The present disclosure relates to compressed coconut coir pith granules for use as growth media and to methods for producing such granules or flakes. More particularly, the compressed granules or flakes produced in accordance with the present invention exhibit enhanced size, density, flowability and abrasion resistance characteristics which render the granules highly desirable for use in seeding mulch, potting mix, garden soil and flower and vegetable furrow covering applications.
Coconut coir pith is a by-product of the coconut husk fiber processing industry. Coir is the name given to the fibrous material that constitutes the thick mesocarp (middle layer) of the coconut fruit (Cocos nucifera). In processing, the long fibers of coir are extracted from the coconut husk for use in the manufacture of brushes, upholstery stuffing, filters, twine and like products. The short fibers (10 mm or less) and dust (collectively referred to herein as “pith”) traditionally have accumulated in large piles or “dumps” as a waste product resulting from the processing of coconut husks to obtain the industrially valuable long fibers.
It has been recognized that coconut coir pith material provides an excellent growing medium for plants and it has been suggested that coconut coir pith can provide an effective alternative to previously standard growing media such as peat moss. Coconut coir pith is very similar to sphagnum peat moss in appearance, having a light to dark brown color and consisting primarily of particles in the size range of 0.2-2.0 min (75-90%). Unlike sphagnum peat, however, there are no sticks or extraneous matter in the coconut coir pith. Furthermore, sphagnum peat moss has a density of about 7 lbs/cu ft when fluffed (30-50% moisture content) whereas coir pith is much denser (i.e., about 43 lbs/cu ft when compressed at a ratio of 5:1 on volume to volume basis and about 12 lbs/cu ft when fluffed and having a 50-55% moisture content).
Coir pith as an amendment has many benefits for all types of soil. It increases the organic matter content and due to its high lignin to cellulose ratio, it remains in the soil significantly longer than peat. It improves water-holding capacity of sandy soils. The drainage of clay soils is improved with its inclusion due to its air porosity and agglomeration with clay particles. However, the use of compressed coir pith bricks is cumbersome for use by consumers. The entire brick must first be expanded with water for a relatively long period of time. Then, the consumer must physically fluff and mix the coir pith for complete wetting and expansion. Only then can the wet, expanded coir pith be spread on and incorporated into the soil.
As employed herein the term “coconut coir pith” is intended to refer to both the coconut husk pith and the short coir fibers which are known to provide an excellent growing medium and to provide a suitable and sustainable substitute for soilless growing media such as peat moss (sphagnum, sedge, hypnum and the like) for growing plants. Coconut coir pith has many physical and horticultural characteristics that make it an ideal growing medium for plants. Coconut coir pith has a high water holding capacity, ideal porosity, high cation exchange capacity and high stability (slow rate of degradation due to high lignin to cellulose ratio which prevents oxidation).
However, coconuts are typically only grown in tropical and sub tropical regions, while demand for the substrate is in the United States and Europe, which entails significant shipping and handling costs.
Presently, the forms in which coconut coir pith is available for import into the United States and Europe are rather limited. Due to the low bulk density of loose coconut coir pith at moisture contents acceptable for shipping, coconut coir pith has been compressed into discs, bricks, or blocks at a compression ratio typically of about 5:1 to enable economical overseas shipping costs. It has been known that compressed coconut coir pith in this form must be mechanically out-turned or exposed to water for a lengthy period to decompress the coconut coir pith before use as such or for inclusion in a consumer product. This processing step is relatively slow and requires the entire disc, brick, or blocks to be out-turned at once. Also, coconut coir pith that is outturned is either dry and dusty or wet and heavy which contributes to further processing problems. Furthermore, coconut coir pith is not commonly baled in the manner of sphagnum peat because this form is less compressed and, therefore, less economical to ship.
Attempts have been made to compress and form coir pith into pellets using pellet mills or extruders as, for example, disclosed in U.S. Published Patent Application 2004/0025422. Those processes require use of high shear compaction methods which generate high levels of heat through friction. Such high temperature processing alters the physical properties of the coconut coir pith substrate. The pellets produced have been found to exhibit undesirable physical characteristics such as relatively slow expansion after compaction, and the coconut coir pith normally does not expand back to its pre-compacted volume after such compaction.
For example, the use of pellet mills or extruders for compaction of coir into small compressed particles has been suggested heretofore. However, pellet making processes use high pressure to extrude the material through small orifices. Unlike roll compaction, pelletizing is a high shear process that produces significant friction and heat in the material. The friction and heat from this process may produce a coir pith pellet with undesirable physical and horticultural properties. Although comparable compression ratios can be achieved, the expansion ratio after the addition of water, water holding capacity of the material, and the rate of expansion of the granules may be reduced.
Accordingly, it is an object of the present disclosure to provide more convenient forms of coconut coir pith for horticultural use which expand rapidly upon contact with moisture.
It is a further object to provide economically effective production methods for producing compacted granular coconut coir pith products which have the desired physical and horticultural properties necessary for final product application, for example, as growth media.
Compacted granular coconut coir pith products produced in accordance with the disclosure are highly desirable for use in providing growing media in such applications as seeding mulch, potting mix garden soil, flower and vegetable furrow covering applications and the like. More particularly, the present disclosure is generally directed to methods for producing granular coconut coir pith products by subjecting raw coconut coir pith material to roll compaction under specified operating conditions as opposed to the prior art pellet mill compaction or extrusion processes. Roll compaction of the coconut coir pith is followed by subsequent granulation of the compacted granules to provide plant growth media which expand immediately upon exposure to moisture or water.
The compressed granular coconut coir pith products produced in accordance with the present disclosure may be composed of coconut coir pith only or may contain other horticulturally acceptable media such as fertilizers, micronutrients, pH adjusting agents, wetting agents, biostimulents, microbes and other bioactive materials. The granules produced in accordance with this invention have a bulk density in a range of between about 240 kg/m3 and 600 kg/m3 and expand rapidly when exposed to moisture.
The disclosure provides a method for preparing compressed coir granules that expand readily with exposure to water. The granules are formed by roll compaction and subsequent granulation (milling and screening). This process has been shown to produce compacted coir granules with superior characteristics to coir pellets that are manufactured with a pellet mill or extruder.
Coconut coir pith has a unique microstructure composed of a relatively uniform pore structure. With application of high pressure, the pore structure can be compressed and the resulting compressed coconut coir pith product will expand back to its original volume upon exposure to moisture. However, we have found that it is critical to employ certain operating conditions to achieve compression of the coconut coir pith substrate to avoid excessive heat generation through friction that could denature the desired physical and horticultural characteristics of the material.
The compressed granules (including flakes, particles, pellets and the like) produced in accordance with this invention are formed from a variety of coconut coir pith substrate materials. It should be noted that as employed herein the term “granules” is intended to include of all granular forms and shapes including flakes, particles, pellets and the like. Typically, the substrate materials employed herein comprise mixtures of coir fiber and coir pith (with pith being the more desirable component of the mixture). However, the substrates may comprise other mixtures such as coconut coir pith and up to about 50% (by weight) of a horticulturally acceptable organic or non-organic media such as sphagnum peat, humus peat, sedge peat, bark fines, rice hulls and mixtures thereof or, in addition, any other material familiar to those skilled in horticulture.
The compressed granules formed in accordance with the present disclosure, may be randomly shaped and angular in surface appearance and may contain pieces of coir fiber. The compressed flakes may contain additives such as fertilizers, micronutrients, pH adjusting agents such as lime, and/or various wetting agents including horticulturally acceptable surfactants and other additives designed to enhance or protect the germination, development, and/or growth of seeds and plants implanted in a growth media formed from the compressed products. The additives also may be used to improve the physical and horticultural characteristics of the granules. The additives alternatively may comprise pesticides or herbicides.
Typically, the concentration of the additives in the compressed products should not exceed about 10% of the total weight of the product, but could comprise up to about 50% (by weight) of the flake.
In a preferred embodiment, the compressed coconut coir pith granules are formed by roll compaction and subsequent granulation as described in further detail below. Preconditioning of the coconut coir pith is an optional step with the major purpose of reducing the length of the coir fibers present in the coir pith whereby efficiency of compaction and subsequent granulation is increased. Most preferably, the coir pith contains less than about 10% by weight of coir fiber, but could contain up to about 50% by weight of coir fiber.
The compressed flakes formed by employing the methods of the present invention are useful for various horticultural applications when they are sized greater than about 32 mesh (US sieve size) and pass through about a 1½ inch screen. The particle size distribution may be adjusted within this range to accommodate specific product application requirements by changing the process conditions of the post-compaction granulation milling and screening loop.
The moisture content of loose coir pith in the coconut coir pith substrate may be less than about 25% water by weight for compaction of the substrate. Preferably, the range of moisture content should be between about 8 and about 15% water (by weight). The compaction itself may not significantly affect the moisture content of the coir pith; however, if desired, steps can be taken to adjust the moisture content during any preconditioning and/or blending stages prior to compaction.
Depending on the intended application of the compressed coconut coir pith produced by employing the methods of the present disclosure, the granules produced thereby should have sufficient physical integrity and abrasion or attrition resistance to satisfy the requirements of the intended use.
In order to quantify the abrasion or attrition resistance of compressed granules and the ability of the compressed granular products to withstand mechanical processing the following procedure may be employed wherein a limit screen size that retains 90% of a granular material is determined by particle size analysis prior to testing. Then, granular test samples are placed on the limit screen with stainless steel balls of a specific size. The screen may be placed in a RoTap®-style Sieve Shaker for a specified amount of time. The abrasion resistance may be expressed as a percent of material remaining on the limit screen. The abrasion resistance should be sufficient to maintain integrity throughout additional processing, typically blending with other components, and final consumer or professional packaging.
A distinction of the compressed coir pith granules produced by employing the methods of the present invention as compared with extrusion of compressed coir pith disks, bricks, and blocks, is that the extrusion method products are slow to expand when exposed to moisture whereas the roll compacted compressed granules (including flakes, particles, pellets and the like) produced in accordance with the present disclosure have been found to expand within seconds of exposure to moisture.
For example, a compressed single granule of this invention which is dropped in sufficient water to expand it fully may typically be substantially completely expanded within about 15 seconds. This quick expansion can be attributed to the method of compaction and the high surface to volume ratio of the products produced. Specifically, granules of less than ¼″ in diameter may be completely expanded within less than about 10 seconds while larger granules may require longer periods to fully expand than the smaller granules or flakes. The expanded granules may de-granulate or fall apart into smaller pieces readily after being submerged in water.
Bulk compressed granules of the present disclosure may have an apparent expansion ratio when exposed to moisture of between about 2:1 and about 5:1, with expansion ratios of about 3.5:1 and about 4:1 being typical for compressed granules containing 100% coir pith. Expansion ratios are measured by taking a known volume of compressed coir pith granules and mixing by hand while adding the minimum amount of water to expand the coir pith until no palpable granules remain. The volume of the expanded material is then compared to the original compressed material. Inclusion of high percentages of other growing media such as sphagnum peat or bark fines in the granular composition may result in lower expansion ratios.
The expanded coir particles formed from the compressed granules of this invention may have a high water holding capacity of up to about 8 times their weight. The compressed granules produced may have a bulk density that ranges from about 240 kg/m3 to about 600 kg/m3.
In accordance with the present disclosure, the compressed coir pith granules can, for example, be blended with grass or other seeds or plant propagules and optionally nutrients and other commonly known horticulturally acceptable ingredients to produce a seeding mulch or a bare spot repair product for use in treating lawns and other areas requiring soil amendment or plant establishment. Fertilizer, pH adjustment agents such as lime, micronutrients, wetting agents (horticulturally acceptable surfactants), and other plant or biological growth enhancers may be included in the granules or the product mix. The resulting product mix may be a physical blend of compressed coir pith granules, seed or other plant propagules, and other additives (fertilizer, micronutrients, lime for pH adjustment, and other horticulturally acceptable ingredients). In addition, granules of acceptable size may be matched with other horticultural, agricultural, or garden seeds or plant propagules to enhance germination and establishment of lawns, gardens or other areas to be amended or vegetated.
The granules can range in size from less than about 1½″ to greater than about 32 mesh. The size of the granules can be adjusted based on application. For example, inclusion of the granules as mulch in a combination grass seed, fertilizer, and mulch product, the granule sizes would preferably be in the range of about less than about 4 mesh and to greater than about 18 mesh which would be relatively similar to the size of the seeds. The free flowing nature of the granules allows the user to sprinkle the product on a bare spot in a lawn with minimal effort. Once water contacts the granules either through overhead irrigation, rain, or moisture in the soil, the compressed granules expand and may help protect the seed from desiccation. Due to its high moisture holding capacity, the expanded coir pith may function as seed mulch that holds moisture near the seeds necessary for germination, early establishment, and healthy growth.
The coir pith's high water holding capacity may also help trap moisture in the root zone of the seedling by reducing evaporation from the soil. The nutrients in the product mix may be released directly into the soil and are less likely be adsorbed or tied up in the mulch layer. These unique properties enable the germinating grass to establish its roots directly in the soil and less so into the mulch, increasing the survival rate of seedlings introduced therein as compared to other known products. Results with trials using the products of the present invention have shown strong improvements over bare seed and currently available seeding mulches.
Coir pith in its raw form may not contain all the necessary nutrients for healthy plant growth. By including fertilizers and appropriate nutrients in the compaction process herein, a suitable potting mix may be made. The fertilizer chosen could be a slow release type fertilizer to provide plant nutrition for an extended period of time. Additions (fertilizers, lime for pH control, micronutrients, surfactants and biologically active ingredients) made prior to compaction of the coconut coir pith may result in production of homogeneous granules. The granules could range in size from less than about 1½″ to greater than about 18 mesh (US Sieve Series), however they would preferably be less than about ½″ to greater than about 6 mesh. The resulting products may have improved water-holding capacity over existing potting soils based on the natural properties of coir pith. Due to the high water-holding capacity, favorable air porosity, and correct nutrient additions, this product could result in improved results for consumers over ordinary potting soil. The compressed potting soil may be free flowing and may be easily poured from the package into a pot or container. When watered, the potting soil may rapidly expand to fill the container.
By using coir pith in the form of compressed granules produced in accordance with the methods of the present disclosure, the consumer would need to simply incorporate the granules into the soil. When the granules contact water, either through irrigation, rain, or available soil moisture, they may expand and improve the soil structure, water holding capacity, cation exchange capacity and other soil properties, such as tilth, depending on the nature of the soil being amended. The granules could range in size from less than about 1½″ to greater than about 18 mesh, preferably, less than about ¾″ to greater than about 6 mesh.
Additionally, the products of the present invention may be used as garden amendments such as for several vegetable species (radish, carrot, lettuce, etc.) which lend themselves to planting in a row or furrow followed by coverage of the seed with soil. Seedlings may be thinned over time. In this regard, it should be noted that by mixing the seed with an appropriate coir granule size fraction that matches the vegetable seed size, the seed and expandable soil mix can be effectively poured into the furrow or even onto the soil surface. Watering would then expand the coir and as a result the seed would be buried under a protective mulch cover that facilitates germination. Similar results could be obtained with flower seed.
Thus, it should be noted that the compressed coir pith granules of the present disclosure can be used more effectively and efficiently than previously known products in a variety of commercially and horticulturally significant applications including, for example, expandable potting mixes; garden soil amendments and flower and/or vegetable furrow coverings and the like.
A process in accordance with the present invention is provided in the flow diagram 100 shown in
The preconditioned coir pith which may be blended with additive materials may then be subjected to compaction into a large ribbon by means of a roll compactor, shown in step 105. The roll compactor applies pressure to the material in the range of about 1500 to about 2500 psi, preferably, about 1800 psi to about 2200 psi. The roll compactor may form the material into a semi-continuous ribbon or sheet. The compacted ribbon may be broken into granules or flakes, typically less than about 2″ in diameter with a mixture of smaller pieces, by a flake-breaker or other means to improve the ability to convey the material to the milling and screening loop. Then, the granules or flakes may be fed through a conventional milling and screening loop, shown in step 107, for granulation to a desired size range.
Once in the milling and screening loop, shown in step 107, the screen may separate the pieces into three streams: oversized pieces, on-size granules, and undersized fines. The oversized material may be recycled in the milling and screening loop, step 107, until it is reduced in size, and the fines are returned to the feed of the compactor of step 105. The desired size distribution of the compressed granules can be controlled by process changes in the milling and screening loop. The compressed granules preferably have a bulk density of between about 400 kg/m3 and 500 kg/m3, but could be anywhere in the range of 240 kg/m3 and 600 kg/m3, but more ideally in the range of 300 kg/m3 and 500 kg/m3. When exposed to water, the granules may quickly expand to about 3 to 4 times their compressed volume.
The density of the granules produced in accordance with the methods of the present disclosure and their free flowing physical properties may enable optimization of the filling of shipping containers resulting in economic savings compared to compressed disks, bricks and blocks. Furthermore, such compressed disks, bricks and blocks are typically stacked on pallets for shipment in cargo containers whereas the compressed granular products produced in accordance with the present invention can be bulk filled into containers to be dumped on arrival at their destination resulting in considerable cost and efficiency savings such as the cost of pallets.
Coir pith bricks of Sri Lankan origin were obtained from Haymark (Spring, Tex.). The bricks were out turned using a pin mill and screened through ⅜″ screen. The loose coir had a moisture content of between 10 and 17% by weight. A horticulturally acceptable surfactant was obtained from BASF, Pluronic L-62 is the name of the proprietary non-ionic surfactant. The coir was blended with 1% by weigh solution of a 1:1 mixture of surfactant and water. The surfactant treated coir was then fed into a Chilsonator Model 1.5L×8D Roll Compactor manufactured by Fitzpatrick Co. The roll pressure (oil pressure) was operated at between 1200 and 1800 psi. The feed screw was turning at 70 rpms. The coir left the compactor as a mixture of fines and semi-continuous ribbons. The compacts were collected and screened using a Sweco vibratory screener to +¼″. The fines were recycled back to the compactor. After about 20 lbs of compacts larger than ¼″ were collected, the material was milled in a Fitzmill (Fitzpatrick Co.) with knives installed and a ¼″ perforated plate for classification. After milling the granules were screened to −¼″, +30 mesh. A sample of the granules was then expanded by adding water and mixing by hand until no palpable granules remained. The expansion volume ratio was measured to be 3.25:1 versus the original compressed granules.
Coir pith bricks of Sri Lankan origin were obtained from Haymark (Spring, Tex.). The coir bricks were outturned using an Extructor Model RE-12 manufactured by Bepex (Minneapolis, Minn.). The coir was then milled using a Pulvicron, PC-20 (Bepex) in order to reduce the length of fibers present with the pith. The pulvicron is an air-swept mill with and internal classifier. Use of this mill is effective at reducing the fiber length and adjusting the moisture content of the coir pith by controlling the temperature and/or humidity of the air stream. Moisture content of the coir pith was typically between 10% and 15% by weight after milling. The pith was then batch blended in a ribbon blender with pulverized dolomite lime to adjust pH and 15-15-15 fertilizer (containing ammonium nitrate, ammonium sulfate, diammonium phosphate, and potassium chloride). The blended coir was compacted into ribbons using a Model MS-75 Compactor (Bepex) with a medium compression feed screw and flat (smooth surfaced) rolls. The roll pressure was set at 2300 psi and 6 rpm, and the feed screw was running at 35 rpm. The result was a semi-continuous ribbon of compressed coir pith. The ribbon was fed into a Jacobsen Crusher (Carter Day, Minneapolis, Minn.) with a 1″ square grate which reduced the ribbon into smaller pieces to enable conveying via screw conveyors and bucket elevators. The compacted coir pieces were then conveyed to a milling and screening loop consisting of a 60″ Sweco Screener and a Bepex Disintegrator RD-8 as a granulation mill. The screener separated the compacted coir into three streams; oversized pieces, on-size granules, and fines. The oversized pieces were sent to the granulation mill and subsequently returned to the screen. The fines were returned to the compactor, and the on size material was collected. In this example the on-size material was −6 mesh, +12 mesh with a loose bulk density of 370 kg/m3 (23 lbs/ft3). The expansion ratio of the compacted material after wetting and fluffing by hand was 3.75:1.
Typical ranges of process conditions for the compaction and granulation for the equipment in Example 2 are listed below. The ranges listed below are not the only conditions under which compressed coir pith granules with useful properties can be produced, and are exemplary only.
The table below provides a comparison of expansion ratios and expansion times for coir pith pellets formed from a pellet mill, and coir granules formed from a roll compactor:
Although the invention has been described in its preferred forms with a certain degree of particularity, it is to be understood that the present disclosure has been made by way of example only. Numerous changes in the details of the compositions and ingredients therein as well as the methods of preparation and use will be apparent without departing from the spirit and scope of the disclosure, as defined in the appended claims.
The present application claims priority to and incorporates by reference in its entirety U.S. Provisional Patent Application No. 61/000,818 entitled “Compressed Coconut Coir Pith Granules and Methods for the Production and Use Thereof” to Marcus Bertin, et al. filed Oct. 29, 2007.
Number | Name | Date | Kind |
---|---|---|---|
507144 | Lundell | Oct 1893 | A |
605640 | Houghton et al. | Jun 1898 | A |
940631 | Aylsworth | Nov 1909 | A |
1105047 | Thomson | Jul 1914 | A |
1827051 | Thomas | Mar 1928 | A |
1790111 | Pike | Jan 1931 | A |
2450830 | Helberg et al. | Oct 1948 | A |
2508414 | Meyer | May 1950 | A |
2664404 | Blatz et al. | Dec 1953 | A |
2917379 | Ryker | Dec 1959 | A |
2971292 | Malecki | Feb 1961 | A |
2998550 | Collins et al. | Aug 1961 | A |
3284209 | Kelley | Nov 1966 | A |
3375607 | Melvold | Apr 1968 | A |
3396810 | Andrews | Aug 1968 | A |
3502458 | Schenk | Mar 1970 | A |
3524279 | Adams | Aug 1970 | A |
3590937 | Andrews | Jul 1971 | A |
3615809 | Nagle et al. | Oct 1971 | A |
3653459 | Andrews | Apr 1972 | A |
3656930 | Martin | Apr 1972 | A |
3669204 | Andrews | Jun 1972 | A |
3703464 | Ferm | Nov 1972 | A |
3809175 | Andrews | May 1974 | A |
3842537 | Bishop | Oct 1974 | A |
3960722 | Tomikawa et al. | Jun 1976 | A |
3973355 | McKenzie | Aug 1976 | A |
4063919 | Grano, Jr. | Dec 1977 | A |
4072794 | Tomita et al. | Feb 1978 | A |
4098398 | Myers | Jul 1978 | A |
4123518 | Behrenz et al. | Oct 1978 | A |
4172039 | Akiyama | Oct 1979 | A |
4174957 | Webb et al. | Nov 1979 | A |
4185987 | Tilkanen | Jan 1980 | A |
4258659 | Rowell | Mar 1981 | A |
4277345 | Heitkamp et al. | Jul 1981 | A |
4318248 | Muldner | Mar 1982 | A |
4341180 | Cortigene et al. | Jul 1982 | A |
4473390 | Teufel | Sep 1984 | A |
4537877 | Ericsson | Aug 1985 | A |
4551165 | Warner | Nov 1985 | A |
4570573 | Lohman | Feb 1986 | A |
4570578 | Peschka et al. | Feb 1986 | A |
4579578 | Cooke | Apr 1986 | A |
4591635 | Greve et al. | May 1986 | A |
4627382 | Muzzey | Dec 1986 | A |
4643811 | Langlois | Feb 1987 | A |
4643814 | Goldstein | Feb 1987 | A |
4675388 | Greve | Jun 1987 | A |
4705248 | McIntyre | Nov 1987 | A |
4721059 | Lowe et al. | Jan 1988 | A |
4723510 | Skillestad | Feb 1988 | A |
4734393 | Lowe et al. | Mar 1988 | A |
4738286 | McIntyre | Apr 1988 | A |
4762155 | Gruber | Aug 1988 | A |
4786308 | Colling | Nov 1988 | A |
4875537 | Garnatz et al. | Oct 1989 | A |
4895250 | Schifrin | Jan 1990 | A |
4921831 | Nakai et al. | May 1990 | A |
4925343 | Raible et al. | May 1990 | A |
5037690 | Van der Kooy | Aug 1991 | A |
5060598 | Richards | Oct 1991 | A |
5074379 | Batrice | Dec 1991 | A |
5092457 | Islava et al. | Mar 1992 | A |
5106648 | Williams | Apr 1992 | A |
5180033 | Wilson | Jan 1993 | A |
5195465 | Webb et al. | Mar 1993 | A |
5215407 | Brelsford | Jun 1993 | A |
5218783 | Langezaal et al. | Jun 1993 | A |
5300127 | Williams | Apr 1994 | A |
5307577 | Werling | May 1994 | A |
5337416 | Ryan et al. | Aug 1994 | A |
5337496 | Glorioso | Aug 1994 | A |
5338131 | Bestmann | Aug 1994 | A |
5340642 | Baumgartl et al. | Aug 1994 | A |
5404209 | Matsuoka et al. | Apr 1995 | A |
5419945 | Lopez | May 1995 | A |
5422330 | Kaylor | Jun 1995 | A |
5424404 | Ruske et al. | Jun 1995 | A |
5425597 | Bestmann | Jun 1995 | A |
5458662 | Teyone | Oct 1995 | A |
5496378 | Hengelsberg et al. | Mar 1996 | A |
5516486 | Wright | May 1996 | A |
5587277 | Yamashita et al. | Dec 1996 | A |
5630377 | Kumlin | May 1997 | A |
5658571 | Gopalan et al. | Aug 1997 | A |
5678954 | Bestmann | Oct 1997 | A |
5710190 | Jane et al. | Jan 1998 | A |
5716840 | Kahler et al. | Feb 1998 | A |
5727499 | Armington et al. | Mar 1998 | A |
5728790 | Seki et al. | Mar 1998 | A |
5747549 | Tsurugai et al. | May 1998 | A |
5750661 | Schloesser et al. | May 1998 | A |
5750742 | Schroder et al. | May 1998 | A |
5772721 | Kazemzadeh | Jun 1998 | A |
5839674 | Ellis | Nov 1998 | A |
5840632 | Miller | Nov 1998 | A |
5843203 | Lindsay et al. | Dec 1998 | A |
5860391 | Maxwell | Jan 1999 | A |
5883025 | Karstens | Mar 1999 | A |
5922189 | Santos | Jul 1999 | A |
5927049 | Simard | Jul 1999 | A |
5942457 | Santos | Aug 1999 | A |
5976210 | Sensibaugh | Nov 1999 | A |
6019063 | Haubensak et al. | Feb 2000 | A |
6027652 | Hondroulis et al. | Feb 2000 | A |
6032409 | Obonai | Mar 2000 | A |
6036971 | Kimoto et al. | Mar 2000 | A |
6041546 | Baranova | Mar 2000 | A |
6048968 | Etzbach et al. | Apr 2000 | A |
6053125 | Kory et al. | Apr 2000 | A |
6071487 | Campion et al. | Jun 2000 | A |
6076299 | Spittle et al. | Jun 2000 | A |
6083621 | Sugimoto | Jul 2000 | A |
6085806 | Davis et al. | Jul 2000 | A |
6107242 | Ackerman et al. | Aug 2000 | A |
6189260 | Kusey et al. | Feb 2001 | B1 |
6197081 | Schmidt | Mar 2001 | B1 |
6218321 | Lorcks et al. | Apr 2001 | B1 |
6219968 | Belger et al. | Apr 2001 | B1 |
6271190 | Boskamp et al. | Aug 2001 | B1 |
6286626 | Evans | Sep 2001 | B1 |
6322734 | Zanten et al. | Nov 2001 | B1 |
6357176 | Baldwin et al. | Mar 2002 | B2 |
6360478 | Spittle | Mar 2002 | B1 |
6391120 | Silva | May 2002 | B1 |
6395166 | Haydock | May 2002 | B1 |
6403134 | Nayyar et al. | Jun 2002 | B1 |
6408568 | Kusey et al. | Jun 2002 | B1 |
6444467 | Fan et al. | Sep 2002 | B1 |
6455149 | Hagen et al. | Sep 2002 | B1 |
6472588 | Haigler et al. | Oct 2002 | B1 |
6479433 | Hann et al. | Nov 2002 | B1 |
6491840 | Frankenbach et al. | Dec 2002 | B1 |
6495058 | Frankenbach et al. | Dec 2002 | B1 |
6508306 | Reddy et al. | Jan 2003 | B1 |
6517600 | Dinel | Feb 2003 | B1 |
6539882 | Layt et al. | Apr 2003 | B2 |
6547493 | Spangler et al. | Apr 2003 | B2 |
6596324 | Homan | Jul 2003 | B1 |
6609331 | Stamp | Aug 2003 | B1 |
6620507 | Kadowaki et al. | Sep 2003 | B2 |
6645392 | Frankenbach et al. | Nov 2003 | B2 |
6652766 | Frankenbach et al. | Nov 2003 | B1 |
6689609 | Fan et al. | Feb 2004 | B1 |
6695544 | Knudson et al. | Feb 2004 | B2 |
6696284 | Haridas et al. | Feb 2004 | B2 |
6709202 | Spangler et al. | Mar 2004 | B2 |
6711850 | Yelanich et al. | Mar 2004 | B2 |
6732666 | Layt | May 2004 | B2 |
6773594 | Van der Wijngaart | Aug 2004 | B1 |
6790819 | Trinh et al. | Sep 2004 | B2 |
6851221 | Layt et al. | Feb 2005 | B2 |
6861131 | Evans | Mar 2005 | B2 |
6863027 | Silva | Mar 2005 | B1 |
6863816 | Austin et al. | Mar 2005 | B2 |
6881338 | Austin et al. | Apr 2005 | B2 |
6893193 | Santha | May 2005 | B2 |
6896805 | Austin | May 2005 | B2 |
6903197 | Tresch et al. | Jun 2005 | B2 |
6910835 | Spangler et al. | Jun 2005 | B2 |
6913423 | Spangler et al. | Jul 2005 | B2 |
6933371 | Schroder et al. | Aug 2005 | B2 |
6946295 | Polonenko et al. | Sep 2005 | B2 |
7005410 | Trinh et al. | Feb 2006 | B2 |
7141659 | Lynch et al. | Feb 2006 | B2 |
7012053 | Barnabas et al. | Mar 2006 | B1 |
7029586 | Austin et al. | Apr 2006 | B2 |
7036272 | Stoever | May 2006 | B2 |
7087169 | Austin | Aug 2006 | B2 |
7091400 | Haigler et al. | Aug 2006 | B2 |
7098324 | Haigler et al. | Aug 2006 | B2 |
7109015 | Liao | Sep 2006 | B2 |
7117634 | Pelton | Oct 2006 | B2 |
7119166 | Lin | Oct 2006 | B2 |
7165358 | Wright | Jan 2007 | B2 |
7485171 | Lynch et al. | Feb 2009 | B2 |
7587856 | Rubin et al. | Sep 2009 | B2 |
7607258 | Holmenlund | Oct 2009 | B2 |
20010013198 | Krysiak et al. | Aug 2001 | A1 |
20010053545 | Engwar | Dec 2001 | A1 |
20020007592 | Mischo | Jan 2002 | A1 |
20020011024 | Baldwin et al. | Jan 2002 | A1 |
20020062770 | Layt | May 2002 | A1 |
20020073616 | Pelton | Jun 2002 | A1 |
20020112293 | Trinh et al. | Aug 2002 | A1 |
20020129545 | Morris | Sep 2002 | A1 |
20020131826 | Spangler | Sep 2002 | A1 |
20020131827 | Spangler | Sep 2002 | A1 |
20020194649 | Fan et al. | Dec 2002 | A1 |
20030031511 | Tyler | Feb 2003 | A1 |
20030061639 | Polonenko et al. | Mar 2003 | A1 |
20030070191 | Haigler et al. | Apr 2003 | A1 |
20030086764 | Knudson et al. | May 2003 | A1 |
20030089152 | Yelanich et al. | May 2003 | A1 |
20030106097 | Haigler et al. | Jun 2003 | A1 |
20030140553 | Moore | Jul 2003 | A1 |
20030146164 | Robson | Aug 2003 | A1 |
20030146405 | Frankenbach et al. | Aug 2003 | A1 |
20030157668 | Polonenko et al. | Aug 2003 | A1 |
20030172699 | Phinney | Sep 2003 | A1 |
20030183140 | Layt | Oct 2003 | A1 |
20030209686 | Frankenbach et al. | Nov 2003 | A1 |
20030230529 | Austin et al. | Dec 2003 | A1 |
20040000517 | Austin et al. | Jan 2004 | A1 |
20040005198 | Spangler et al. | Jan 2004 | A1 |
20040025422 | Macquoid et al. | Feb 2004 | A1 |
20040040209 | Layt et al. | Mar 2004 | A1 |
20040049808 | Haigler et al. | Mar 2004 | A1 |
20040049980 | Principe | Mar 2004 | A1 |
20040065005 | Morris | Apr 2004 | A1 |
20040098270 | Obayashi et al. | May 2004 | A1 |
20040111967 | Raap et al. | Jun 2004 | A1 |
20040141816 | Spangler et al. | Jul 2004 | A1 |
20040156687 | Knudson et al. | Aug 2004 | A1 |
20040209991 | Piret et al. | Oct 2004 | A1 |
20040211721 | Stamets | Oct 2004 | A1 |
20040216374 | Davids | Nov 2004 | A1 |
20040221397 | Trinh et al. | Nov 2004 | A1 |
20040228692 | McCamy | Nov 2004 | A1 |
20040237387 | McCamy | Dec 2004 | A1 |
20040237388 | Moore | Dec 2004 | A1 |
20050034367 | Morrow | Feb 2005 | A1 |
20050060811 | Smith et al. | Mar 2005 | A1 |
20050061045 | Lynch et al. | Mar 2005 | A1 |
20050076564 | Castleberry | Apr 2005 | A1 |
20050082222 | Austin | Apr 2005 | A1 |
20050098759 | Frankenbach et al. | May 2005 | A1 |
20050102895 | Bissonnette et al. | May 2005 | A1 |
20050124065 | Fan | Jun 2005 | A1 |
20050141966 | Greene | Jun 2005 | A1 |
20050161407 | McPhillips | Jul 2005 | A1 |
20050176583 | Stamets | Aug 2005 | A1 |
20050183331 | Kania | Aug 2005 | A1 |
20050204620 | Butterfield et al. | Sep 2005 | A1 |
20050218071 | Austin et al. | Oct 2005 | A1 |
20050235558 | Carrillo | Oct 2005 | A1 |
20050236315 | McPhillips | Oct 2005 | A1 |
20050241231 | Bissonnette et al. | Nov 2005 | A1 |
20050246954 | Bissonnette et al. | Nov 2005 | A1 |
20050246955 | Bissonnette et al. | Nov 2005 | A1 |
20050254899 | Tyler | Nov 2005 | A1 |
20050257424 | Bissonnette et al. | Nov 2005 | A1 |
20050269260 | Austin | Dec 2005 | A1 |
20050274074 | Stamp | Dec 2005 | A1 |
20060032804 | McPhillips | Feb 2006 | A1 |
20060070294 | Spittle | Apr 2006 | A1 |
20060088935 | Fan et al. | Apr 2006 | A1 |
20060101881 | Carin et al. | May 2006 | A1 |
20060107589 | Rubin | May 2006 | A1 |
20060112629 | Wright | Jun 2006 | A1 |
20060160907 | Stamp | Jul 2006 | A1 |
20060168881 | Straumietis | Aug 2006 | A1 |
20060174379 | Haigler et al. | Aug 2006 | A1 |
20060179711 | Bissonnette et al. | Aug 2006 | A1 |
20060185235 | Bono | Aug 2006 | A1 |
20060207170 | Smith | Sep 2006 | A1 |
20060237363 | Austin et al. | Oct 2006 | A1 |
20060248796 | Hashimoto et al. | Nov 2006 | A1 |
20070022661 | Slater | Feb 2007 | A1 |
20070094928 | Hunter | May 2007 | A1 |
20070209277 | Schuck et al. | Sep 2007 | A1 |
20080039605 | Qiu | Feb 2008 | A1 |
20080155897 | Van de Wetering | Jul 2008 | A1 |
20080202024 | Spittle et al. | Aug 2008 | A1 |
20080216404 | Jarvis | Sep 2008 | A1 |
20080236037 | Rose | Oct 2008 | A1 |
20080280760 | Oliver | Nov 2008 | A1 |
20080287295 | Rubin | Nov 2008 | A1 |
20090019765 | Kosinski | Jan 2009 | A1 |
20090113791 | Bertin et al. | May 2009 | A1 |
20090139927 | Kania et al. | Jun 2009 | A1 |
20090200241 | Harman et al. | Aug 2009 | A1 |
20090253576 | Ikin | Oct 2009 | A1 |
Number | Date | Country |
---|---|---|
1328744 | Apr 1994 | CA |
1145193 | Mar 1963 | DE |
10063017 | Jul 2002 | DE |
102004038299 | Mar 2006 | DE |
0487655 | Jun 1992 | EP |
512272 | Nov 1992 | EP |
0640280 | Mar 1995 | EP |
736494 | Oct 1996 | EP |
0786496 | Jul 1997 | EP |
849243 | Jun 1998 | EP |
0867112 | Sep 1998 | EP |
849243 | Dec 1998 | EP |
0962129 | Mar 2003 | EP |
1625785 | Feb 2006 | EP |
393783 | Jun 1933 | GB |
1491940 | Nov 1977 | GB |
2137609 | Nov 1984 | GB |
2272903 | Jun 1994 | GB |
2308538 | Jul 1997 | GB |
2332353 | Jun 1999 | GB |
10042689 | Feb 1998 | JP |
11056017 | Mar 1999 | JP |
2002238347 | Aug 2002 | JP |
960013590 | Oct 1996 | KR |
20020002030 | Jan 2002 | KR |
20020068556 | Aug 2002 | KR |
20020085189 | Nov 2002 | KR |
20020092752 | Dec 2002 | KR |
20030052374 | Jun 2003 | KR |
20030052375 | Jun 2003 | KR |
20040062497 | Jul 2004 | KR |
20040067336 | Jul 2004 | KR |
PA02004768 | Dec 2004 | MX |
9401955 | Jul 1996 | NL |
WO 9103149 | Mar 1991 | WO |
WO 9412576 | Jun 1994 | WO |
WO 9412576 | Jun 1994 | WO |
WO 9612687 | May 1996 | WO |
WO 9907943 | Feb 1999 | WO |
WO 0113706 | Mar 2001 | WO |
WO 0157156 | Aug 2001 | WO |
WO 0202889 | Jan 2002 | WO |
WO 03037069 | May 2003 | WO |
WO 2004037748 | May 2004 | WO |
WO 2004078892 | Sep 2004 | WO |
WO 2004098270 | Nov 2004 | WO |
WO 2005070852 | Aug 2005 | WO |
WO 2005095337 | Oct 2005 | WO |
WO 2006025657 | Mar 2006 | WO |
WO 2007009249 | Jan 2007 | WO |
WO 2008025027 | Feb 2008 | WO |
WO 2008048778 | Apr 2008 | WO |
WO 2008114953 | Sep 2008 | WO |
WO 2009009805 | Jan 2009 | WO |
Number | Date | Country | |
---|---|---|---|
20100180501 A1 | Jul 2010 | US |
Number | Date | Country | |
---|---|---|---|
61000818 | Oct 2007 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 12260605 | Oct 2008 | US |
Child | 12749222 | US |