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WO1997015242A1 - Porous material product and process - Google PatentsPorous material product and process Download PDF
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- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
- B29C67/202—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising elimination of a solid or a liquid ingredient
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/0077—Special surfaces of prostheses, e.g. for improving ingrowth
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2210/00—Particular material properties of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
- A61F2210/0004—Particular material properties of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof bioabsorbable
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2240/00—Manufacturing or designing of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
- A61F2240/001—Designing or manufacturing processes
- B29L2031/00—Other particular articles
- B29L2031/753—Medical equipment; Accessories therefor
The present invention relates to a device, at least a portion of which is porous, for use as a prosthesis, treatment implement, and other utility, and a process of fabricating such device.
The applications and uses of synthetic biocompatible implements and devices adapted for implantation or installation in or on a human body have dramatically increased in recent years. Such implements and devices include soft tissue implants for use, for example, in breast augmentation, chin, nose, ear and other body part reconstruction and the like, nerve cuffs and scaffolds, lymphedema shunts, percutaneous skin and blood access devices, insulin cell producing implants and other cell sequestrating cage devices, artificial tendon and ligament and tendon and ligament repair prostheses, artificial heart and vascular prostheses, burn dressings, and drug infusing, releasing or delivery devices.
Oftentimes, devices of the type described above fail due to problems at the implant-tissue interface. As early as 1970, Homsey, recognized that if the implant size is in the order of centimeters, a "fibrocartilaginous" membrane or capsule isolates the implant from normal tissue. If the implant is perforated so that the interstices (pores and pore interconnections) are ofthe order of 1mm or less, the implant becomes woven with the tissue, rather than encapsulated as above (Homsey, C.A., 1970, J. Biomed. Mater. Res.. 4:341-356). Smooth-walled silicone breast implants fail in the order of silicone shell surrounding gel, were developed, but with mixed results. For the prostheses using a silicone shell, the polyurethane foam was mechanically fixed to the shell with silicone adhesive. However, the interface between the foam and shell was weak and oftentimes resulted in delamination, sometimes with leakage ofthe silicone gel into the surrounding tissue. For the prostheses not utilizing a silicone shell, the gel would typically leak or "bleed" through the polyurethane cover into the surrounding tissue. Such "contamination" of the surrounding tissue with the gel caused local inflammation and gel migration to distant organs. Also, because ofthe three-dimensional interlocking nature ofthe pores within the polyurethane foam, the relatively inelastic nature ofthe polyurethane, and the large ratio of ingrown tissue compared to the amount of material in the foam, a "Chinese handcuff' type situation (ingrown tissue locked with foam) was created with the tissue, making it very difficult to remove or change the prostheses. Further, polyurethanes, as a class, are biologically unstable and will chemically degrade, giving rise to structure breakdown, sometimes with severe inflammation. A recent concern with such chemical degradation is the potential for release of toluene diamine (TDA), a chemical which, even in small amounts, is known to cause cancer in laboratory animals.
Previous approaches to forming porous materials (for implants or other uses) have typically included use of bubble-40-60 percent due to this thick "fibrocartilaginous" membrane (capsule) which forms around the implant creating a hard, inelastic, and often painful feeling implant. This fibrous capsule also creates other problems around implants in general because it is composed mainly of dense compacted collagen, and fibroblasts, with little or no vascularity. This leads to isolation ofthe implant, the implant-capsule interface, and the capsule itself from the nutrient, metabolic, and cellular advantages of good blood supply, making the implant site more prone to infection, and the infections less amenable to treatment by natural resistance mechanisms and/or blood borne antibiotics.
Porous devices known under the trade names Ivalon Sponge (polyvinylchloride) and Ashley breast prosthesis (polyurethane) were created to allow tissue ingrowth into the pores within the implant. These devices were totally porous, sponge-like devices which didn't limit the tissue ingrowth into the pores or limit implant access to bodily fluids and, with nothing to stop or control such ingrowth or fluid access, poor quality ingrown tissue, with interior calcification and hardening, resulted. Such hardening is not only uncomfortable to the recipient but also unnatural in appearance and function.
In an attempt to solve some ofthe above problems, at least with breast prosthesis, polyurethane foam covered silicone rubber breast protheses, both with and without a forming technology, sintering of metal or polymer particles into a partially fused body, expansion of polymer melts or solutions (such as used to produce Gortex), processing fibers to produce fabric felts, velours, meshes or weaves, and replicating or duplicating the microstructure of carbonate animal skeletal material. See, for example, White, R.A., Weber, J.N. and White, E.W., "Replanineform: A New Process for Preparing Porous
Ceramic, Metal, and Polymer Prosthetic Materials," Science, Vol. 176, pp. 922-924; U.S. Patent No. 3,890,107; Leidner, J. et al., "A Novel Process for the Manufacturing of Porous Grafts: Process Description and Product Evaluation," Journal of Biomedical Materials Research. Vol. 17, pp. 229-247 (1983). Among the problems of using bubble technology to produce porous materials is the difficulty of separately controlling pore size, pore shape, and pore interconnections. Also, the resulting pores typically include shaφ edges and terminations which can cause accelerated inflammation and thus problems and/or discomfort when implanted. The sintering and polymer expansion approaches are limited to the use of only certain kinds of materials, typically metals for sintering and polytetrafluoroethylene for polymer expansion, and these may not be materials having the desired flexibility, resiliency, biocompatibility, or the like. The processing of fibers is limited because only materials which can be made into fibers can be used, and the resulting structure is basically two-dimensional. The replication of carbonate animal skeletal material, although suitable for some uses, requires milling ofthe material to the desired size and shape, and again the pore size and shape cannot be controlled. Two recently issued patents, Nos. 4,859,712 and 4,889,744, disclose the use of dissolvable particles initially placed on uncured silicone, curing the silicone, and then dissolving the particles to yield a silicone product having a puφortedly open-cell porous surface. The particles mentioned in both patents as the preferred solid soluble particles are crystalline sodium chloride (salt) and no other exemplary particles are identified. A number of problems or difficulties are present with the methods disclosed in the two patents including the difficulty of obtaining a completely open-cell structure since the salt particles are simply placed in the surface ofthe implant before curing, and then the implant is cured and the salt particles dissolved. Since many of the particles will not touch, a mostly closed-cell section is produced except at the surface layer. With this technique, it is also difficult, if not impossible, to premold the solid particles into predetermined desired shapes (since salt particles do not hold together and therefore cannot be molded), and the depth of the porous portion, and the size and shape of the structural interconnections surrounding the individual open cells cannot be controlled (since salt crystals can only be pressed into contact with one another but do not inherently stick together).
Since the treatment possible with the approaches disclosed in the above two patents is only at the surface and doesn't extend in a true three-dimensional direction, the fibrous capsule created after implantation has essentially the same thickness and density as with a smooth surfaced implant. A true three-dimensional unitary porous silicone rubber prosthesis has not been available until the technology ofthe present invention was developed.
The above and other objects, features and advantages ofthe invention will become apparent from a consideration of the following detailed description presented in connection with the accompanying drawings in which:
FIG. 1 shows a side, cross-sectional view of a container in which is deposited sugar mold material for making a porous material product, and an enlarged view of a portion of a solidified sugar mass, in accordance with the principles of the present invention: FIGS 2 A, 2B and 2C show fragmented, cross-sectional views of a sugar mass in a container, and resulting final porous products, respectively,
FIGS 3 A and 3B show an elevational, cross-sectional view of a container with sugar mold material and final product material, and an elevational, cross-sectional and fragmented view ofthe final product, respectively,
FIG 4 shows an enlarged cross-sectional, fragmented view of final product material which includes fiber fragments, in accordance with the present invention
FIGS 5 A, 5B, 5C and 5D show elevational, cross-sectional views of a mold container shown in the open position, two closed positions, suitable for use in accordance with the process ofthe present invention, and a final product, respectively,
FIG 6 shows a side, cross-sectional view of a product having top and bottom porous sections with a middle, nonporous section,
FIGS 7A 7B and 7C show cross-sectional views of a mold container with an implant model, a mold container filled with the final product material, and the resulting final product implant, respectively,
FIGS 8A, 8B, 8C and 8D show elevational, cross-sectional views of a mold container for constructing a mold form, the mold form with the final product material applied, and two versions of the final prosthesis, respectively, in accordance with the present invention, FIG 9 shows an elevational, cross-sectional and fragmented view of a prosthesis for use as a drug delivery implant,
FIG 10 is a side, cross-sectional view of a porous metal alloy product made in accordance with the present invention,
FIG 11 shows a cross-sectional and fragmented view of a doubly-porous prosthesis, with mold form still in place, made in accordance with the present invention,
FIG 12 shows a cross-sectional, fragmented view of a final porous product with a coating of material on the pore surfaces, made in accordance with the principles ofthe present invention, and
FIG 13 is a side, cross-sectional, fragmented view of two interlocking materials produced in accordance with the present invention
In carrying out the process of constructing porous or partially porous products in accordance with the present invention, a first step is simply to select the mold material for use in forming the selectively removable open-celled porous mold form (SRO-CPMF) from which the final product will be molded. Such mold material, advantageously, is readily available, inexpensive, and resistant to dissolution by the liquid form (or the dissolved or dispersion form) of final product material. Also, the mold material should be available in selectively sized and shaped particles which may readily adhere together (or be made to adhere together) to thereby assure a continuous and entire open-cell product when the mold material is removed or dissolved away. Finally, the mold material, when in the mold form, should be readily removable without significantly altering the final product (or product material) . This removal may be by dissolution by some solvent which does not significantly dissolve the final product material. Alternatively, the mold material may be melted (or burned) out ofthe final product material if the melting point (or burning point) ofthe mold material is below that ofthe final product material.
The final product material likewise would be selected to have the desired characteristics, for example, flexible and resilient for some applications in which case silicone rubber might be selected, and rigid in other applications in which case a polyester resin, epoxy resin, metal or metal alloy or ceramic may be selected
In the first example to be discussed, a partially porous device will be described, as well as a method of controlling the location of porous and nonporous sections. In this illustrative embodiment, sugar is selected as the mold material or SRO-CPMF, and silicone rubber is selected as the final product material. Sugar may be obtained with fairly uniform particle size and faceted crystal shapes and, if even greater uniformity of size is desired, then the particle size may be selected using standard screen-sizing techniques.
Once the desired particle size and size distribution for the sugar mold material are obtained, the sugar particles are mixed with de-ionized or purified water in a volume ratio of from 8 to 25 parts sugar to 1 part water. If a higher percentage of porosity in the final product is desired, then more water is added to the mixture to produce greater surface contact and fusing ofthe sugar particles, and this, in turn, produces more numerous and larger pore interconnections. A lower percentage of porosity in the final product is achieved by using less water, thus resulting in less contact and more space between the SRO-CPMF particles. If a larger pore size in the final product is desired, a larger particle size is chosen. Conversely, if a smaller pore size in the final product is desired, a smaller particle size is chosen.
The sugar and water are thoroughly mixed until all ofthe sugar particles have been contacted by the water and to some extent partially dissolved resulting in a saturated sugar solution (no more dissolution can take place). When the desired consistency is reached and the mixture is stabilized, the resulting moist semi-solid mass (moldable mass) may be molded into any desired shape by placing it in a pre-shaped mold and allowing it to solidify into the mold form, i.e., allowing or causing the water within the mold form to evaporate and the sugar n solution to recrystallize and precipitate on and between the sugar particles. FIG. I shows a cross-sectional view of a conventional cylindrically- shaped container 4 in which is deposited a moistened mass of sugar 8 Section 12 ofthe sugar mass represents a magnified portion of the sugar granules 20, with the voids 16 between the granules.
Solidification ofthe moldable mass into the SRO-CPMF may be accelerated by supplying dry air (which may be heated) to the mass, for example. Freezing, freeze drying or vacuum desiccation, with or without added heat, may also be utilized to cause the mass to solidify. Enlarged view 12 ofthe SRO-CPMF shows the sugar granules or particles 20 fused together, leaving voids 16 between the particles.
After solidification, the sugar mold form may either be left in place in the container 4 (FIG 1) or removed from the container 4 (as will be the case in the FIG. 3 description hereafter), depending on the nature ofthe final product desired. For example, by leaving the sugar mold form in the container 4, the mass will maintain contact with and adhere to the container walls 24 (FIG. 2 A) so that supply ofthe final product material to the mold form (to be described momentarily) will result in a porous surface 28 in the final product (FIG. 2B), with the surface pores 30 being formed by the sugar particles 26 ofthe mold form (FIG. 2A) in contact with the Container wall 24. On the other hand, if the sugar mold form 8 is removed from the container (or the adherent surface at the container wall is eliminated) and the final product then supplied to the mass for example, as it is held in a larger container 38 (FIG. 3 A), the surface exterior 40 (FIG 3B) ofthe final product (covering the sugar mold form) will not have pores. FIG. 3B shows this nonporous surface area and section 40, with a porous interior 42; the thickness of this nonporous section 40 will depend upon the quantity of final product material applied to the outside ofthe mold form.
Another illustrative method for forming the SRO-CPMF involves placing pure sugar particles ofthe desired size in a metal container and then heating the particles slowly to slightly below or just at the sugar melting point. While this is being done, the sugar particles are compressed and forced to contact each other, and then the mass is allowed to cool. The more the sugar particles are compressed together, the more numerous and larger will be the size ofthe particle connections, the more dense will be the SRO-CPMF, and the greater will be the percentage porosity ofthe porous portion ofthe final product, and vice versa. After cooling, the mold form may either be removed from the container or left in contact with the container as discussed above. After the sugar mold form is completed, a medical grade silicone rubber is catalyzed, mixed and de-bubbled in a conventional manner to achieve a liquid state and to prepare the silicone rubber for subsequent polymerization, i.e., conversion from liquid to solid state. The prepared, catalyzed silicone rubber is then forced into and through the interstices or pores ofthe sugar mold form, for example by pressure application to the silicone rubber, vacuum application to the mold form, gravity flow, mechanical agitation or a combination of these techniques, all of which are well-known. The thickness ofthe porous portion ofthe final product can be less than or equal to the thickness ofthe SRO- CPMF. This can be specifically controlled by controlling the depth of penetration into the SRO-CPMF ofthe liquid form ofthe final product material. If the liquid is forced to completely penetrate the mold form, the specific thickness ofthe SRO-CPMF itself can be used to control the thickness ofthe porous portion ofthe device.
Following supply of liquid silicone rubber to the mold form, the silicone rubber is allowed (or caused) to polymerize after which the sugar mold form is dissolved by a suitable solvent (in this case de-ionized water) and agitation. What is left after this step is the desired silicone rubber final product. A number of washings may be required to completely remove all ofthe residual sugar and ultrasonic water baths or other agitation is especially effective to do this. Also, hot de-ionized water or steam rinses could be utilized, after which the final product would be dried. If the combined structure of the SRO-CPMF and final product material was developed by removing the mold form from the container before applying the final product material to the mold form (FIG. 3 A), then a coating of final product material would surround the mold form resulting in a nonporous covering 40 so that there would be no access for the solvent to reach and dissolve the mold form 8 (FIG. 3A) . In this case, a small portion ofthe final product material would be removed at a surface location to allow access ofthe water solution to the interior. Alternately, needle penetration ofthe solid product material 40 could provide the desired access for the water solution, and removal ofthe dissolved sugar.
The thickness and shape of a nonporous surface portion of a final product can be readily adjusted by standard molding or injection molding die techniques, such as by selecting an appropriately sized and shaped container in which to place the mold form and then filling the container or mold with the unpolymerized silicone rubber. If the SRO- CPMF occupies only a small volume of the container, then the thickness of the non¬ porous portion ofthe final product will be great. The size and shape ofthe non-porous portion ofthe final product is determined by the size and shape ofthe container in which the mold form is placed less the size and shape ofthe mold form placed in the container. The shape and the amount of the porous portion of the final product will be determined by the shape and the portion ofthe mold form filled with the final product material. Any portion ofthe mold form not filled with the final product material will result in a void 142 in the final product (see FIGS. 8C and 8D) . The position ofthe porous portion relative to the non-porous portion ofthe final product will be determined by the placement ofthe mold form within the mold.
Except in a case to be described later (where a gas is forced through the mold form), one portion ofthe surface ofthe final product material will be non-porous. This portion corresponds to the location of introduction ofthe liquid form ofthe final product material into the mold form. By controlling the adherence of the mold form to the container or mold surfaces, the completeness of penetration ofthe liquid form into the mold foπn, and by controlling which surface area and the size of that surface area at which the liquid form ofthe final product material is introduced into the mold form, the location ofthe opened-cell surfaces and the location ofthe non-porous surfaces may be controlled. For example, a product made into a sheet may be entirely porous on the lower surface and non-porous on the upper surface. As an example, using the adherent container wall 4 to the mold form 8 in FIG. 1, this would be done by introducing the final product material to completely penetrate the mold form 8 on its entire upper surface, keeping the lower surface ofthe mold form adherent to the container walls. Alternatively, the final product material could be applied to penetrate only partway into the mold form. Either example results in a partially porous final product (FIG. 2C) with a nonporous upper surface 32, and a porous portion 34, with porous surfaces on the sides and bottom of the porous portion 34. However, if the final product material is introduced from the side, with an otherwise adherent (to all the container walls) mold form within the rest ofthe mold, the upper and lower surfaces of the sheet, as well as the sides where the liquid is not introduced will be porous. In this manner, the surfaces ofthe porous portions versus non¬ porous surface portions ofthe device can be controlled.
The final silicone rubber product which is at least partially porous is cured (polymerized), for example, in a drying oven for 15 minutes to 1 hour at a temperature ranging between 275 degrees F. and 425 degrees F., depending upon the specific silicone rubber used. The final product can be further formed or sculpted by cutting or adding to the product or by gluing other solid or porous silicone rubber parts or materials. However, the advantage ofthe method ofthe present invention is that rarely would one need to cut, glue, sculpt or add to the final product, since the variables between the porous and non-porous portions can be separately controlled. Cutting, gluing and sculpting, etc. also add interfaces and irregularities, stress risers and contour defects. In the method ofthe present invention, the porous and the non-porous portions ofthe device can be unitary, without interfaces, defects or contour irregularities. Standard packaging and sterilization procedures can then be performed if desired.
With the above-described process for forming open-cell porous products, complex shapes, forms and sizes may be readily fabricated. Also, there is no limitation as to the location ofthe porous portions ofthe product as there is with prior art methods.
A second example ofthe present invention will now be described in which the pore size ofthe porous portion ofthe final product will vary, initially, small particles of sugar (e.g., 50-75μ) are placed in a container to a depth of, for example, 0.2mm. Another size range of particles of sugar (e.g., 100-150μ) are then placed to another specified depth, say
0.3mm, over the first layer. This is continued until a final layer is added, say 200-300μ particles size, for a depth of 0.6mm. The SRO-CPMF particles in the container are then made to stick together, either by adding a saturated solution of sugar to all ofthe particles and draining it off the bottom by vacuum, or by exposing the container and graduated sized particles to near 100 percent humidity for 15 minutes to 4 hours, and then allowing the SRO-CPMF to dry (harden) . Altematively, the particles may be heated just to the melting point, compacted and cooled as described previously. The SRO-CPMF is then filled with the liquid form of the final product material as previously described—here silicone rubber. The resultant product is a partially porous device where the porosity varies selectively or continuously as desired, from one area to another. This is illustrated in FIG. 3B where the pore size varies from smaller to larger in the direction away from the nonporous section 40.
With the above-described method, many useful devices have been produced, such as vascular graft prostheses made from medical grade silicone rubber, Biomer, and Biolon (medical grade polyurethanes). The blood-facing surface of vascular devices have been constructed as above with pore sizes of 25μ, 50μi, 75μ and lOOμ. The porosity through the rest ofthe product may range from 30μ to 300μ, with a wall thickness 1/2 to 2mm. Cell cultures of endothelial and smooth muscle cells have been grown on the blood-facing surface ofthe device, where the porosity assists the attachment and, subsequently during implantation, the porosity adds to the nutrition of these cells during and after the ingrowth of tissue and neovascularity.
With larger pore sizes (50A to 100A) on the blood-facing surface of vascular grafts, pre-clotting the graft is necessary. After tissue ingrowth, the neovascularity may support neointimal cellular regeneration on the blood-facing surface ofthe device with or without cell culture seeding. The vascular prostheses described above may be implanted into subcutaneous or intramuscular positions. After the prosthesis walls become filled with tissue (from several minutes [pre-clotting] to several days [cell seeding] to several weeks [tissue ingrowth] depending on the type of tissue desired) , the prosthesis may be removed from its position and transplanted as a composite (composed of two types of material—tissue and polymer) graft into the recipient site, in this case a blood vessel. In this way, a vascular graft composed of tissue (as well as polymer) can be used as a live autogenous graft without creating the donor site morbidity of sacrificing a blood vessel. In a similar fashion, many types of tissue may be transplanted including bone marrow, liver, pancreas, collagen, or neovascularity or any tissue or cell culture which can be made to grow into the porosity ofthe implant.
A third example of the invention involves the use of fibers disposed within, or within and extending from, the porous section of the final product, for reinforcing or changing the characteristics ofthe porosity ofthe final product. The construction of such a final product will now be described.
After mixing the sugar moldable mass, as in the first example (see FIG. 1) , commercially available fiberglass or carbon graphite fibers are cut to the desired length, for example, 1cm., and mixed randomly with the moldable mass. The moldable mass is then placed in a container as before and allowed to solidify, forming the SRO-CPMF. For any given fiber, part ofthe fiber is within the sugar, either resting on a particle which has been partially dissolved and subsequently has some additional sugar deposited and recrystallized on its surface, or within sugar deposited and solidified at the particle surface and or the particle connection. Also for any given fiber, part ofthe fiber may not be in contact with sugar but rather simply extend into the voids ofthe SRO-CPMF. If a flexible reinforced porous section is desired in the final product, final product material, such as silicone rubber is selected. If a rigid final product is desired, polyester or epoxy resin, is introduced into the voids ofthe SRO-CPMF as previously described. The part ofthe fiber which is exposed within the void becomes coated and incoφorated within the matrix of the final product material. The sugar ofthe SRO-CPMF is then dissolved so that that part of the fiber 41 (FIG. 4) within the sugar becomes exposed within voids 43 of the final device 45— these exposed fibers can be ingrown by and fixed to tissue after implantation.
The proportion of fibers mixed into the SRO-CPMF may be varied greatly depending on the stickiness availed to the particles within the SRO-CPMF (either inherently or by the binding medium used), and the wetability, diameter, and stiffness of the fiber itself. If the fiber to moldable mass particle ratio becomes too great, the moldable mass particles become non-adherent to each other and the interconnecting open- celled nature ofthe SRO-CPMF breaks down, i.e., it can no longer be used as a porous mold form.
The length of the fibers used can also vary greatly. They can be oriented, pre- stretched or pre- woven, and placed within the container before the introduction ofthe moldable mass to thereby fix their position, orientation, etc. within the SRO-CPMF, and thus within the final product. The fibers can also be disposed to extend out ofthe SRO- CPMF, and thus out ofthe voids ofthe final product and into non-porous portions or outside the final product itself.
Similarly, a medical grade Dacron mesh (hole size about 1mm) may be formed into a cylinder, for example, having a diameter about 2mm less than the diameter ofthe inside walls of a container in which it is placed. After placement in the container, a moldable mass is placed in the container about and within the mesh cylinder, compacted, and allowed to solidify. This results in the mesh resting 1mm from the container wall within its circumference and within the SRO-CPMF, with sugar particles and sugar particle connections being in continuity on each side and through the mesh. The SRO-CPMF is then removed and placed into another container, for example about 1mm larger in diameter than the SRO-CPMF. Final product material, such as catalyzed liquid silicone rubber, is then forced about and into the SRO-CPMF to a depth of, for example, 2mm and allowed to solidify (polymerize). The SRO-CPMF is then dissolved as described above and the ends ofthe tube are cut off. The resulting prosthesis is inverted (turned inside out) yielding a device which is smooth and nonporous to a depth of l/2mm on the inside, with a porous section to a depth of 2mm on the outside. The central portion of the porous section is reinforced circumferentially by Dacron mesh, but with the porous section positioned on both sides and continuous through the mesh. The device described above has been used as a percutaneous cuff prosthesis for artificial heart drive lines; it is slid over and glued to the lines at their exit point through the skin and this allows tissue ingrowth and fixation at and below the skin, similar reinforced and fiber-modified porous prostheses have been made as vascular prostheses from medical grade blood compatible polyurethanes. In the earlier example in which the sugar SRO-CPMF mold material was removed from the container before applying the liquid silicone rubber, one ofthe options for the final product was to make it porous on the inside and nonporous on the outside (FIGS. 3 A and 3B). However, in many biomaterial uses, it is desirable to have a porous section on the outside and h nonporous section on the inside, in various shapes and ratios. An example ofthe use for such a final product is a dorsal nasal augmentation implant, and the process for fabricating such a final product (as well as similar final products) will next be described.
The first step in the process is to form a positive model in the exact size and shape ofthe desired final implant, made from substantially any material, although the clay-like thermoplastic material known as Sculpey Modeling Compound has proven to be most satisfactory. Such material is formed and sculpted by hand or with molding tools into the desired shape and then solidified by heating the material to 300 degrees F. for about 15 to 20 minutes. A single positive model may be used to fabricate a number of SRO-CPMF molds and therefore a number of final products, and the thickness, position and shape of the porous versus non-porous sections may be controlled.
The positive model is then placed in a hinged rectangular container 44 made of polyethylene (FIG. 5A), in one half of which is placed the mold material for the SRO- CPMF 48, such as sugar moldable mass. The positive model 52 (in this case a nose implant) is then pressed partway into the mold material 48 so that only its top (concave) surface is exposed. A thin layer of polyethylene sheeting or similar non-adhering material
56 is then placed over the mold material 48 and positive model 52 The other half of the hinged container is then filled (or overfilled) with sugar moldable mass 60 after which the container is closed, as shown in FIG. 5B, so that the moldable mass 60 is forced tightly over the sheeting 56 to conform to the shape ofthe exposed surface ofthe positive model 52. The mold material 48 and 60 is then allowed to dry (solidify) and the two halves of the hinged container 44 are reopened to allow removal ofthe sheeting 56 and the positive model 52 to leave the SRO-CPMF 48 and 60 in place in the container. Alternatively, the hinged container 144 could be first carefully opened, and the sheeting 56 and model 52 removed to allow drying ofthe moldable mass into the SRO-CPMF. A medical grade elastomer such as RTV silicone rubber is then forced into the mold form 48 and 60 to a depth equal to the desired thickness ofthe porous surface area ofthe final product. Silicone rubber is also placed in the void in the mold material 48 and 60 left by the positive model 52 and then the container 44 is again closed, as shown in FIG. 5C. The silicone rubber is allowed to polymerize while in the mold 48 and 60 of FIG. 5C, after which the container 44 is opened, the mold form dissolved, and the final product implant removed to form a silicone rubber nasal implant having a solid interior 64 and a porous outside surface area 68 in FIG. 5D.
In addition to the above-described process for forming a nasal implant or similar final product, conventional injection molding techniques are also effective in forming with the SRO-CPMF, by sintering sugar or other removable materials with heat and pressure in dies and molds in the desired shapes and with the desired voids or models to create the voids. The final product material, i.e., silicone rubber, is then pressure injected into the voids and into the mold form to the desired depth, with the same molds or dies used in forming the mold form or other dies or molds as needed. The resultant device using either process is a partially porous final product in which the locations and thicknesses ofthe porous section and the solid nonporous core and/or voids have been effectively controlled.
A more viscous mass can be made by using com syrup rather than water as the sugar binding dissolution medium and this will provide larger particle contacting in the mold form and therefore larger pore interconnections in the final product. The viscosity ofthe final product material will also affect the porosity ofthe final product when solidified if a thick viscous silicone rubber solution is used, for example, then larger pores will be produced in the final silicone rubber product since the more viscous unpolymerized silicone rubber will contact the SRO-CPMF particles over less surface area to effect incomplete surface molding. Also the pores will be smoother and more rounded as will be the pore interconnections. A doubly porous membrane (porous on each side but separated by an impermeable membrane) can be formed as in the steps just described for the nose implant. Here, the process is essentially the same except the positive model 52 (FIGS. 5 A and 5B) is eliminated; rather, the two halves ofthe hinged container are closed over the nonadherent sheeting 56, causing the two opposing surfaces ofthe moldable mass material 48 and 60 (separated by sheeting 56) to conform to each other. The hinged container 44 is then opened, the sheeting 56 removed, and the mold materials 48 and 60 allowed to solidify. The final product material is then placed between the two mold material 48 and 60 and then forced thereinto to the depth desired. Upon curing, a final product as in FIG. 6 of a nonporous membrane 65 with two porous surfaces 67 and 69 is produced. The thickness ofthe non-porous membrane 65 can be controlled by controlling the thickness ofthe non¬ adherent sheeting 56 and the degree to which the two opposing surfaces of the SRO- CPMF are forced together. Complex shapes and implements such as tubes and extemal surfacing for use in artificial hearts and vessels, porous on one or both sides, have been created in a similar manner utilizing silicone and biocompatible polyurethanes. Another example of a partially porous device made in accordance with the present invention is a breast implant. The beginning positive solid model, for example, polymethylmethacrylate formed with the desired curvatures and dimensions by machining or other suitable forming techniques, is polished and cleaned so that there is no contamination. Then, as with the formation of the nose-bridge implant, a hinged rectangular container 74 (FIG. 7 A) somewhat larger than the positive model 82 is filled with the sugar moldable mass 78 and 80 on each side. The polymethylmethacrylate breast implant model 82 is then pressed partway into the moldable material 78, in one half of the container so that the upper convex surface of the model is exposed. A thin layer of polyethylene sheeting 86 or other thin, non-adhering sheeting material is then placed over the model and the container 74 is closed tightly over the polyethylene sheeting. The moldable mass 78 and 80 is then allowed or caused to solidify as in the previous examples, after which the container 74 is opened and the model 82 and the sheeting 86 removed. A medical grade elastomer 90 (FIG. 7B) is then forced into the SRO-CPMF 78 and 80 to a depth equal to the desired thickness of the porous coating of the resulting final product (any excess is drained off, depending on the desired thickness ofthe nonporous portion), after which the parts of the container 74 are again closed tightly and the elastomer is allowed to polymerize. Additional coats of polymer may be applied to the inside ofthe SRO-CPMF to build up the nonporous shell thickness ofthe final product to the desired specifications. (A small hole must be left at some location if introduction of additional liquid form ofthe final product material into the void and onto and into the surfaces of the mold forms 78 and 80 created by model 82, as will be discussed momentarily, is needed.) The layers may be added before final polymerization, so that there may be no interfaces between the porous and nonporous portions or between the nonporous portions ofthe device.
The container 74 is again opened and the mold forms 78 and 80 are dissolved from the elastomer 90 by multiple washings, etc. The resultant breast implant device seen in
FIG. 7C is partially porous, having a predetermined thickness of porosity on the entire outside surface 94, a next interior layer of non-porous elastomer 98, and an interior void 102. The void may be left or later filled with some type of material to provide a breast implant with the desired feel, malleability and function. For example, the void 102 might be filled with a normal saline solution to yield a saline-filled breast prosthesis. The void
102 might also be filled or partially filled with a semi-solid such as a partially cross-linked silicone elastomer creating a silicone gel-filled implant. Finally, the void 102 could be filled with a catalyzed unpolymerized elastomer and allowed to polymerize and fully cross¬ link to create a rubbery, nonporous form with a porous covering. For some applications, it might be necessary to leave the void or to fill the void with a gas such as air.
Another specific illustrative embodiment ofthe method ofthe present invention for making a breast implant involves use of a two-part polyethylene mold 114 (FIG. 8 A) defining a cavity 118 having an oval cross-section, into which is placed the sugar moldable mass 122. Also disposed to extend from the mold form 122 through an opening in the mold 1 14 is a handle 126 made of stainless steel or other stable, corrosive resistant material. After forming, the SRO-CPMF 122 with attached handle 126 is removed from the mold 114.
Alternatively, to prepare the SRO-CPMF 122 of FIGS. 8A and 2B, the polymethylmethacrylate model 82 of FIG. 7 A as fixed with stainless steel handle 126, as in FIG. 8 A, may be used by slightly roughening and/or coating the surface ofthe model with com syrup to encourage adherence, and then spraying the surface with specific sized sugar particles under air pressure,, intimately mixed with a small amount of de-ionized water (in a manner similar to mixing gunite cement). The surface moistened sugar particles, upon striking the model surface 82, adhere to the model and to each other. The thickness ofthe layer of particles can be controlled to produce a desired thickness sugar
SRO-CPMF shell on the outside ofthe model 82. This sugar shell would then be allowed to dry to form the SRO-CPMF as previously described in FIGS. 8 A and 8B.
In either example above-described, the mold form is dipped into a medical grade silicone dispersion, by holding onto the handle 126 by hand. Vacuum application to the mold form 122 during or immediately after dipping can increase the depth of penetration ofthe silicone dispersion and eliminate bubbles and coating irregularities within the mold form. The mold form can be redipped into the silicone dispersion, after drying, from two to six times, depending on the desired thickness ofthe silicone shell being formed. The first one or two times the mold form 122 is dipped into the dispersion, the silicone flows into the voids in the mold form to develop what will ultimately be the porous portion of the device 138 (FIGS. 8C and 8D). The subsequent dipping ofthe mold form 122 will simply add nonporous layers 134 (FIGS. 8C and 8D) about the mold form. The thickness ofthe porous portion in the first example may be controlled by controlling the viscosity of the silicone dispersion and the amount of time and pressure or vacuum application during or shortly after the initial coats, which in turn determines the extent of penetration of dispersion into the mold form 122 and in the second example by controlling the thickness ofthe SRO-CPMF shell on the polymethylmethacrylate model 82.
After conclusion ofthe dipping steps, the silicone dispersion is vulcanized in an oven at, for example, 275 degrees F. for about one hour. Then a small (1-1/2 to 2 cm) hole 130 (FIG. 8B) is cut into the nonporous silicone covering around the dipping handle and then hot, de-ionized water is applied to the hole to reach and dissolve the SRO-CPMF material 122. Multiple washings may be required for this. The resulting silicone device consists of a shell whose outer surface 134 (FIG. 8C) is nonporous and whose inner surface 138 is porous. The positions ofthe nonporous and porous surfaces are reversed, however, by inverting the device through the hole 130 (FIG. 8D) formed to allow entry of hot water to dissolve the mold form 122, so that the porous portion 138 (FIG. 8D) of the device is now on the outside and the nonporous portion 134 (FIG. 8D) is on the inside, of course, a void or cavity 142 is still present in either device in FIG. 8C or 8D. To close the hole or opening 130, a small solid silicone patch 146 is glued with a medical grade silicone adhesive (or a patch of unvulcanized silicone rubber is vulcanized) in place over the opening. Of course, the outer patch surface 146 could be made either porous or nonporous depending upon the need. Also, conventional self-sealing valves could be included in the patch 146 so that previously described materials could be inserted into the void 142 at any time.
Another example ofthe use ofthe present invention involves utilizing the SRO- CPMF particles 150 (FIG. 9) within the final product material 152 by leaving at least some of the SRO-CPMF material in the final product to be dissolved over time, after implantation of the product in a person's body. In effect, the device becomes a drug delivery system for implantation in which the SRO-CPMF material consists of or includes drugs to be delivered in or on the human body. Examples of such drugs which might be included in a device during fabrication are gentamicin, tetracycline or cephalosporin crystals, but many other drugs available or drugs which can be disposed in crystalline form could also be used. Most drugs such as antibiotics, which are usually supplied in a powder form, would be dissolved and recrystallized into larger crystals. Depending on their inherent stickiness and heat stability, the crystals would then be partially dissolved and mixed and formed as a moldable mass or heated and compacted, to be used as the
SRO-CPMF as described for sugar. (A filler medium such as dextrose crystals can be mbced with the drug to get a smaller concentration of drug if needed.) Altematively, the crystals can be bound together with a neutral, non-drug interacting, biologically compatible binding medium, such as a concentrated dextrose solution in a ratio of 1 part saturated dextrose solution to between 4 and 40 parts drug crystal. Still another alternative is to dissolve or suspend the drug particles in powder form in the dextrose solution and then use this solution to coat other particles, such as another drug or dextrose crystals to form a SRO-CPMF with precipitated dextrose and drug particles on the surface. The dissolved or suspended drug within the dextrose solution may also be recrystallized, sized and made into a SRO-CPMF itself as in the previous examples of sugar SRO-CPMF. Specifically, an example of such a combination would be the dissolution of gentamicin crystals in a pharmaceutically pure saturated dextrose (sugar) solution, recrystallization and molding of these particles into a SRO-CPMF into which a silicone or other final product material is then placed. Differing concentrations of drug in different layers (in the same manner in which graduated sizes of particles are used in making a SRO-CPMF as in FIG. 3B) or different drugs in different layers may be produced within the SRO-CPMF mold material so that a different concentration of a certain drug, or a different drug will be encountered as ingrowth proceeds depending on the mechanism used by the body for removing the selected SRO-CPMF. As indicated, the drug or drug infiltrated mass may be used as the moldable mass for the SRO-CPMF, and a biologically compatible material, such as Medical Grade Silicone Rubber, used as the final product material. An RTV (room temperature vulcanizing) silicone is the preferred material for the final product so that the heat required for other forms of silicone won't be needed—such heat polymerization might otherwise denature or alter the active form of the drug. Altematively, a polyvinyl alcohol or polyglycolic or polylactic acid, or other absorbable final product material, might be used. To insure sterility, the fabrication ofthe SRO-CPMF is done under sterile conditions (all materials and appliances of fabrication are sterilized and the drug is supplied as sterile), or altematively, the device is fabricated under "clean room" conditions and the device sterilized by accepted techniques which do not alter the bio-activity of the drug. The device is then implanted in or placed on the human body, or into a body cavity, to allow tissue to grow into or fluids to penetrate, so that the body will passively and/or actively dissolve the SRO-CPMF to cause release ofthe drug. Again, the prevention ofthe thick capsule formation and the lack of isolation of the vascularity from the implant, characteristics which can be built into the porous portion ofthe device with the above- described methods, is an important key to the success of such an implanted device. By controlling the size of the implant, the amount of surface area of porosity exposed for passive dissolution or tissue ingrowth, the size of the pores, the size , of the pore interconnections, the concentration of the drug in the SRO-CPMF, the water-soluble versus fat soluble form of the drug, and the site of implantation, control of the pharmacokinetics are made possible. Also, a combined device where drugs are incoφorated into both the SRO-CPMF and the final product material resulting in a biphasic adsoφtion can be made by physically mixing the drug particles or using concentrated drug solutions and mixing then with the final product material and processing them as described above.
Another example of the use of the present invention involves production of a porous metal or metallic alloy device 154 (FIG. 10) , which in this example includes a nonporous section 156 and a porous section 158, for use in or on the human body as an electrode or battery plate, etc. To produce metallic partially porous devices, the sugar SRO-CPMF is first vacuum-impregnated with wax. The SRO-CPMF is then removed by dissolution and dried. A conventional ceramic refractory material, taking the place ofthe SRO-CPMF, is then vacuum impregnated into the wax. The metal, such as silver, gold, Vitallum or other castable metals are then heated to their molten phase and cast into the negative wax replica ofthe SRO-CPMF made by ceramic refractory material, by standard centrifugal casting techniques taking the place ofthe wax This creates the same porous form as would have resulted if silicone rubber had been introduced into the SRO-CPMF as described earlier, but out of metal.
To create ceramic partially porous devices, the SRO-CPMF is vacuum impregnated with wax as above, the SRO-CPMF dissolved, and the wax dried. A concentrated suspension of fine particle-sized (5mm) ceramic, e.g., «-alumina, is then vibrated into the pores ofthe wax open-cell porous mold form, and the ceramic is allowed to dry. The combination ofthe wax mold form and ceramic are then heated to about 400 degrees C. and the wax allowed to melt and/or bum off. The ceramic is then sintered at 1650-1700 degrees C. The porosity this time is the negative replica ofthe SRO-CPMF, with the sintered ceramic essentially resulting in a duplicate ofthe SRO-CPMF. With the above type construction techniques with sugars, waxes, refractories and other selectively removable materials serving as the SRO-CPMF or filling the spaces between the SRO-CPMF, positive or negative copies ofthe SRO-CPMF can be created. All of the other previously described control techniques as to porous and non-porous portions, size and position ofthe open-cell surface area, etc. are applicable to producing the metallic or ceramic devices described. These devices, as already mentioned, could be used in a variety of situations where large surface area exposure ofthe device is desired.
Another example of the use of the method of the present invention involves construction of a device as with any ofthe previous examples but adapted for use as a dialysis device or a blood oxygenation device. These devices utilize a doubly porous membrane, such as illustrated in FIG. 11. Mold form material 164 is created as described with any ofthe above methods. The liquid phase final product material (illustratively RTV silicone rubber) is then forced into the interstices ofthe mold form 164. Then, most of the silicone rubber is forced out ofthe interstices ofthe mold form by a liquid or gas, such as compressed nitrogen gas, leaving the mold form with a very thin coat ofthe silicone rubber 162. This reproduces the open-celled structure on the side ofthe silicone rubber coat or membrane, opposite the location ofthe mold form material— forms a secondary porosity 160 (see FIG. 1 1). The next step in the process, as described earlier, is to cure or polymerize the silicone rubber 162 and to dissolve out the mold form material 164 creating the primary porosity (where the mold form material was) . It is helpful to use some kind of surfactant, such as a weak soap solution, in both the solution dissolving out the mold form material and on the secondary porosity side to prevent adherence ofthe silicone rubber to itself which would close off the porosities thus created.
When the dissolution of the mold form material is complete, there remains a doubly porous silicone rubber membrane 162, with no communication between the two porosities. The primary porosity 164 (visualized without the mold form material) on the one side of the membrane 162 has its porosity, created by the mold form, whereas the secondary porosity 160 on the other side of the membrane has its porosity created by removing much ofthe silicone rubber within the interstices ofthe mold form. This side ofthe membrane may then be isolated by standard molding or construction techniques so that a gas, such as oxygen, or a liquid, such as a kidney dialysis solution, can be circulated through this secondary porosity, without cross-circulation into the primary porosity. Such a device may then be implanted so that the primary porosity 164 is filled intimately with new blood vessels and loose connective tissue. It has been found that this device is very tissue-compatible, with no fibrosis developing within the primary portion, and with capillaries and blood vessels literally within close proximity of the silicone rubber membrane.
With the prosthesis described above used as a dialysis device, a standard dialysis solution would be circulated through the secondary porosity 160. The membrane 162 between the porosities 160 and 164 acts like a dialysis membrane in a standard artificial kidney, removing the unwanted ureas, nitrogen compounds and ions, based on the standard difiusion principles. Due to the large surface area ofthe primary porosity, and the fact that a capsule doesn't form between the neovascularity and the silicone rubber membrane, an implantable dialysis device is now made practical.
Likewise, a similar device may be constructed for use in blood oxygenation. The device would be implanted and a specific oxygen concentration circulated through the secondary porosity 160. This time, with the thin silicone rubber membrane 162 acting as a gas transfer membrane, oxygen is transferred into the capillaries and vessels ingrown in the primary porosity 164 and carbon dioxide is removed from the vessels into the circulating oxygen in the secondary porosity 160. The carbon dioxide is then subsequently removed. Using the previous example, a layered membrane or a final product with a layer coating, such as shown in FIG 12, may be created as follows. After the thin membrane ofthe final product of silicon rubber 170 has been applied to the mold form, as in the previous example, and cured, but before the mold form is removed, a secondary material in its liquid form, e.g., aBiomer polyurethane solution 174 is vacuum- impregnated into the secondary porosity. This may either be partially blown out as described for forming the membrane in the previous example, or a thin (i.e., 10 to 15 percent) solution of the Biomer may be vacuum-impregnated and dried (resulting in removal ofthe 85 to 90 percent solvent) in an oven at 50 degrees C. for two hours This leaves a double-layered, interlocking membrane with separate porosity on each side, as shown in FIG. 12. Similarly, the physical interweaving of two materials processed as above can be used to advantage in joining two dissimilar materials (which do not readily adhere) to each other. This can be done so that there is double porosity left as in the FIG 12 example Two other methods can also be used to join the two materials, and give a porous or a nonporous surface on one side Using the example described for FIG. 11, the thin silicone rubber membrane is applied to the mold form and cured, but the mold form is kept in place The next material, say a catalyzed polyester resin, is vacuum-impregnated into the secondary porosity and allowed to polymerize The mold form is removed, resulting in a nonporous polyester surface and polyester interlocking structure in intimate contact with the thin silicone membrane, with porosity on the side of the membrane away from the polyester resin
In a similar manner, two sheets or structures can be joined utilizing the porosity This is done by creating a partially porous sheet of silicone rubber, as described in the example accompanying FIG 6, having a nonporous section 186 (FIG 13) and a porous section 184 After drying, a catalyzed polyester resin is vacuum-impregnated into the porosity of the silicone rubber. After polymerization, the resultant structure has two nonporous surfaces, 186 for the silicone rubber 186, and 180 for the polyester resin, with their associated porosities 184 and 182 respectively being in intimate contact mechanically to interlock the two materials together
It is to be understood that the above-described arrangements are only illustrative ofthe application ofthe principles ofthe present invention Numerous modifications and altemative arrangements may be devised by those skilled in the art without departing from the spirit and scope ofthe present teaching and the appended claims are intended to cover such modifications and arrangements
Priority Applications (1)
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|PCT/US1995/013846 WO1997015242A1 (en)
|Porous material product and process
Applications Claiming Priority (9)
|Application Number
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|DE1995632390 DE69532390T2 (en)
|A process for producing an article made of a porous material
|DE1995632390 DE69532390D1 (en)
|A process for producing an article made of a porous material
|ES95939606T ES2213756T3 (en)
|Process for preparing a device of porous material.
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|Porous material products
|PCT/US1995/013846 WO1997015242A1 (en)
|Porous material product and process
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|A method for producing an article of porous material
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|Porous material product and process
|AT95939606T AT257001T (en)
|A process for producing an article made of a porous material
|EP19950939606 EP1003443B1 (en)
|Method of preparing a porous material device
Publications (1)
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|WO1997015242A1 true WO1997015242A1 (en)
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|PCT/US1995/013846 WO1997015242A1 (en)
|Porous material product and process
Country Status (8)
|EP1003443B1 (en)
|JP3817267B2 (en)
|AT257001T (en)
|CA2235616C (en)
|DE69532390D1 (en)
|DK1003443T3 (en)
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|Graham Francois Duirs
|Drug delivery system
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|Ashby Scientific Ltd.
|Textured and porous silicone rubber
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|Medtronic, Inc.
|Transmural concentric multilayer ingrowth matrix within well-defined porosity
|US6589998B1 (en)
|Cytyc Health Corporation
|Gel composition for filling a breast milk duct prior to surgical excision of the duct or other breast tissue
|US6616699B2 (en)
|Peter Paul Zilla
|Foam-type vascular prosthesis with well-defined angio-permissive open porosity
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- 1995-10-25 AT AT95939606T patent/AT257001T/en not_active IP Right Cessation
- 1995-10-25 WO PCT/US1995/013846 patent/WO1997015242A1/en active IP Right Grant
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- 1995-10-25 DE DE1995632390 patent/DE69532390T2/en not_active Expired - Lifetime
- 1995-10-25 EP EP19950939606 patent/EP1003443B1/en not_active Expired - Lifetime
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|WO2018130947A1 (en) *
|Sil-Co S.R.L.
|Auditory prosthesis for middle-ear and related coating method
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|CA2235616C (en)
|JPH10512176A (en)
|CA2235616A1 (en)
|ES2213756T3 (en)
|AT257001T (en)
|DK1003443T3 (en)
|EP1003443A1 (en)
|DE69532390D1 (en)
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This is America, a country where people could speak, write, assemble, demonstrate without fear. It was in the Constitution, the Bill of Rights. We were a democracy. The state and its police were not neutral referees in a society of contending interests. They were on the side of the rich and powerful. Free speech? Try it and the police will be there with their horses, their clubs, their guns, to stop you. From that moment on, I was no longer a liberal. I was a radical, believing that something fundamental was wrong in this country—not just the existence of poverty amidst great wealth, not just the horrible treatment of minorities, but something rotten at the root. The situation required not just a new president or new laws, but an uprooting of the old order, the introduction of a new kind of cooperative society.
America is at a crossroads. History may show that from this point forward, we will have left behind any semblance of constitutional government and entered into a militaristic state where all citizens are suspects and security trumps freedom. Certainly, this is a time when government officials operate off their own playbook with little in the way of checks and balances, while American citizens are subjected to violations of their civil rights with little hope of defending themselves.
We have moved beyond the era of representative government and entered a new age—the age of authoritarianism. Even with its constantly shifting terrain, this topsy-turvy travesty of law and government has become America's new normal.
The Executive Branch: Whether it's the Trump administration's war on whistleblowers, the systematic surveillance of journalists and regular citizens, the continued operation of Guantanamo Bay, or the occupation of Afghanistan, Donald Trump has surpassed his predecessors in terms of his abuse of the Constitution and the rule of law. President Obama, like many of his predecessors, has routinely disregarded the Constitution when it has suited his purposes, operating largely above the law and behind a veil of secrecy, executive orders and specious legal justifications.
The policies of the American police state will continue under Donald Trump.
The Legislative Branch: Congress may well be the most self-serving, corrupt institution in America. Abuses of office run the gamut from elected representatives neglecting their constituencies to engaging in self-serving practices, including the misuse of eminent domain, earmarking hundreds of millions of dollars in federal contracting in return for personal gain and campaign contributions, having inappropriate ties to lobbyist groups and incorrectly or incompletely disclosing financial information. Pork barrel spending, hastily passed legislation, partisan bickering, a skewed work ethic, graft and moral turpitude have all contributed to the public's increasing dissatisfaction with congressional leadership. No wonder 86 percent of Americans disapprove of the job Congress is doing.
The Judicial Branch: The Supreme Court was intended to be an institution established to intervene and protect the people against the government and its agents when they overstep their bounds. Yet through their deference to police power, preference for security over freedom, and evisceration of our most basic rights for the sake of order and expediency, the justices of the United States Supreme Court have become the guardians of the American police state.
Sound judgment and justice have largely taken a back seat to legalism, statism and elitism, while preserving the rights of the people has been deprioritized and made to play second fiddle to both governmental and corporate interests.
America's is a bitterly divided nation teetering on the brink of financial catastrophe.
We have a shadow government, one that is fully operational and staffed by unelected officials who are running the country. Referred to as the Deep State, this shadow government is comprised of unelected government bureaucrats, corporations, contractors, paper-pushers, and button-pushers who are actually calling the shots behind the scenes right now.
Law Enforcement: "law enforcement" encompasses all agents within a militarized police state, including the military, local police, and the various agencies such as the Secret Service, FBI, CIA, NSA, etc. Having been given the green light to probe, poke, pinch, taser, search, seize, strip and generally manhandle anyone they see fit in almost any circumstance, all with the general blessing of the courts, America's law enforcement officials, no longer mere servants of the people entrusted with keeping the peace but now extensions of the military, are part of an elite ruling class dependent on keeping the masses corralled, under control, and treated like suspects and enemies rather than citizens.
In Virginia lawmakers are considering legislation to keep police officers' names secret, ostensibly creating secret police forces.
A Surveillance Society: Every dystopian sci-fi film we've ever seen is suddenly converging into this present moment in a dangerous trifecta between science, technology and a government that wants to be all-seeing, all-knowing and all-powerful. By tapping into your phone lines and cell phone communications, the government knows what you say. By uploading all of your emails, opening your mail, and reading your Facebook posts and text messages, the government knows what you write. By monitoring your movements with the use of license plate readers, surveillance cameras and other tracking devices, the government knows where you go. By churning through all of the detritus of your life—what you read, where you go, what you say—the government can predict what you will do. By mapping the synapses in your brain, scientists—and in turn, the government—will soon know what you remember. And by accessing your DNA, the government will soon know everything else about you that they don't already know: your family chart, your ancestry, what you look like, your health history, your inclination to follow orders or chart your own course, etc. Consequently, in the face of DNA evidence that places us at the scene of a crime, behavior sensing technology that interprets our body temperature and facial tics as suspicious, and government surveillance devices that cross-check our biometrics, license plates and DNA against a growing database of unsolved crimes and potential criminals, we are no longer "innocent until proven guilty."
Military Empire: America's endless global wars and burgeoning military empire—funded by taxpayer dollars—have depleted our resources, over-extended our military and increased our similarities to the Roman Empire and its eventual demise. The U.S. now operates approximately 800 military bases in foreign countries around the globe at an annual cost of at least $156 billion. The consequences of financing a global military presence are dire. David Walker, former comptroller general of the U.S., believes there are "striking similarities" between America's current situation and the factors that contributed to the fall of Rome, including "declining moral values and political civility at home, an over-confident and over-extended military in foreign lands and fiscal irresponsibility by the central government." I haven't even touched on the corporate state, the military industrial complex, SWAT team raids, invasive surveillance technology, zero tolerance policies in the schools, overcriminalization, or privatized prisons, to name just a few, but what I have touched on should be enough to show that the landscape of our freedoms has already changed dramatically from what it once was and will no doubt continue to deteriorate unless Americans can find a way to wrest back control of their government and reclaim their freedoms. That brings me to the final and most important factor in bringing about America's shift into authoritarianism: "we the people." We are the government. Thus, if the government has become a tyrannical agency, it is because we have allowed it to happen, either through our inaction or our blind trust. Essentially, there are four camps of thought among the citizenry when it comes to holding the government accountable. Which camp you fall into says a lot about your view of government—or, at least, your view of whichever administration happens to be in power at the time. In the first camp are those who trust the government to do the right thing, despite the government's repeated failures in this department. In the second camp are those who not only don't trust the government but think the government is out to get them. In the third camp are those who see government neither as an angel nor a devil, but merely as an entity that needs to be controlled, or as Thomas Jefferson phrased it, bound "down from mischief with the chains of the Constitution." Then there's the fourth camp, comprised of individuals who pay little to no attention to the workings of government, so much so that they barely vote, let alone know who's in office. Easily entertained, easily distracted, easily led, these are the ones who make the government's job far easier than it should be. It is easy to be diverted, distracted and amused by the antics of the presidential candidates, the pomp and circumstance of awards shows, athletic events, and entertainment news, and the feel-good evangelism that passes for religion today. What is far more difficult to face up to is the reality of life in America, where unemployment, poverty, inequality, injustice and violence by government agents are increasingly norms. The powers-that-be want us to remain divided, alienated from each other based on our politics, our bank accounts, our religion, our race and our value systems. As George Orwell observed, "The real division is not between conservatives and revolutionaries but between authoritarians and libertarians." The only distinction that matters anymore is where you stand in the American police state. In other words, you're either part of the problem or part of the solution

subset: commoncrawl


text:
Change the venue and you change a lot.
This is exactly what WinterKids did Thursday night when it moved its annual summer fundraiser from the white linen world of the country club to the quirky confines of Bubba's Sulky Lounge in Portland. Crammed from floor to ceiling with an mind-boggling mix of antiques and collectibles, Bubba's has been a Portland institution since 1959 and in recent years has reinvigorated its timeworn lounge by bringing in revelers with Zodiac parties and '80s and '90s dance nights.
"Bubba's is really Portland's best-kept secret for this kind of thing," WinterKids Executive Director Julie Mulkern told me. With two bars, a lighted dance floor and three main party rooms (plus endless nooks and crannies filled with old appliances, stuffed toys and the much-talked about lunch boxes), Bubba's looks radically different from other function halls. Sure, the upholstery at Bubba's may be ripped and the antiques a little dusty, but such a venue helps make a party more memorable.
"There are so many auctions, but this stands out," Dani Kolben told me.
Her husband, Eric Kolben, is on the board and he and fellow board member Will Stiles came up with the idea to move the party to Bubba's.
"Our mission (as WinterKids) is to get kids off the couch," Stiles told me. "Tonight our mission is to get the parents of the WinterKids out of the house."
Ryan Keith of Turner told me the location helped convince a couple of his friends to attend the License to Chill party.
"They asked if the dance floor was going to be lit up," Keith said.
"The last time I was here was for an '80s night," Rebecca Daigle of South Portland told me. "It's a fun venue."
In addition to a funky atmosphere, the party served up a silent auction and eats from Buck's Naked BBQ and Portland Pie. About halfway through the party, the 250 guests were treated to a zany (and slightly naughty) improv comedy performance by Dennis Hunt, Tuck Tucker and Tom Walsh, who are members of Running With Scissors.
This was followed by a short live auction, handled by Maine's Funniest Mom (and newly minted Old Port ice cream shop owner) Karen Morgan. The premier item was a chance to enjoy 18 holes of golf and dinner with two-time Olympic snowboardcross gold medalist Seth Wescott.
When he addressed the party guests, Wescott, who volunteers his time for the organization, told us: "It's amazing to see this grow over time. Being home and hurt this winter was kind of a blessing because I got to visit more schools."
After the auction, the band North of Nashville, a favorite with the Sugarloaf crowd, took to the stage and got people dancing on the illuminated disco floor.
WinterKids provides all Maine 5th through 7th graders with free and discounted admission to slopes and trails. The organization also introduces Maine children, particularly new immigrants, to the state's rich tradition of winter sports.
"Without all of you here supporting us, we couldn't have reached 17,000 kids this year," Mulkern told the crowd.
"People know us for the Passport program," incoming board president Michael Peisner told me. "Our mission is to get kids of all backgrounds to know the outdoors."
One way the nonprofit achieves this, Peisner told me, is by collecting "winter outerwear, because one of the barriers is when families don't have warm clothes."
Since the License to Chill party raised more than $20,000 for the organization, I'd say the forecast looks good for introducing even more kids to Maine's winter wonderland once the snow starts to fly.
Staff Writer Avery Yale Kamila can be contacted at 791-6297 or at:
Twitter: AveryYaleKamila
Maine expects another record year for cruise ships
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In wildly popular game, you kill a journalist: 'Make him famous in a different way'
Preakness winner likely heading to Belmont
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Pill abortions in Missouri decreased after pelvic exam requirement
Local & State
Westbrook adopts property tax relief for seniors


text:
eople just love to watch computer screensavers. Other than their functional
purpose, screensavers have been used since their creation as a marketing tool
for business. In fact, many computer stores cleverly use screensavers to lure
customers, with their bright and crisps images and fast animation. Computer
owners like to change screensavers every now and tend so they're always on the look out for cool screensavers.
If you're someone who's artistic and loves animation, then you could potentially make money creating your own screensavers. Your basic tools would be a computer and whichever software you choose to generate the screensavers. You could create packages based on different themes like nature scenes, abstract designs or cartoons and sell them. The easiest and most logical way to get your beautiful screensavers would be to sell them on the Internet. You would need to set up a simple website where people could buy your screensavers.
Keep in mind though, that there are literally millions of FREE screensavers
floating around in cyberspace. They're mainly a marketing tool to attract visitors to websites. To be different, you will need to let your creativity stand out. Perhaps you could sell your skills and design corporate screensavers for companies to enhance their corporate image. It's a pretty nice way to let your creative juices earn you money!


text:
Taster SessionsIf you have little or no riding experience, our 'Taster Sessions' are ideal. Suitable for both children and adults it is tailored to your individual requirements. During a session you will learn more about this special native pony, pony handling and care and have hands on experience grooming and tacking the pony. The highlight of the session is the chance to ride in a comfortable and controlled environment in our indoor arena. A memory that will stay with you for a long while.
Suitability: For all abilities and ages from 4 years upward. Previous riders have ranged in age from 4 to 78 years! There is a weight limit of 12 stone / 76 kilos.
Cost for 1 hour session: £30 for one or two participants with one pony.
Cost for 40 minute session: for 4 and 5 year olds £20 for 1 or 2 children with one pony.
Advance Booking Essential: To avoid disappointment, we recommend early booking due to their popularity, especially during holiday periods.
Riding hats are provided. Please wear suitable clothing and footwear.
Availability: Taster Sessions can be booked from mid February until the end of October.
Please call 01398 323093 to book. In order to choose a suitable pony you will be asked for the rider's age, weight and height.
We carry full insurance and are licensed by West Somerset Council.


text:
I have been very deficient in making posts and I wish to apologize. It is my intent to always attempt to make regular and hopefully daily posts. However, many of my posts require significant research and organization and then hours to actually write. The "Leftovers" posts from the Radio Show take 2-3 hours minimum.
Since April I have been heavily involved in research on the European Credit Crisis looking at not just the countries but the banks in the countries, the ECB, the EU, the eurozone, account imbalances within the eurozone, the monetary and fiscal structure of the eurozone, interbank lending, country and bank exposure to deficit countries encountering credit confidence problems, interbank lending, liquidity issues, and trying to identify trends and the reasons effective solutions were or were not emerging.
The European Credit Crisis is now at a lull, but credit and liquidity issues remain and they present potentially global ramifications, particularly as China and India attempt to control inflation internally, China attempts to control its real estate bubble, and political internal pressures build within France, Germany, the UK, Greece, not to mention India, China (a major competitor with Germany for the export market), and other countries. In the meantime, Russia has been exerting its energy muscle to build relationships within the EU and eurozone to benefit its own economic interests which could eventually put enormous pressure on NATO.
Professionally, I have had to get Quarterly investment management reports out and otherwise earn a living.
I have almost 20 articles outlined and/or researched and waiting for the hours to write them. Although I have not been posting, I still spend significant hours during normal sleeping hours working and doing research. One article on Germany and how its history is consistent with the current Credit Crisis has been ready to write for over three weeks and will undoubtedly be relatively long while still concise. I have another I want to do as soon as possible on Spain and its importance in how the European Credit Crisis winds down or proceeds. I have at least two more planned and researched on the Pan-European Credit Crisis. I have another on The Great Moderation as the Great Enabler. I have one planned on China and its currency. I have another on rethinking macro policy; another on wages, aggregate demand, and unemployment.
I intend to post all Leftovers from the Radio Show even though I am a half box behind in getting it done, because I think it is important to see how the data and facts have evolved. When I get commentaries on the market from various sources, I like to read them and then hold them for at least a month and then read them again. It can be very insightful.
I intend to make it worthwhile to check this Blog on a regular and, hopefully, a daily basis.
Print Page
- ProMarket.org - The blog of the Stigler Center at the University of Chicago Booth School of Business


text:
Answered By: Sarah Aitchison Last Updated: Jul 18, 2017 Views: 37
The Institute of Education holds collections of archive materials ranging in date from 1797 to the present day.
These archives are intended to reflect the broadest possible range of issues and concerns surrounding teaching and lifelong learning in past, present and future societies. This includes all levels of education from pre-school and school through to further, higher, teacher and adult education, in formal, informal and experimental settings. It includes research, practice, policy and thought in education and related areas. They provide a rich resource for the history of education and educationists both in this country and abroad.
Broadly speaking, the archives are split into 2 groups:
Deposited Collections, given to us by people and organisations related in some way to education. There are over 130 of these, ranging in size from one box to over 300.
The Institute Archive, comprising the records of the Institute of Education itself, dating from its creation in 1902.
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text:
Twelve Days of Christmas book - mainly because of the flickering "Ani-Motion" technology (also called "scanimation") used for the cute illustrations.
Watch as the three french hens peck the ground and the drummers drum - the story literally springs to life as you turn the pages!
And that's good news for a parent looking for a way lure their child onto their lap for a fun moment in the midst of all the after-Christmas-commotion-and-gift-opening-hubbub!
My 3-year-old grandson absolutely loves this book and already has the song memorized. He sings right along with him mommy!


text:
Cllr King has asked if I could put up a note telling readers that the next Westgate & Westbrook Residents' Association (WWWRA) meeting will be this coming Monday, 2nd April at the Westbrook Bowls Club.
This is because Easter Monday falls on the second week of the month when the meeting is normally held.
As this is such a short entry, I will leave you with Friday's weather forecast for the south-east.


text:
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Jake AdelsteinJake Adelstein (born March 28, 1969) is an American journalist, crime writer, and blogger who has spent most of his career in Japan. He is the author of ''Tokyo Vice: An American Reporter on the Police Beat in Japan.'' Provided by Wikipedia
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Young Women Camp is an outdoor experience for young women ages 12 to 18. It gives young women opportunities to:
- Draw closer to Heavenly Father and His Son, Jesus Christ
- Feel the influence of the Spirit.
- Serve others.
- Build friendships and unity
- Learn skills.
- Appreciate God's creations.
- Have fun!
Girls Camp Craft Supplies
Camp Crafts are a tradition at girls camp. Check out these supplies that can help you create easy camp crafts. We even have several How To's for each of these items to make your camp crafting easy!
- How to make a girls camp necklace for less than $2.00
- Make a CTR necklace in less than 15 seconds
- How to assemble the Young Women Jewelry Kit
- Mia Maid Rose Necklace Kit
Make your own craft with our inexpensive kits:
LDS Girls Camp Pillow Treats
Many Girls Camp leaders love to place a little treat on the pillow of each young woman. Here are some inexpensive ideas for pillow treats:
LDS Girls Camp Shirts and Hoodies
Girls Camp Printables and Links
- 2015 Mutual Theme Poster – By LDS.org, 6×9 inches
- Make an LDS Necklace for less than $2.00
- 2015 Mutual Theme Glass Tile Necklaces
- Young Woman reading part of D&C 4:2
- 2015 Mutual theme Poster
- New Beginnings 2015- Embark Airlines
- 2015 Mutual Theme Candy Bar Wrappers [5 Sizes!]
- Embark Invitation
- 2015 mutual theme – Five Quotes
- 2015 mutual theme – Five Quotes
- A Couple of Sneak Peeks and Some Updates
- YW Newsletter Template [Editable PDF: Including Mutual Theme]
- 2015 Mutual Theme Photo Posters [Horizontal]
- 2015 Mutual Theme Photo Posters [Vertical]
- 2015 Mutual Theme Calendars: Vertical [Editable PDF & JPEGS]
- 2015 mutual theme
- 2015 Mutual Theme Calendars: Horizontal [Editable PDF & JPEGS]
- Embark in the Service of God – Boat Logo
- 2015 Mutual Theme Calendar Sneak Peek
- 2015 Fabrics + BOGO Fat Quarters (Limited Time)
- 2015 Mutual Theme Logos: Embark in the Service of God
- YW Personal Progress V{owl}ues 2015 Mutual Theme Logos
- Serve Him – Heart Might Mind Strength
- Embark – Heart, Might, Mind, Strength
- 2015 Mutual Theme: Embark in the Service of God
- 2015 Mutual Theme Announced!
LDS Girls Camp Ideas
Check out our crazy huge list of YW Camp Themes, tips and Ideas!
Camp Help from LDS.org
- LDS.org: NEW Camp Leadership and Planning Guide in PDF
- LDS.org: Camp Basics
- LDS.org: How to Plan a Young Women Camp
- LDS.org: How to Invite the Spirit at Girls Camp
- LDS.org: Safety, etc.
- LDS.org: Camp Music
- LDS.org: Helping Young Women with Disabilities at Girl's Camp


text:
|wasp nest II
photo: Katie Barnes
A wasp rises to its papery
nest under the eaves
where it daubs
at the gray shape,
but seems unable
to enter its own house.
--Jane Kenyon
|wasp nest I
photo: Katie Barnes
|wasp nest II
photo: Katie Barnes
|wasp nest I
photo: Katie Barnes
Dear Heather,
this is all such wonderful news. I'd say God bless but it appears he has already. :)
59 not 19 - yeah, sounds groovy to me.
What I happy about for you in all of this is that you are being enabled to flow in your creativity which usually begets more of the same.
I loved this post! Except for the wasp nest, they scare the heck out of me, but that's okay. I'm glad you're getting editing work. IMHO you seem to be writing a lot ... maybe I missed something. Interested in your summer reading recommendations. I read Amagansett by Mark Mills, set on Long Island, which might count as New England.ReplyDelete
You go Heather. Maybe you could get an interview with Mary Karr? She's fantastic. She was giving a talk at a church and I walked up to her and said: "Mary Karr you're the best thing that happened to me today." And we sat and talked like girlfriends.
Turns out we were both born the same year:)
You're busy-good. Good busy. Love the news. The poem from Jane Kenyon is quite good. She and Donald Hall were together a long time.
:) May God continue to pour His blessings out on you and through you!ReplyDelete
I am taking my daughters to Hampton Beach tomorrow, Heather. I'll be thinking of you!
Happy Almost Birthday, Heather. I love that "Polish over here.." quote. You just generally rock!ReplyDelete
yeah, people! Thank you so much. And Barbara, how lovely that Mary Karr was so kind to you...ReplyDelete


text:
From: clayton stirling bartholomew (email@example.com)
Date: Sat May 20 2000 - 15:39:12 EDT
on 05/20/00 11:08 AM, Hultberg, Alan wrote:
> By the way, Clay, how would you respond?
It has been my habit on b-greek to just throw out a molatov cocktail while
driveing by at high speed and then retire to some vantage point where I can
observe the conflagration from a safe distance.
My jaundice view of translation as a stage in exegesis is born out of years
of doing it. Over a period of several years of stagnation and plateauing it
gradually dawned on me that I was going to make no further progress in my
language competence as long as I kept falling back on English.
This is not a theory it is just a testimony about personal experience.
Clayton Stirling Bartholomew
Three Tree Point
P.O. Box 255 Seahurst WA 98062
B-Greek home page: http://sunsite.unc.edu/bgreek
You are currently subscribed to b-greek as: [firstname.lastname@example.com]
To unsubscribe, forward this message to email@example.com
To subscribe, send a message to email@example.com
This archive was generated by hypermail 2.1.4 : Sat Apr 20 2002 - 15:36:26 EDT