ES2585236B1 - High-density non-toxic composites for hunting, shooting, fishing and other sports uses composed of biodegradable or recycled matrix and ceramic loading - Google Patents
High-density non-toxic composites for hunting, shooting, fishing and other sports uses composed of biodegradable or recycled matrix and ceramic loading Download PDFInfo
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- ES2585236B1 ES2585236B1 ES201630061A ES201630061A ES2585236B1 ES 2585236 B1 ES2585236 B1 ES 2585236B1 ES 201630061 A ES201630061 A ES 201630061A ES 201630061 A ES201630061 A ES 201630061A ES 2585236 B1 ES2585236 B1 ES 2585236B1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F42—AMMUNITION; BLASTING
- F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
- F42B12/00—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material
- F42B12/72—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the material
Abstract
La presente invención titulada "Composites no tóxicos de alta densidad para caza, tiro, pesca y otros usos deportivos compuestos por matriz biodegradable o reciclada y carga cerámica" dispone una serie de materiales compuestos de alta densidad diseñados para la sustitución del plomo en la caza, el tiro, la pesca y otros usos deportivos. Estos materiales están compuestos por matriz polimérica, preferiblemente biodegradable o reciclada y carga cerámica, concretamente partículas de carburo de wolframio. La matriz polimérica puede estar constituida a partir de cualquier polímero ecológico conocido o incluso mezclas entre varios de ellos. A diferencia del plomo, estos compuestos son completamente respetuosos con el medio ambiente, carecen de toxicidad y sus propiedades mecánicas son variables dependiendo del polímero empleado como matriz, el porcentaje de carga y el tamaño de las partículas de esta. Por lo tanto las propiedades del material podrán ajustarse fácilmente en función del uso que vaya a desempeñar.The present invention entitled "High-density non-toxic composites for hunting, shooting, fishing and other sports uses composed of biodegradable or recycled matrix and ceramic loading" provides a series of high-density composite materials designed for the replacement of lead in hunting, shooting, fishing and other sports uses. These materials are composed of polymeric matrix, preferably biodegradable or recycled and ceramic filler, specifically tungsten carbide particles. The polymer matrix can be constituted from any known ecological polymer or even mixtures between several of them. Unlike lead, these compounds are completely environmentally friendly, lack toxicity and their mechanical properties are variable depending on the polymer used as a matrix, the percentage of charge and the particle size of the latter. Therefore the properties of the material can be easily adjusted depending on the use it will perform.
Description
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D E S C R I P C I O ND E S C R I P C I O N
COMPOSITES NO TOXICOS DE ALTA DENSIDAD PARA CAZA, TIRO, PESCA Y OTROS USOS DEPORTIVOS COMPUESTOS POR MATRIZ BIODEGRADABLE O RECICLADA Y CARGA CERAMICAHIGH DENSITY NON-TOXIC COMPOSITES FOR HUNTING, SHOOTING, FISHING AND OTHER SPORTS USES COMPOSED BY BIODEGRADABLE OR RECYCLED MATRIX AND CERAMIC LOAD
SECTOR DE LA TECNICATECHNICAL SECTOR
La presente invention se encasilla entre el sector de la industria metal-ceramica y la de procesos de trasformacion de compuestos plasticos y pertenece al campo de aquellos materiales de alta densidad empleados en el mundo cinegetico y del deporte, en especial aquellos materiales que experimentan durante su vida util un vertido o exposition prolongada al medio ambiente inherente a la naturaleza de utilization, concretamente materiales empleados en la fabrication de munition ecologica para actividades como la caza o tiro y en la fabricacion de pesos ecologicos para la pesca entre otros usos deportivos.The present invention is classified between the metal-ceramic industry and the process of transformation of plastic compounds and belongs to the field of high density materials used in the cinematic and sports world, especially those materials that experience during their useful life a prolonged discharge or exposure to the environment inherent in the nature of utilization, specifically materials used in the manufacture of ecological munition for activities such as hunting or shooting and in the manufacture of ecological weights for fishing among other sports uses.
ANTECEDENTES DE LA INVENCIONBACKGROUND OF THE INVENTION
Actualmente el plomo es el material mayormente empleado en la fabricacion de municion de caza o tiro, al igual que en la de pesos para la pesca. Su alta densidad y ductilidad hacen que haya sido el material idoneo para este fin. Sin embargo, presenta una alta toxicidad que implica cierta contamination del medio ambiente y la muerte de multitud de especies, principalmente aves.Currently, lead is the material mostly used in the manufacture of hunting or shooting ammunition, as in the case of fishing weights. Its high density and ductility make it the ideal material for this purpose. However, it has a high toxicity that implies some environmental contamination and the death of many species, mainly birds.
Algunas patentes han apostado por la sustitucion del plomo realizando compuestos mediante mezclas de diferentes metales y aleaciones de alta densidad como es el caso de la patente ES2223305A1.Some patents have opted for the replacement of lead by making compounds using mixtures of different metals and high density alloys such as the ES2223305A1 patent.
Otras, como la patente US006101949A incorporan polvos de metales y aleaciones de metales no toxicos como son el wolframio y el ferrowolframio en matrices polimericas con caracter biodegradable. De esta forma los inventores consiguen una municion que se desintegrara por completo tras permanecer expuesta al medio durante un tiempo determinado y sin contaminarlo, aunque su fabricacion suponga la incorporation deOthers, such as US006101949A, incorporate metal powders and non-toxic metal alloys such as tungsten and ferro-tungsten in polymeric matrices with biodegradable character. In this way the inventors achieve a munition that will disintegrate completely after being exposed to the environment for a certain time and without contaminating it, even if its manufacture involves the incorporation of
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dicho metal virgen o aleacion metalica fabricada exclusivamente con este fin.said virgin metal or metal alloy manufactured exclusively for this purpose.
La recientemente solicitada patente ES2540789A1 describe la fabrication de munition de caza en su totalidad, tanto la vaina o carcasa como los proyectiles a partir de pollmeros biodegradables como la policaprolactona y cargas minerales inertes y no toxicas del grupo de los carbonatos y sales minerales, tales como el carbonato calcico, bicarbonato sodico o sulfato de bario. Dada la baja densidad de los materiales utilizados como carga, el rango de densidades que esta patente propone para sus proyectiles no excede de 6 g/cm3, densidad inferior a la del acero y por tanto altamente ineficaz en terminos de ballstica.The recently applied patent ES2540789A1 describes the manufacture of hunting munition in its entirety, both the sheath or shell and the shells from biodegradable polymers such as polycaprolactone and inert and non-toxic mineral fillers of the group of carbonates and mineral salts, such as Calcium carbonate, sodium bicarbonate or barium sulfate. Given the low density of the materials used as cargo, the range of densities that this patent proposes for its projectiles does not exceed 6 g / cm3, a density lower than that of steel and therefore highly inefficient in terms of ballistics.
La US5859090A es la principal patente en conflicto con la anterior ES2540789A1. Esta describe unicamente la fabricacion de la vaina o carcasa de proyectiles para caza a partir de pollmeros biodegradables como la policaprolactona, por lo que no tiene mayor relevancia ante la presente invention.US5859090A is the main patent in conflict with the previous ES2540789A1. This describes only the manufacture of the sheath or shell of projectiles for hunting from biodegradable polymers such as polycaprolactone, so it has no greater relevance to the present invention.
EXPLICACION DE LA INVENCIONEXPLANATION OF THE INVENTION
La presente invencion tiene como objeto el desarrollo y la fabricacion de materiales compuestos ecologicos alternativos al plomo principalmente para municion de caza o tiro y para pesos de pesca, empleando materiales polimericos y ceramicos no toxicos, reciclados o biodegradables, totalmente respetuosos con el medio ambiente. Tambien el diseno y fabricacion de dicha municion o pesos a partir del nuevo material compuesto desarrollado.The present invention has as its object the development and manufacture of ecological composite materials alternative to lead mainly for hunting or shooting ammunition and for fishing weights, using non-toxic, recycled or biodegradable polymeric and ceramic materials, totally respectful of the environment. Also the design and manufacture of said ammunition or weights from the new composite material developed.
La presente invencion dispone materiales compuestos ecologicos que comprenden una matriz polimerica biodegradable o reciclada y partlculas ceramicas incorporadas en su seno como refuerzo o carga. El principal uso de la invencion es la sustitucion del plomo y/o otros materiales de alta densidad en la fabricacion de los proyectiles contenidos en la municion de caza o tiro, ya sean balas, postas, perdigones, etc. Tambien en la fabricacion de todo tipo de pesos empleados en la pesca.The present invention provides ecological composite materials comprising a biodegradable or recycled polymer matrix and ceramic particles incorporated therein as reinforcement or filler. The main use of the invention is the replacement of lead and / or other high density materials in the manufacture of projectiles contained in the hunting or shooting ammunition, be they bullets, poles, pellets, etc. Also in the manufacture of all types of weights used in fishing.
La composition de estos materiales compuestos varla en funcion de las propiedades finales deseadas.The composition of these composite materials varies depending on the desired final properties.
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En su fabrication particular se emplean como matriz pollmeros reciclados (poliolefinas, poliesteres, poliamidas, poliuretanos, etc.) y/o biodegradables (derivados de los poliesteres alifaticos, almidones, etc.), no obstante cualquier pollmero termoplastico comercial o mezclas de varios pueden ser empleadas, siempre que no experimenten toxicidad o problemas ambientales derivados de su vertido al medio. Tambien es posible la adicion de plastificantes, lubricantes, antioxidantes y cualquier otro aditivo en la matriz polimerica, siempre y cuando estos no supongan un riesgo medioambiental.In its particular fabrication, recycled polymers (polyolefins, polyesters, polyamides, polyurethanes, etc.) and / or biodegradable (derivatives of aliphatic polyesters, starches, etc.) are used as matrix, however any commercial thermoplastic polymer or mixtures of several can be used, provided they do not experience toxicity or environmental problems arising from their discharge into the environment. It is also possible to add plasticizers, lubricants, antioxidants and any other additive in the polymer matrix, as long as these do not pose an environmental risk.
En su fabrication particular se emplea como carga o refuerzo polvo de carburo de wolframio reciclado de la industria metal-ceramica, este puede contener pequenos porcentajes de cobalto con poca influencia sobre el resultado final. Tambien puede emplearse polvo de carburo de tungsteno virgen, aunque de esta forma el producto final pierde parte de su caracter sostenible. La granulometrla del polvo de carburo de tungsteno a emplear es variable entre 0,1-500 pm, incluso se pueden combinar diferentes tamanos de polvo. La incorporation de estas partlculas ceramicas de alta densidad (en torno a 14,5 g/cm3) en el seno de la matriz polimerica, permite la obtencion de un material compuesto con una densidad y propiedades aptas para su uso como munition o peso en aplicaciones cinegeticas y deportivas.In its particular fabrication, recycled tungsten carbide powder from the metal-ceramic industry is used as filler or reinforcement, this may contain small percentages of cobalt with little influence on the final result. Virgin tungsten carbide powder can also be used, although in this way the final product loses part of its sustainable character. The granulometrla of the tungsten carbide powder to be used varies between 0.1-500 pm, even different sizes of powder can be combined. The incorporation of these high density ceramic particles (around 14.5 g / cm3) within the polymer matrix, allows obtaining a composite material with a density and properties suitable for use as munition or weight in applications cinegetics and sports.
En la fabrication particular del material compuesto de la invention, las fracciones volumetricas de polvo de carburo de wolframio empleado como carga o refuerzo oscilan entre 0,10 y 0,70. Las fracciones masicas de polvo de carburo de wolframio empleado como carga o refuerzo oscilan entre 0,60 y 0,98. La densidad final del material compuesto puede oscilar entre 2 y 11 g/cm3, en funcion de la proportion de material ceramico de refuerzo y de la densidad del pollmero empleado como matriz.In the particular manufacture of the composite material of the invention, the volumetric fractions of tungsten carbide powder used as filler or reinforcement range between 0.10 and 0.70. Mass fractions of tungsten carbide powder used as filler or reinforcement range between 0.60 and 0.98. The final density of the composite material can range between 2 and 11 g / cm3, depending on the proportion of ceramic reinforcement material and the density of the polymer used as matrix.
REALIZACION PREFERENTE DE LA INVENCIONPREFERRED EMBODIMENT OF THE INVENTION
EJEMPLO 1. (Datos exactos, fabrication de referencia)EXAMPLE 1. (Exact data, reference fabrication)
Se ha fabricado granza del material de la invention empleando matriz biodegradable, concretamente PLA Ingeo® 3260HP con densidad 1,24 g/cm3. Como carga se ha empleado carburo de wolframio en polvo (diametro aprox. 17-23 pm), gradoThe material of the invention has been manufactured using biodegradable matrix, specifically PLA Ingeo® 3260HP with a density of 1.24 g / cm3. As a load, tungsten carbide powder (diameter approx. 17-23 pm), grade has been used
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WCCT1850 suministrado por la empresa Ceratizit S.A. Su densidad real es de 14,5 g/cm3.WCCT1850 supplied by the company Ceratizit S.A. Its real density is 14.5 g / cm3.
Los compuestos han sido procesados a aproximadamente 200 °C mediante una extrusora de doble husillo corrotativa de laboratorio Prism Eurolab 16 con relacion L/D 25:1. Dosificando los componentes a las proporciones deseadas se han obtenido los compuestos preferidos de la Tabla 1.The compounds have been processed at approximately 200 ° C by means of a Prism Eurolab 16 laboratory corrotative double screw extruder with a 25: 1 L / D ratio. By dosing the components at the desired proportions, the preferred compounds of Table 1 have been obtained.
Tabla 1: Compuestos preferidos obtenidos.Table 1: Preferred compounds obtained.
- Muestra Sample
- Pollmero Matriz Fraccion masica refuerzo WC Fraccion volumetrica refuerzo WC Densidad real (g/cm3) Polymer Matrix Mass fraction reinforcement WC Volumetric fraction reinforcement WC Real density (g / cm3)
- PLA+70WC PLA + 70WC
- PLA 70 17 3,35 PLA 70 17 3.35
- PLA+80WC PLA + 80WC
- PLA 80 25 4,62 PLA 80 25 4.62
- PLA+90WC PLA + 90WC
- PLA 90 43 6,98 PLA 90 43 6.98
- PLA+95WC PLA + 95WC
- PLA 95 62 8,83 PLA 95 62 8.83
La granza del material compuesto obtenido con las diferentes proporciones de refuerzo fue obtenida cortando el hilo de compuesto a la salida de la extrusora mediante una pelletizadora. Esta granza fue empleada en la fabricacion de probetas para caracterizar el material mediante diferentes tipos de ensayos: densidad, resistencia a impacto y traccion, bio-desintegracion, SEM, etc.The pellet of the composite material obtained with the different reinforcement ratios was obtained by cutting the compound thread at the exit of the extruder by means of a pelletizer. This pellet was used in the manufacture of specimens to characterize the material through different types of tests: density, impact and tensile strength, bio-disintegration, SEM, etc.
Ensayos de desintegracion llevados a cabo segun normativa europea (UNE-EN ISO 20200:2006) han determinado que existe una considerable perdida de masa a lo largo del tiempo lo cual indica que existe una tendencia a la desintegracion total de las muestras si son expuestas durante periodos de tiempo mas largos. El polvo de carburo de wolframio permanecera en el medio como unico residuo sin presentar ningun riesgo para la flora ni la fauna ya que carece de toxicidad y posee una alta estabilidad qulmica.Disintegration tests carried out according to European regulations (UNE-EN ISO 20200: 2006) have determined that there is a considerable loss of mass over time, which indicates that there is a tendency for the total disintegration of the samples if they are exposed during longer periods of time. The tungsten carbide powder will remain in the medium as the only residue without presenting any risk to the flora or fauna since it lacks toxicity and has high chemical stability.
EJEMPLO 2. (Datos exactos, fabricacion de referencia)EXAMPLE 2. (Exact data, reference manufacturing)
Se ha fabricado granza del material de la invencion empleando matriz reciclada, concretamente polietileno de alta densidad (HDPE) reciclado grado de inyeccion con densidad de 0,97 g/cm3. Como carga se ha empleado carburo de wolframio en polvoThe material of the invention has been manufactured using recycled matrix, specifically high density polyethylene (HDPE) recycled injection grade with a density of 0.97 g / cm3. As a load, tungsten carbide powder has been used
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(diametro aprox. 17-23 pm), grado WCCT1850 suministrado por la empresa Ceratizit S.A. Su densidad real es de 14,5 g/cm3.(diameter approx. 17-23 pm), grade WCCT1850 supplied by Ceratizit S.A. Its real density is 14.5 g / cm3.
Los compuestos han sido procesados a aproximadamente 200 °C mediante una extrusora de doble husillo corrotativa de laboratorio Prism Eurolab 16 con relacion L/D 25:1. Dosificando los componentes a las proporciones deseadas se han obtenido los compuestos preferidos de la Tabla 2.The compounds have been processed at approximately 200 ° C by means of a Prism Eurolab 16 laboratory corrotative double screw extruder with a 25: 1 L / D ratio. By dosing the components at the desired proportions, the preferred compounds of Table 2 have been obtained.
Tabla 2: Compuestos preferidos obtenidos.Table 2: Preferred compounds obtained.
- Muestra Sample
- Pollmero Matriz Fraccion masica refuerzo WC Fraccion volumetrica refuerzo WC Densidad real (g/cm3) Polymer Matrix Mass fraction reinforcement WC Volumetric fraction reinforcement WC Real density (g / cm3)
- HDPE+70WC HDPE + 70WC
- HDPE 70 14 2,68 HDPE 70 14 2.68
- HDPE+80WC HDPE + 80WC
- HDPE 80 21 3,77 HDPE 80 21 3.77
- HDPE+90WC HDPE + 90WC
- HDPE 90 38 5,86 HDPE 90 38 5.86
- HDPE+95WC HDPE + 95WC
- HDPE 95 56 8,04 HDPE 95 56 8.04
La granza del material compuesto obtenido con las diferentes proporciones de refuerzo fue obtenida cortando el hilo de compuesto a la salida de la extrusora mediante una pelletizadora. Esta granza fue empleada en la fabricacion de probetas para caracterizar el material mediante diferentes tipos de ensayos: densidad, resistencia a impacto y traccion, bio-desintegracion, SEM, etc.The pellet of the composite material obtained with the different reinforcement ratios was obtained by cutting the compound thread at the exit of the extruder by means of a pelletizer. This pellet was used in the manufacture of specimens to characterize the material through different types of tests: density, impact and tensile strength, bio-disintegration, SEM, etc.
Ademas se conformo granza parcialmente esferica del compuesto de mayor densidad (HDPE+95WC con 8,04 g/cm3) con la cual se rellenaron algunos cartuchos de caza con exactamente 32 g y fueron disparados a modo de prueba para confirmar que la maleabilidad e integridad del material era similar a la de los proyectiles de plomo.In addition, partially spherical pellets of the highest density compound (HDPE + 95WC with 8.04 g / cm3) were formed with which some hunting cartridges were filled with exactly 32 g and were fired as a test to confirm that the malleability and integrity of the material was similar to that of lead shells.
En una fabricacion preferida en la que se desea obtener granza esferica para emplearla directamente como perdigones o postas para la caza/tiro, o pesos para la pesca, se incluira tras el proceso de extrusion un sistema periferico de corte en cabeza (Underwater Pelletizing System) que permite el corte del material compuesto bajo un flujo constante de agua. Mediante una serie de ajustes, este proceso de corte permite obtener granza practicamente esferica de diametro variable segun el tamano de los orificios de extrusion.In a preferred manufacture in which it is desired to obtain spherical pellets to be used directly as pellets or poles for hunting / shooting, or weights for fishing, a peripheral head cutting system (Underwater Pelletizing System) will be included after the extrusion process which allows the cutting of the composite material under a constant flow of water. By means of a series of adjustments, this cutting process allows to obtain practically spherical pellet of variable diameter according to the size of the extrusion holes.
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ES2585236B1 true ES2585236B1 (en) | 2017-10-11 |
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US6048379A (en) * | 1996-06-28 | 2000-04-11 | Ideas To Market, L.P. | High density composite material |
FR2763675B1 (en) * | 1997-05-23 | 1999-06-18 | Poudres & Explosifs Ste Nale | NON-TOXIC COMPOSITE PROJECTILES WITH BIODEGRADABLE POLYMERIC MATRIX FOR HUNTING OR SHOOTING CARTRIDGES |
DE19832456A1 (en) * | 1998-07-18 | 2000-01-20 | Bayer Ag | Biodegradable molding composition containing metallic or mineral filler useful for the production of molded articles has a high density and low toxicity |
US7392746B2 (en) * | 2006-06-29 | 2008-07-01 | Hansen Richard D | Bullet composition |
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