P.O. Box 100125
Gainesville, FL 32610
*Please make out checks to: University of Florida Foundation.
OR make a phone payment by calling: 1-877-351-2377 (This contribution is for FUND# 5847)
Feel free to contact us with any questions, remarks or concerns.
Phone: 352.294.4256
Email: firstname.lastname@example.com


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Home > Working Dogs
Part Number: BCVEG
Weight: 10kg
In stock - despatch available Monday to Thursday *See delivery FAQs
Our beef chunks are all from UK cows and human grade.
They consist of cow's lips and cheeks and make a very meaty, chunky food, just defrost and feed.The chunks are roughly 3" square.
I also find this product very good dogs also love it.
Was this helpful to you? Yes / No
This review has not been appraised.
Live the handy chunks delivery was really quick will defiantely use again x
My dogs would not touch the huge lumps of cow lips. Utterly revolting. Not explained how disgusting it was. Ended up with large pieces hidden in my bedroom. Would give a - review rating if option available
We're sorry you feel this way. The Beef Chunks are a very popular product and there is a photo on the website showing exactly what they are like so you know what to expect. They are extremely nutrious and most raw food companies sell them. I know you explained to me that you are a Vegetarian so it would have been good to mention that in your review so that other customers would understand the content of your review more as to why you found them so 'vile'
The chunky meat comes in frozen blocks which defrost into good size pieces. Both my dogs love them, gives them something to chew on. They take a piece out of their bowl,go off to their own space & have a good munch
Mostly large, about 100g a peice, a few smaller and a few larger. Makes guesstimation nice and easy. Dog will be sampling them for the first time tonight!
Good quality food at a value price. We bring the bone % down when we add our own offal and other protein such as fish, lamb or beef
Excellent service beeen using these guys for about 2 years never let us down on delivery or value for money
Brilliant quality of product, excellent price. Good value and judging by the dogs reactions it tastes good too!
Fantastic service and great value and quality.Would recommend to anyone
Really good quality tripe, good product good communication and delivery
I have got 3 dogs and they all love this meat.
Mollie our 10 year old JRT started her new raw diet three days ago after taking delivery of the chicken mince with added offal. It's her first time eating Raw food, and she loves it bless her. It's easy to use and at a great price, which includes dilivery. Thanks. Will be ordering again soon!Regards Adrian.
Beef & Chicken Complete (5kgs) Chicken Mince & Veg (5kgs) Variety Box 10kgs for Working Dogs£27.00
Beef & Chicken Mix & Lamb/Chicken Complete 10kgs (22lbs) Variety Box Working Dog£29.00
Chicken Mince & Veg (5kgs) & Chicken, Bone & Offal (5kgs) Variety Box 10kgs for Working Dogs£26.00
Minced Chicken with bone, Carrot, Sweet Potato & Spinach 10kgs (22lb) 24 x Small blocks£23.50
Minced Chicken with bone, Carrot, Sweet Potato & Spinach 20kgs (44lb)£40.00
Pure Beef Mix (5kgs) Chicken Mince & Veg (5kgs) Variety Box 10kgs for Working Dogs£29.00
Beef & Chicken Mix 10kgs (22lb) 24 x Small Blocks - Working Dog£26.00
Boneless Duck (5kgs) & Turkey (5kgs) Variety Box 10kgs for Working Dogs£32.00
Frozen Whole Scad Fish 1kg (2.2lbs) Working Dog *ADD ON ITEM£3.40
Minced Chicken with Bone 100kgs (220lb) Working Dog£105.00
Minced Pure Green Beef Tripe 40kgs (88lb) Working Dog£93.00
Minced Chicken with Bone 80kgs (176lb) Working Dog£83.00
Minced Chicken with Bone 60kgs (132lb) Working Dog£69.00
Minced Chicken with bone 40kgs (88lb) Working Dog£55.00
Pure Beef 20kgs (44lb) Working Dog£54.00
Green TripeOur raw beef tripe is just that and nothing else.We take fresh whole English beef tripes and then mince, pack and freeze them, to keep our mince as pure and unprocessed as possible.Green tripe is a very nutritious food for dogs of all ages.Raw green tripe offers beneficial bacteria and enzymes. It has a desirable calcium:phosphorus ratio of 1:1. Green tripe's pH is acidic, the protein is 16.2%, and the fat is 12.1%. It also has the correct proportions of Omega-3 and Omega-6 fatty acids.Protein 16.2 g/100gFat 12.1 g/100gEnergy kcal 174 kcal/100gOne of the best constituents of raw green tripe is lactobacillus acidophilus. This is one of the intestinal bacteria that keep unwanted bacteria such as e-coli, salmonella and listeria from overpopulating and causing health problems.A balance of microflora in the gut is extremely important to maintaining good health.These probiotics help keep the animal's immune system in top shape.Digestive enzymes. The enzymes that help the ruminant digest its meal will give the pet the same benefit. Dogs and cats do not naturally produce amylase, so the nutrients present in vegetative matter are not readily available to them. Raw green tripe contains these digestive enzymes.It contains the following vitamins and minerals:Vitamin E, Riboflavin, Niacin, Folate, Vitamin B12, Pantothenic, Acid, Choline, Calcium, Iron, Magnesium, Phosphorus, Potassium, Sodium, Zinc, CopperManganese, Selenium


text:
The first glimpses of Benedict Cumberbatch playing Wikileaks founder Julian Assange have been released by DreamWorks Studios. The Sherlock star appears in the film, The Fifth Estate, which depicts the foundation and early days of the controversial website.
Cumberbatch acts alongside Inglourious Basterds star Daniel Brühl, who plays Wikileaks co-founder Daniel Domscheit-Berg. Domscheit-Berg, who later became WikiLeaks spokesman, separated from the website in 2010. Assange is currently residing in the Ecuadorian Embassy in London after facing extradition from the British government regarding an investigation for sexual assault.
The Fifth Estate is the work of West Wing screenwriter Josh Singer and is director Condon, who was also responsible for The Twilight Saga: Breaking Dawn. Condon said of the film, "It may be decades before we understand the full impact of WikiLeaks and how it's revolutionised the spread of information. So this film won't claim any long-view authority on its subject, or attempt any final judgment. We want to explore the complexities and challenges of transparency in the information age and, we hope, enliven and enrich the conversations WikiLeaks has already provoked."
Singer used Domscheit-Berg's 2011 book Inside WikiLeaks: My Time with Julian Assange at the World's Most Dangerous Website to inform the film's plot. The Fifth Estate will be released in US cinemas in mid-November.
Cumberbatch recently appeared in The Hobbit film as Necromancer, and will play the role its two sequels. He is involved in two other films out this year: Twelve Years a Slave set in 19th-century America, and JJ Abrams's new Star Trek sequel.


text:
Friday, September 28, 2007
Know Your Milton: Raccoons!
To See a Raccoon practice for the Circus, Click Here->
The raccoon (Procyon lotor) is a stocky mammal up to three feet in length and weighing between 8-20 pounds. Distinctive markings include a black mask over the eyes and heavily furred tail with black rings. Its fur is grizzled in appearance and coloration can vary from gray to black, although individuals with a somewhat yellow, "tawny" color are common in some areas. Raccoons have pointy, triangular ears and hand-like front paws. Breeding peaks in February and March, but can occur at any time from December to June. Litters of 1-7 "kits" are born after about 63 days. Young are weaned after 10-12 weeks, but can remain with the female as a family unit for up to one year.
Raccoons are found throughout Georgia in rural, suburban, and urban landscapes. They are typically found in habitats closely associated with water, including coastal marshes, swamps, rivers, lakes and streams. They also tend to favor habitats where mature hardwood trees are available. Raccoons are highly adaptable and their populations thrive in most parts of the state. They typically den in hollow trees, ground burrows, or brush piles, but will readily use human structures like a barn, an attic, or an abandoned building. Denned raccoons with young can often be heard "chattering" in the den. Raccoons are active throughout the year in Georgia, but may remain in their dens during extreme winter weather. They are considered nocturnal, but will readily forage during the day when local conditions allow. Raccoons are omnivorous and opportunistic. They feed on a variety of plant and animal matter including berries, fruits, seeds, and insects, as well as other invertebrates and small vertebrates.
As with all wildlife, raccoons should not be approached or handled by humans. One reason for leaving raccoons undisturbed is their susceptibility to numerous diseases including canine distemper and parvovirus, in addition to zoonotic diseases (humans can get from animals) such as rabies and raccoon roundworms. Even though raccoons may be carriers of rabies, not all raccoons have rabies. Typically, rabid raccoons will exhibit aimless wandering and lack of coordination, or they will exhibit aggressive behavior that can include attacks and self-mutilation.
Nuisance raccoons cause health concerns for humans and their pets. Most diseases are transferred only through direct contact. Simply being near a raccoon is not considered a risk. Pets should receive regular vaccinations from your veterinarian to reduce risk. Report any direct contact with your pets to your countys animal control office. Any human contact with raccoons should be reported to the county health department. If you observe an obviously aggressive animal, report this to your regional WRD office.
Because of their adaptability to different habitats and further development of formerly wild areas, raccoons often become a nuisance in urban and suburban areas, around rural homes and in recreation areas. One of the most common conflicts between raccoons and humans occurs when household pets are fed outside. Raccoons are attracted to pet foods and can often congregate in large numbers to take advantage of this easily obtained food source. Other raccoon / human conflicts occur when raccoons den in buildings, raid gardens, harass backyard chicken coops or visit garbage cans in search of food. Given raccoons adaptability to different food sources and their dexterity, eliminating outside food sources can be challenging.
Raccoons are relatively easily captured in cage-style traps baited with moist cat food. However, due to the fact that raccoons can carry rabies and the fact that relocated raccoons often exhibit poor survival in new areas, relocating nuisance raccoons is not an option. Nuisance problems are best dealt with by changing or removing food sources, or excluding raccoons from human structures and garbage containers. Raccoons should never be fed intentionally. Relief of nuisance problems can be alleviated through contract with a WRD permitted nuisance trapper or with a permit for lethal control from a WRD Game Management Office.
As with most furbearers, raccoon fur once was valuable to trappers and resulted in significant trapping pressure. Today their fur has little commercial value. However, they remain a popular game animal in the State of Georgia primarily for sport hunting. There are hunting and trapping seasons for raccoons, which occur from October through February.
Thanks to http://georgiawildlife.dnr.state.ga.us
Posted by Accessmilton Admin at Friday, September 28, 2007
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Plans for a so-called "bullet train" that backers say would carry passengers between Houston and Dallas in 90 minutes are expected to clear an early hurdle.
Federal officials on Wednesday are scheduled to announce if Texas and the private company behind the rail project can begin environmental reviews.
Texas Central Railway has given no cost estimates on the proposed 240-mile route.
The latest news from around North Texas.
Proponents tell the Houston Chronicle that they are expecting the go-ahead for starting the review process.
Backers say construction could begin as soon as 2016 and trains could start rolling by 2021.
Copyright AP - Associated Press


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DU's Shore brothers, Nutini visit local peewees
DU's Drew Shore, Nick Shore and Chris Nutini visited a split-squad peewee practice with the Colorado Thunderbirds and Littleton Hawks A Red on Tuesday night at South Suburban Ice Arena. The Shores' youngest brother, Baker, plays for the triple-A Thunderbirds, and Drew, Nick and Nutini grew up playing for the Hawks.
The Pioneers trio represent the three Littleton double-A national titles won by head coach Kent Murphy, who is now the Thunderbirds' head coach. Nutini was on the 2001 team — Colorado's first double-A national champion. Drew and Nick led the Hawks to the 2003 and 2005 national titles, respectively.
Also pictured is former DU defenseman Zach Blom, a Thunderbirds assistant coach and LHA co-director, and his father, Buddy, the former DU goalie who serves as the T-Birds' goalie coach. The T-Birds also are coached by former LHA star Kevin Fredrick and former Avalanche defenseman Curtis Leschyshyn.
Great staff, eh?
The LHA peewees are coached by Kevin Whalen, who was the bench boss last season for the Thunderbirds' U18 team.


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For the perfect fit and maximum performance at an affordable price, the Gavin Elite Road Cycling Shoes are the best choice! The fastening system features a micro adjustable buckle and two hook and loop straps for a comfortable and secure fit every ride. The uppers are made of synthetic microfiber leather and have mesh panels to encourage air circulation. The nylon fiberglass outsoles have air flow vents. These cycling shoes are compatible with Look, SPD, SPD-R and SPD-SL cleats.
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Dr. Anne C. Poinier reviews medical content for Healthwise, a nonprofit organization with a mission to help people make better health decisions. Dr. Poinier has been a board-certified general internist at St. Luke's Regional Medical Center in Boise, Idaho since 2001.
MD: University of Washington School of Medicine, Seattle, WA, 1998
Residency in Internal Medicine: University of Washington, Seattle, WA, 1998-2001
American Board of Internal Medicine
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Veterinarian Reviewed on June 20, 2012 by Paulina Nelega, RH
Posted in Uncategorized
Methylisothiazolinone or simply called MIT is classified as a preservative. It belongs to a group of isothiazolinones which are used in many personal care products such as shampoos and soaps. These chemicals have the amazing ability to control the growth of microbes in a solution. It may also be added to products to preserve its smell.
Methylisothiazolinone is used in many industries such as paper, fuels as well as in the mining industry. Although the chemicals that belong to the isothiazolinones are perfect in preserving products and in keeping them microbe free, they are however toxic to fish and the environment as well. Methylisothiazolinone is found to have caused many occupational illnesses and researchers have found this product to be an allergenic and a cytotoxic as well.
History and Origin
The use of isothiazolinones especially methylisothiazolinone in many industries is definitely indispensable. Its use has been widely accredited especially in the field of preservation and anti-fouling. The major setback with the use of this chemical is the effect of its use for environment and at the same time to humans who come in contact with isothiazolinones in many industries. There are also trace non-occupational hazards of isothiazolinones in the many products that we use in our homes, such as in air conditioning units, paper, adhesives and also in leave-on personal products and cosmetics.
Ancient Uses
The use of methylisothiazolinone was unheard of during the ancient times. Preservation of food however was already done to make harvested foods last throughout the season. Salt was the main preserving agent and it was usually used to preserve fish, meat, game, fruits and also some vegetables.
Modern Uses
Methylisothiazolinone is used in industries where microbial growth must be controlled over a water-containing solution. In personal care products, it has been effectively used in shampoos, soaps, liquid detergents and in cleaning solutions for the home. Methylisothiazolinone is also used for the production of paper; it is used to control slime development on production. It is found in adhesives that we use in the home and in industrial settings; it controls microbial development in these products.
There are still leave-on cosmetics that use methylisothiazolinone such as hand creams, moisturizing lotions and even make-up. Food labels and containers may also contain traces of methylisothiazolinone as well.
Side Effects
Methylisothiazolinone is found to be toxic in both animals and in humans. In many countries like Japan and Canada, this product along with its counterparts, are restricted to use. Thus, it would be best to check labels of personal care products for these chemicals along with other isothiazolinones.
If you have sensitive skin, it is best to consult a dermatologist regarding the ideal skin care products to use. If you wear makeup, it is always a very good habit to remove every trace of makeup before retiring at night. Never leave makeup on your face for an extended period of time.
If you work in an industry which uses isothiazolinones for preserving and preserving the smell of products, wear protective equipment to prevent direct contact with these chemicals. Always consult a medical professional for any contact injury with methylisothiazolinone at work.
Our Expert
Paulina Nelega, RH, has been in private practice as a Clinical Herbalist for over 15 years. She has developed and taught courses in herbal medicine, and her articles on health have appeared in numerous publications. She is very passionate about the healing power of nature. Ask Dr. Jan


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This is our B Arnold Plumber page. We have listed the full address of B Arnold, phone numbers and websites. B Arnold is in Enfield and can fix leaking pipes, burst pipes, install kitchens and showers and bathrooms. | [Edit Text]
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- Description
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Big on beauty and low on maintenance, this lovely basket is a sure way to make anyone smile.
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Well, it's clear now: The Gods hate the replacement refs. That probably was obvious enough before Monday night's catastrophe, before the Green Bay-Seattle finish that turned the NFL into a laughingstock once and for all. The Greek Gods had already sent down Herculean labors for the replacement referees -- fumbles that did not look like fumbles, pass interference temptations, screaming players and coaches -- and these replacement referees essentially failed every test.
But Monday night's ending, well, if that doesn't end this farce, then it's clear that the people who run the NFL have simply decided that they don't owe the fans, the players or anyone else legitimacy.
First, a quick recap of the play: Seattle trailed Green Bay by five with time for one last play. The Seahawks had the ball on the Green Bay 24. Seattle quarterback Russell Wilson dropped back, spun around, ran left and then threw a sort of mini-Hail Mary toward the left corner of the end zone.
Here's what followed, at least to the naked eye (and the many replay cameras):
One: Seattle receiver Golden Tate literally shoved down a Green Bay defensive back in one of the most blatant offensive pass interference penalties the world has ever seen. The replacement officials, who have and will call pass interference on ordinary lamp posts, somehow missed this.
Two: Green Bay defensive back M.D. Jennings jumped up with Tate and pulled the ball into his chest. There were numerous replays from numerous angles, but no perfect one. Still every bit of evidence suggested that Jennings caught the ball, pulled it to his chest and fell on top of Tate. Interception. Game over.
Three: Tate, meanwhile, was grabbing for the ball too. Again, the replays were not ideal, but it certainly seemed like Tate had just one hand on the ball and then was reaching his second hand in there. The rule is that if there is simultaneous possession, it goes to the offensive receiver. Nothing in the original viewing or the replays suggested, though, that this was simultaneous possession. Everything in the replays suggested that after Jennings landed with the ball, Tate wriggled his arms while they were on the ground in a bold effort to fool someone clueless enough to fall for it.
Four: Enter replacement officials!
Five: Two replacement officials ran over to look at the play. And at the same time, with comedic flair, one official waived his arms over his head, which appeared to signal "interception," while the other held his arms above his head, which appeared to signal "touchdown."
Five: Planets exploded, Jor-El sent his only son to Earth, Seahawks coach Pete Carroll was way too happy, NFL owners counted and pocketed another week of referee discounts, and Seattle somehow won the game.
You know, it's hard to remember a time when the NFL wasn't the biggest thing going in American sports. But there was such a time. There was a time in the not-so-ancient past when pro football was way behind baseball … and also behind boxing and horse racing and college football and perhaps track and field.
How did pro football take over America? There are great books on the subject, but I think you could probably reduce it to this: Pro football has managed in a perhaps unprecedented way to balance itself right on the American edge. And it has stayed there for 40 years.
I mean, it's RIGHT THERE on the brink. Look: The NFL is extraordinarily violent … but not so unchecked that people turn away in disgust.
Look: The NFL is extraordinarily random -- everyone concedes that penalties could be called on every play, footballs are spotted by sight and measured by chains, teams have so many players injured that they rarely can field the same team twice -- but not so random that it becomes too erratic to enjoy.
Look: The NFL is driven by gambling and vice -- point spreads, parlays, fantasy games, alcohol ads, erectile dysfunction ads, unspoken steroid use -- but not so much that we find it corrupt.
Look: The NFL is big-time television, constantly interrupted by commercials and stoppages and huddles and warnings, only a few minutes of action for every hour of broadcasting … but we still find it absolutely mesmerizing television. Last year, Sunday Night Football was the No. 1 show on television. Not in sports. All of television.
The NFL owners, curators, players … they've made a lot of harmful mistakes and done a lot of pea-brained things. The replacement player fiasco. The insistence that season ticket holders buy meaningless and stupid exhibition games at full price. The league's public fight with its former players who are living in great pain (or dying young) from what they say is the savagery of pro football. The way the league has handled -- or not handled -- the incredible dangers of concussions. Through it all, though, you would have to say that the NFL never lost middle America, never fell over the cliff. No, pro football managed to stay right on the edge -- dangerous but not perilous, chaotic but not out of control, hyped but not outrageous.
And then … these guys allowed this replacement referee fiasco to happen.
Before Monday night, you could say that these officials were slowly but surely destroying the rhythms, integrity and enjoyment of pro football. Slowly, at least. They made their dumb calls, yes -- 11-yard penalties, bizarre decisions on fumbles, pass interference calls for everybody!
They failed to take charge of games, yes. This is not entirely their fault, maybe not even mostly their fault. They are simply too inexperienced, too raw and too confused to hold the attention and respect of men who are playing and coaching a dangerous game under the most intense scrutiny in American sports. These coaches and players -- like the league itself -- are just on the edge, and having substitute teachers calling the games just isn't going to keep them calm.
And they made the games all but unwatchable. Reviews. Meetings. Conferences. More reviews. More meetings. Football has always walked that tightrope anyway … the game has so many interruptions already. Who doesn't kick the wall just a little bit when there's a commercial, then a kickoff, then ANOTHER commercial? But now these replacement referees, just desperately trying to keep their heads above water, have slowed the game down to 12th-grade chemistry class. You half expect one of them to start saying "Bueller? Bueller?" before finally telling us what the call is.
These things, I believe, and others have made the replacement referees a real danger to the NFL's balance. The NFL was on the edge in so many ways … the replacement referees pushed them over. For most of America, the game was ALMOST too dangerous before; the replacements make it more dangerous. The game was ALMOST too slow and plodding before; the replacement refs make it slower. The game was ALMOST too convoluted before; the replacement refs make it more convoluted. The NFL owners and executives were ALMOST too greedy and self-serving and dismissive of the fans before; the replacement refs make it all the more true.
This WAS the problem. But now, after Monday night, the NFL has a whole new problem. Because this was not subtle. This was in-your-face fraud. On Monday night -- in a perfect visual that had to be sent down from the Gods -- one of the league's most popular teams got jobbed by the sheer incompetence of the replacement refs. And this happened at the end of a generally disastrous night when those refs called 8,394 penalties (I don't have the box score in front of me, but that's how many I counted) and turned a tense football game into four-hour torture chamber.
I honestly cannot see how the NFL can let this stand. Then again, I have not been able to understand how the NFL has allowed this sporting travesty to go on for three weeks. When that last pass landed in Jennings' arms, when Tate tried to take it away, when one referee signaled interception and another signaled touchdown, I looked up to Olympus and thanked whichever of the Greek Gods set that up. It was said that Zeus turned Pandareus to stone for stealing the golden dog that had once guarded Zeus. Sure, it would have been good to see Roger Goodell turned to stone. But this was good, too.


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A table showing the education materials and courses available to the organisation via IT Academy.
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Posts Tagged 'williamsburg'
don't worry williamsburg, your seat is saved
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Better safe than sorry on Bedford Ave.
Because when you want to sit down, you need your chair.
Tagged as: Tags: Bedford, chair, williamsburg
cooking with kenny
Miss this face?
Kenny of Brick Oven Gallery and Kenny's Trattoria
Or at least the cavatelli with broccoli rabe and the most generous arugula salad this side of the Newtown Creek?
Then, you're in luck- Kenny is the 'guest chef' at Pinkerton wine bar – 263 North Sixth Street at Havemeyer St in Williamsburg. He will be cooking up a storm for the duration of The Feast of Our Lady of Mount Carmel (the pride of Williamsburg!) running from July 6th to July 17th. While you may be tempted by the drinks with the really long straws, the copious amounts of fried dough and the miraculously incorporated oreo cookies or the clams! peppers and onions! fried! dough! – do check out the feast for the tshirts, the really big chair that makes you look really small and 112 men carrying around a very large boat with a statue on it. But go see Kenny for food.
Tagged as: Tags: Giglio, Kenny's Trattoria, Our Lady of Mount Carmel, williamsburg
bumper to bumper
Brooklyn, June 29, 2011, 11:45 am: blue skies
Williamsburg Bridge: city-bound, bumper to bumper traffic
You should probably ride your bike today.
Tagged as: Tags: bicycle, brooklyn, williamsburg


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Saunders: The moral cliff
Much has been made of the fiscal cliff but little about the moral cliff. That is the ethics of our decisions and how they will impact our children and their children. In a recent CNBC interview Arthur Brooks, a social scientist, said, "We're stealing from our kids. We're doing something that's profoundly immoral to the future of our country." Will we have the moral fortitude of other generations? Almost gone now is the Greatest Generation forged by the Great Depression and WWII. Only at the end of their lives did I begin to appreciate what they went through and how they sacrificed for us. They leave a legacy of relentless resolve and dedication to make our lives better than theirs. Yet their sons and daughters are about to push the next generations off a cliff. We will be crushing our children with an unsustainable debt and trillions of dollars in unfunded liabilities. Is this really the morality of our generation?
Jesus said "For where your treasure is, there your heart will be also." So is our treasure in our entitlements or our children? Mr. President, Sen. Reid, Mr. Speaker, Congress, where is your treasure, your heart, your ethics?
Richard Saunders, Silverthorne
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