Title of Invention

NEW METAL STRIP PRODUCT

Abstract

The present invention relates to a coated steel strip product with a dense and hard abrasion resistant coating on one side or both sides of said strip. The thickness of said coating is in total maximally 25 urn, the hardness of said coating is at least 600 HV and the tensile strength of the steel strip substrate is at least 1200 MPa. The coating is preferably applied by electron beam evaporation and the coating may be, e.g., of A1203. The coated metal strip is suitable for shaving equipment, medical instruments, utility and industrial knives as well as saw applications.

Full Text

The present invention relates to a new coated steel strip material with a very hard and dense coating, it also relates to a method of manufacturing such a coated steel strip in a continuous roll-to-roll process which results in a very good adhesion of a hard and dense coating on a metal strip substrate. In particular, it relates to coated steel strips, which have such a good adhesion of the hard coating that they are suitable for use in shaving equipment, medical instruments, utility and industrial knives as well as saw applications. Background to the invention and prior Art Coated steel products can be used in various applications. One example is in the manufacture of knives, such as as utility knives, e.g. slicers, carving knives, bread knives, butcher's knives, mixer blades, hunting and fishing knives, pocket knives, and industrial knives for cutting synthetic fibre, paper, plastic film, fabrics and carpets. Furthermore, these products can be used in saw applications and as medical instruments and surgical knives. Another example is in shaving applications, such as razor blades and cutters. Just to name a few. These are all applications where a hard and dense wear coating may be suitable, or even needed. Wear, which for example can result in that the coating is torn of or cracking. These are also applications which need to have hard and sharp edges and cutting surfaces. Furthermore, many of the applications listed above are used in corrosive environments and are therefore requiring a corrosion resistant surface. For cost reasons, a continuous roll-to-roll coating process, preferably integrated in the production of the stee strip, is required. Further, for quality reasons, a dense coating with very good adhesion to the substrate is of advantage. From a cost perspective, it is also a further advantage if there is such a good adhesion of the abrasion resistant coating that there is no need of any separate bond-coat. The good adhesion of a dense coating is needed for the functional quality of the finished product. A poor adhesion, or a porous or coarse coating, would cause problems during usage of for example an industrial knife or saw, e.g., that the coating starts to flake off, that grains or small pieces are torn off, or that fissure problems occur. All in all, this is not acceptable from a quality and cost perspective. There are several common methods of making a coating and also several different types of coatings that are being used. As examples can be mentioned: ¦ Ceramic coatings, often consisting of AI2O3 with possible additions of T1O2 and/or ZrO2. This type of coating is normally applied by using a thermal spray method. Thermal spray methods have normally some major drawbacks. The formed coating Is rough which means that polishing or other further processing must usually be done to the surface after the coating. A thermal spray coating also usually includes a high degree of porosity, implying that a thin dense coating normally can not be achieved. Furthermore, the thickness of thermal sprayed coatings is normally rather high. During usage, a thick and coarse coating has an increased risk of fissure formation or that grains tear off from the surface. In many cases expensive nickel or nickel alloys must also be used as a bond-coat in order to improve the adhesion of the ceramic coating. ¦ Metallic coatings, often consisting of pure nickel or chromium, or in the form of a compound such as nickel-phosphorus. These types of metallic coatings are normally applied by using a plating method, and especially electrolytic plating. Electrolytic plating methods have some drawbacks, one major being the difficulty to obtain an even thickness and also that the adhesion of the coating can be poor. Also, plating processes are not environmentally friendly, on the contrary, these processes are often causing environmental problems. ¦ Combinations of coatings, such as a nickel coating comprising abrasion resistant particles, e.g., SiC. This method also has some drawbacks, in principle the same drawbacks as for electrolytic plating as described above, but also that nickel is used to a large extent as a bond-coat, meaning that the coating is very expensive. Thus, the methods as described in the examples above are not suitable for the present invention. Therefore, it is a primary object of the present invention to provide a hard and abrasion resistant coated metal strip with improved adhesion between a dense coating and the substrate. A further object of the present invention is to obtain a cost-efficient coating in a continuous roll-to-roll process integrated in the production of a steel strip. A further object of the present invention is to obtain a coating with a thickness as uniform as possible. These and other objects have been surprisingly attained by providing a coated steel product according to claim 1. Further preferred embodiments are defined in the dependent claims. Brief Description of the Drawings Figure 1 shows a schematic cross-section of a metal strip according to one embodiment of the invention. Figure 2 shows a schematic cross-section of a metal strip according to a second embodiment of the invention. Figure 3 shows schematically a production line for the manufacturing of a coated metal strip material according to the invention. Detailed description of the invention A suitable coating for the use in shaving equipment, medical instruments, utility and industrial knives as well as saw applications is a dense and abrasion resistant coating with good adhesion. These are all applications in which wear often arise on the blades. For example in the case of shaving equipment, a razor blade should be able to withstand the wear during shaving, thereby keeping a sharp shaving edge, and at the same time withstand the corrosive environment. A suitable coating for use in the above mentioned applications has a dense layer of an abrasion resistant coating with good adhesion, which is hard but also tough enough to withstand the work-load and pressure during usage, without showing any tendency to brittleness or tearing off. To prevent the end product from wear, it is suitable to have the product coated with at least one layer of abrasion resistant coating. Both one-sided and two-sided coatings can be used. One-sided coatings are preferable from a cost perspective and should be used whenever possible. For blade applications used in more severe conditions, or during longer running times, two-sided coatings may be preferable. Otherwise, problems may occur with, e.g., plastic deformation along the edge on the uncoated side, or that there is a material build-up along the edge of the uncoated side, which occasionally may be ripped off from a spot, causing material to locally be torn away from the edge of the blade. The method described in the present invention is suitable for thin coatings of hard and dense abrasion resistant coatings in thicknesses on each side up to 25 µm in total, normally up to 20 µrn in total, preferably up to 15 µm in total, or at the best maximum 12 µm or even maximum 10 µm in total, is preferable from a cost perspective. If thicker coatings are to be coated, an optimum in cost versus properties may be achieved by using multi-layers with up to 10 layers, and where each layer is between 0,1 to 15 µm thick, suitably between 0,1 to 10 µm, or more suitably 0,1 to 7 µm, preferably 0,1 to 5 µm and even more preferably 0,1 to 3 µrn. The coating should be sufficiently wear-resistant in order to withstand the wear and shear exerted by the treated material, on the other hand it should not be too thick, due to economical reasons and fragility/brittleness. The coating is performed at a rate of minimum 2,5 meters per minute, preferably min 5 m/min, most preferably min 10 m/min. The abrasion resistance can be achieved by depositing at least one layer of dense oxide coating in the form of Al2O3, TiO2 or ZrO2, or mixtures of these oxides, preferably AI2O3-based. Depending on the requirements, an optimum of required hardness and toughness can be achieved by using mixed oxides in the coating. This can be achieved by co-evaporation of aluminum oxide and another selected oxide. Preferably it can be a co-evaporation of aluminum oxide and any other oxide, preferably TiO2 and/or ZrO2. Multi-layers may also be used in order to enable a combination of oxides so as to optimize hardness and toughness by having up to 10 layers with different oxides in the layers. As an alternative to the above-described abrasion resistant layer consisting of essentially oxides, also other dense and hard coatings such as metallic coatings can be used in the present invention. Hard metallic coatings such as essentially pure Cr may be used if a simple and cheap coating is to be preferred in order to reduce cost as much as possible. Yet another embodiment of the present invention is to use coatings of transition metal carbides and/or nitrides, such as e.g. TiN, TiC or CrN, also in some cases in combination with an oxide in the form of AI2O3, TiO2 or ZrO2, or mixtures of these oxides, preferably AI2O3 -based. By using the multi-layer system with up to 10 layers, a coating existing of a combination of several layers of different oxides and nitrides can even further enhance the optimum of desired hardness and toughness. In order to withstand the wear and shear forces, the hardness of the thin coating should be above 600 HV, more suitably above 700 HV, preferably above 800 HV and most preferably above 900 HV. Naturally, the hardness of the coating is suitably adjusted/matched to the requirements of the intended use of the final product. The tolerances of each layer is maximum + /-10% of the layer thickness at strip widths up to 400 mm. This means that very tight tolerances can be achieved, which is of benefit for the precision during usage and the quality of the product. In comparison to plating or thermal spray this represents much higher tolerances. For instance, in plating there is a so called dog-bone effect, which results in varying thicknesses of the layer. In that case, the layer usually varies more than +/- 50% of the layer thickness. There is no need of any separate bond-coat, but nickel may still be used in one of the layers if it is required from a technical perspective, e.g., to enhance toughness. Since nickel is expensive it is usually used in very thin layers only, suitably between 0 to 2 µm, preferably between 0-1 µm and most preferably between 0-0,5 µm. However, any possible nickel layer would not be the layer adjacent to the substrate. Description of the substrate material to be coated The material to be coated should have a good basic mechanical strength, suitable for the intended application. Preferably, it should be a hardenable steel in a hardened and tempered condition, or alternatively a precipitation hardenable steel, which in the end condition can achieve a tensile strength level above 1200 MPa, or preferably more than 1300 MPa, or at the best above 1400 MPa, or even 1500 MPa. If the final coated product is intended for use in a corrosive environment, then the steel alloy should also have a sufficient addition of chromium to enable a good basic corrosion resistance. The Cr content should in this case be above 10% by weight, or at least 11%, or preferably a minimum of 12%. The coating method may be applied on any kind of product made of said type of steel alloy and in the form of a strip that has good hot workability and also can be cold-rolled to thin dimensions. The alloy should also be capable of readily being manufactured to shaving equipment like razor blades and/or cutters, medical instruments, utility and industrial knives as well as various saws, in a manufacturing process including steps such as forming, grinding, shaving, cutting, polishing, stamping, or the like. The thickness of the strip substrate material is usually between 0,015 mm to 5,0 mm and suitably between 0,03 mm to 3 mm. Preferably, it is between 0,03 to 2 mm, and even more preferably between 0,03 to 1,5 mm. Naturally, the thickness of the substrate is adapted to the intended use of the final product. The width of the substrate material depends on if the coating is made before or after the slitting operation. Appropriate widths are 1 to 1500 mm, suitably 1 to 1000 mm, or preferably 1 to 500 mm, or even more preferably between 5 and 500 mm. The length of the substrate material is suitably between 10 and 20 000 m, preferably between 100 and 20 000 m. Description of the Coating Method A variety of physical or chemical vaporation deposition methods for the application of the coating media and the coating process may be used as long as they provide a continuous uniform and adherent coating. As exemplary of deposition methods can be mentioned chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), physical vapor deposition (PVD) such as sputtering and evaporation by resistive heating, by electron beam, by induction, by arc resistance or by laser deposition methods, but for the present invention especially electron beam evaporation (EB) is preferred for the deposition. Optionally, the EB evaporation can be plasma activated to even further ensure good quality coatings of hard and dense coatings. For the present invention, it is a pre-requisite that the coating method is integrated in a roll-to-roll strip production line. The hard coating is then deposited by means of electron beam evaporation (EB) in a roll-to-roll process. If multi layers are needed, the formation of them can be achieved by integrating several EB deposition chambers in-line. The deposition of metallic coatings should be made under reduced atmosphere at a maximum pressure of 1 x 10-2 mbar with no addition of any reactive gas to ensure essentially pure metal films. The deposition of metal oxides should be performed under reduced pressure with an addition of an oxygen source as reactive gas in the chamber. A partial pressure of oxygen should be in the range 1 -100 x 10-4 mbar. If other types of coatings are to be achieved, e.g., transition metal carbides and/or nitrides such as TiN, TiC or CrN, or mixtures thereof with, e.g., metal oxides, the conditions during the coating should be adjusted with regard to the partial pressure of a reactive gas so as to enable the formation of the intended compound. In the case of oxygen a reactive gas such as H2O, O2 or O3, but preferably O2, may be used. In the case of nitrogen a reactive gas such as N2, NH3 or N2H4, but preferably N2, may be used. In the case of carbon, any carbon containing gas may be used as reactive gas, for an example CH4, C2H2 or C2H4. All these reactive EB evaporation processes may be plasma activated. To enable a good adhesion, different types of cleaning steps are used. First of all, the surface of the substrate material should be cleaned in a proper way to remove all oil residues, which otherwise may negatively affect the efficiency of the coating process and the adhesion and quality of the coating. Moreover, the very thin native oxide layer that normally always is present on a steel surface must be removed. This can preferably be done by including a pre-treatment of the surface before the deposition of the coating. In this roll-to- roll production line, the first production step is therefore preferably an ion assisted etching of the metallic strip surface to achieve good adhesion of the first coating [see Fig. 3]. Description of embodiments of the invention Two examples of embodiments of the invention will now be described in more details. The first example (Figure 1) comprises a coating 1,2 for a substrate material 3 in full strip width. The substrate material can be made of different alloys, such as a hardenable carbon steel or a hardenable stainless chromium steel. The other example (Figure 2) comprises a coating 4 of a steel strip 5, which before the coating process, has been both slitted and edge treated. During coating, both the main sides 7,8 and the narrow lateral sides 9,10 are coated, thereby obtaining a full covering coating around the scraping or cutting edges 11,12. Suitably, the lateral sides 9 and 10 are coated simulateneously with the somewhat narrower main side 7. The examples given are only intended as illustrative examples to the invention and may not serve as a limitation to the present innovation. The substrate material should have a composition suitable for hardening, which means: - Hardenable carbon steel of 0,1-1,5% C, 0,001-4% Cr, 0,01-1,5% Mn, 0,01- 1,5% Si, up to 1% Ni, 0,001-0,5%N, rest essentially Fe; or - Hardenable chromium steels of 0,1-1,5% C, 10-16% Cr, 0,001-1% Ni, 0,01- 1,5% Mn, 0,01-1,5% Si, up to 3% Mo, 0,001-0,5% N, rest essentially Fe; or - Precipitation hardenable steels of: 0,001-0,3% C, 10-16% Cr, 4-12% Ni, 0,1- 1,5% Ti, 0,01-1,0% Al, 0,01-6% Mo, 0,001-4% Cu, 0,001-0,3% N, 0,01-1,5% Mn, 0,01-1,5% Si, rest essentially Fe. Example 1 The chemical compositions of the substrate materials in the example are according to the internal Sandvik designation 20C2 and 13C26, with essentially the following nominal composition: Sandvik 20C2:1,0% C, 1,4% Cr, 0,3% Si and 0,3% Mn (by weight); and Sandvik 13C26: 0,7% C, 13% Cr, 0,4% Si and 0,7% Mn (by weight). Firstly, the substrate materials are produced by ordinary metallurgical steelmaking to a chemical composition as described above. After this, they are hot-rolled down to an intermediate size, and thereafter cold-rolled in several steps with a number of recrystallization steps between said rolling steps, until a final thickness of 0,2 mm and a width of maximally 400 mm. Thereafter the strip steels are hardened and tempered to the required mechanical strength level, which according to the present invention should be at least 1200 MPa. The surface of the substrate material is then cleaned in a proper way to remove oil residuals from the rolling and hardening operations. Thereafter, the coating process takes place in a continuous process line, starting with decoiling equipment. The first step in the roll-to-roll process line can be a vacuum chamber or an entrance vacuum lock followed by an etch chamber, in which ion assisted etching takes place in order to remove the thin oxide layer on the substrate material. The strip then enters into the EB evaporation chamber(s) in which deposition of an oxide takes place, in this example AI2O3 is selected as the material to be deposited. An oxide layer of normally 0,1 up to 25 µm is deposited; the preferred thickness depends on the application. In the examples described here, a thickness of 2 µm is deposited by using one EB evaporation chamber. After the EB evaporation, the coated strip material passes through the exit vacuum chamber or exit vacuum lock before it is being coiled on to a coiler. The coated strip material can now, if needed, be further processed by for an example slitting and edge treatment, to obtain the preferred final dimension and edge condition of the intended final application. It is an advantage if an additional coating along the edge of for example a knife blade application can be made in a continuous coating process using EB evaporation, but also other processes may be used. Preferably, an additional coating along the edge of a finished blade is of same type as the coating applied on the strip material according to the present invention. The end product as described in this examples, i.e. a coated 20C2 and 13C26-strip material respectively, in a strip thickness of 0,2 mm and with a thin coating of Al2O3 of 2 µm, has a very good adhesion of the coated layer and is thus suitable to use especially for the manufacturing of industrial knives. The roll-to-roll electron beam evaporation process referred to above is illustrated in Figure 3. The first part of such a production line is the uncoiler 13 within a vacuum chamber 14, then the in-line ion assisted etching chamber 15, followed by a series of EB evaporation chambers 16, the number of EB evaporation chambers needed can vary from 1 up to 10 chambers, this to achieve a multi-layered structure, if so desired. All the EB evaporation chambers 16 are equipped with EB guns 17 and water-cooled copper crucibles 18 for the evaporation. After these chambers comes the exit vacuum chamber 19 and the recoiler 20 for the coated strip material, the recoiler being located within vacuum chamber 19. The vacuum chambers 14 and 19 may also be replaced by an entrance vacuum lock system and an exit vacuum lock system, respectively. In the latter case, the uncoiler 13 and the coiler 20 are placed in the open air. Example 2 The chemical composition of the substrate material in this example is according to the internal Sandvik designation 20C with essentially the following nominal composition: Sandvik 20C: 1,0% C, 0,2% Cr, 0,3% Si and 0,4% Mn (by weight). Firstly, the substrate material is produced by ordinary metallurgical steelmaking to a chemical composition as described above. The material is then hot-rolled down to an intermediate size, and thereafter cold-rolled in several steps with a number of recrystallization steps between said rolling steps, until a final thickness of 0,45 mm and a width of maximum 400 mm are attained. Thereafter, the steel strip is hardened and tempered to the required mechanical strength level, according to the present invention above 1200 MPa. The strip is afterwards slitted to a width corresponding to substantially twice the width of the final blade application. The edges along the slitted strip are then edge-treated, for example shaved, ground and polished, to the conditions and geometry considered suitable for the intended blade application. After this, the strip is submitted to a coating treatment fully analogous to Example 1, cf. also Figure 3. The end product will be a coated strip according to Figure 2, the coating material and thickness being the same as in Example 1. Now, the coated strip material can be slitted in the middle along section 6 to obtain two coated strips, each with the dimension and edge geometry suitable for a finished blade. In principle, only cutting into required final length remains. The end product as described in this example, i.e. a slitted, edge treated and coated strip material, in a strip thickness of 0,45 mm and a final slitted width of 100 mm, has a thin covering aluminum oxide layer of 2 µrn with a very good adhesion of the coated layer. This product can be cut into required length, depending on the final application, without any further processing. It may also, if required, be further processed, e.g., with an additional edge treatment or with additional coatings along the edge, or polishing or the like, in order to meet a specific customer demand. An additional coating along the edge of the finished blade application, can preferably be made in a continuous coating process using EB evaporation, but also other processes may be used. The coated steel product can be used in applications where a hard dense wear resistant coating may be suitable, such as: scissors and pruning shears, kitchen and bakery tools, handtools for plastering, trowels, medical instruments and surgical knives, razor blades, cutters, flapper valves, die cutting tools, saws and various knives in general, such as utility knives, e.g. slicers, carving knives, bread knives, butcher's knives, mixer blades, hunting and fishing knives, pocket knives and industrial knives for cutting synthetic fibre, paper, plastic film, fabrics and carpets. Thus, a strip material according to the present invention is also suitable to use in shaving equipment such as razor blades and cutters, and medical instruments such as thin surgical knives. The thickness of the substrate material is rather thin in these types of applications, normally between 0,015 to 0,75 mm and usually 0,015 to 0,6 mm and preferably 0,03 to 0,45 mm. The thickness of the coating can accordingly preferably be as thin as possible, normally in total between 0,1 to 5 µM and usually 0,1 to 3 µm and preferably 0,1 to 2 µm or even more preferably 0,1 to 1 µm. In this case it is thus preferred to have a small ratio between the thickness of the coating and the thickness of the strip material. The ratio is normally between 0,01% to 7% and preferably between 0,01 to 5%. One further use of the invention in this case is that the coating may be applied before the hardening and tempering treatment of the substrate material. The hard and dense coating should in this case be able to withstand a hardening temperature of minimum 400°C and preferably more than 800°C, and more preferably above 950°C, for holding times at hardening temperatures normally used in a hardening of said substrate material so as to obtain a tensile strength in accordance with the present invention, i.e., a minimum tensile strength of 1200 MPa. After such a hardening procedure, the properties of the thin layer should be maintained in accordance with the description of the present invention, i.e., the coating should have a good adhesion and be hard, dense and abrasion resistant and have a hardness of at least 600 HV, usually 700 HV, preferably 800 HV and more preferably 900 HV. For further illustration, typical dimensions in the case of a strip material for razor blades would be a substrate material with a thickness below 0,15 mm, normally less than 0,10 mm, and a strip width of about 400 mm ,and a coating thickness of below 5 µm, usually 2 µm, normally less than around 1 µm, or even thinner. A strip material according to the present invention is suitable to use also in various utility and industrial knife applications and also saw applications. The thickness of the substrate material is rather thick in this type of application, normally between 0,1 to 5 mm and usually between 0,2 to 3 mm. The thickness of the coating is however kept as thin as possible, normally in total between 0,1 to 10 µrn and usually 0,1 to 5 µrn and preferably 0,1 to 3 µm or even more preferably 0,1 to 2 µm. In this case it is thus preferred to have a small ratio between the thickness of the coating and the thickness of the strip material. The ratio is normally between 0,001% to 7% and preferably between 0,01 to 5%. One further use of the invention is that the coating may be applied before the hardening and tempering treatment of the substrate material. The hard and dense coating should in this case be able to withstand a hardening temperature of minimum 400°C and preferably more than 800°C, and more preferably above 950°C, for holding times at hardening temperature normally used in a hardening of said substrate material so as to obtain a tensile strength in accordance with the present invention, i.e. a minimum of 1200 MPa. After such a hardening procedure, the properties of the thin coating should be maintained in accordance with the description in the present invention, i.e. the coating should have a good adhesion and be hard, dense and abrasion resistant and have a hardness of minimum 600 HV, usually 700 HV, preferably 800 HV and more preferably 900 HV. Examples 1 and 2 above both show embodiments of the invention that in an analogous way apply for razor blades and/or thin surgical knives and/or utility and industrial knives and/or saw applications. Thus, these examples illustrate coating methods and substrate materials suitable for these applications. The only difference is the sequence order for hardening and tempering, which can be altered with the coating, as also decribed above. WE CLAIM : 1. A coated steel strip product with a dense and hard abrasion resistant coating on one side or both sides of said strip wherein the coating is applied directly on said strip substrate, the thickness of said coating is in total maximally 25 µm, the ratio between the thickness of the coating and the thickness of the strip material is 0.001-7%, the hardness of said coating is at least 600 HV and the tensile strength of the steel strip substrate is at least 1200 Mpa wherein said coating being a metallic coating containing essentially Cr. 2. Product as claimed in claim 1 wherein the thickness of the strip substrate is between 0.015 mm and 5.0 mm. 3. Product as claimed in claim 1 or 2, wherein the strip substrate is made of hardenable carbon steel, or hardenable stainless chromium steel, or precipitation hardenable strip steel. 4. Product as claimed in any of the preceding claims, wherein the ratio between the thickness of the coating and the thickness of the strip substrate is 0.01-7%, preferably 0.01-5%. 5. Product as claimed in any of the preceding claims, wherein the coating has a multi-layer constitution of up to 10 layers. 6. Product as claimed in claim 5, wherein the each individual layer has a thickness of between 0.1 to 15 µm. 7. Product as claimed in claim 5, wherein there is also at least one layer of nickel in thickness up to 2 µm, this nickel layer not being adjacent the strip substrate. 8. Method of manufacturing a coated steel strip product as claimed in any of the preceding claims, wherein said product is produced at a rate of at least 2.5 m/min in a continuous roll-to-roll process included in a strip production line using electron beam evaporation including an etch chamber in-line. 9. Product as claimed in claims 1 to 7 wherein the coated steel strip forms a shaving product such as a razor blade or cutter. 10. Product as claimed in claims 1 to 7 wherein the coated steel strip forms a knife such as a utility knife, an industrial knife or a surgical knife. 11. Product as claimed in claims 1 to 7 wherein the coated steel strip forms a saw such as a hand saw or an industrial saw application. The present invention relates to a coated steel strip product with a dense and hard abrasion resistant coating on one side or both sides of said strip. The thickness of said coating is in total maximally 25 urn, the hardness of said coating is at least 600 HV and the tensile strength of the steel strip substrate is at least 1200 MPa. The coating is preferably applied by electron beam evaporation and the coating may be, e.g., of A1203. The coated metal strip is suitable for shaving equipment, medical instruments, utility and industrial knives as well as saw applications.

Documents:

00066-kolnp-2006-abstract.pdf

00066-kolnp-2006-claims.pdf

00066-kolnp-2006-description complete.pdf

00066-kolnp-2006-drawings.pdf

00066-kolnp-2006-form 1.pdf

00066-kolnp-2006-form 2.pdf

00066-kolnp-2006-form 3.pdf

00066-kolnp-2006-form 5.pdf

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00066-kolnp-2006-pct forms.pdf

66-kolnp-2006-granted-abstract.pdf

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66-kolnp-2006-granted-examination report.pdf

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