WO2004012918A1 - Procede de production d'un objet a structure composite a partir de matieres plastiques recyclables et objet produit au moyen de ce procede - Google Patents

Procede de production d'un objet a structure composite a partir de matieres plastiques recyclables et objet produit au moyen de ce procede Download PDF

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Publication number
WO2004012918A1
WO2004012918A1 PCT/IB2003/002975 IB0302975W WO2004012918A1 WO 2004012918 A1 WO2004012918 A1 WO 2004012918A1 IB 0302975 W IB0302975 W IB 0302975W WO 2004012918 A1 WO2004012918 A1 WO 2004012918A1
Authority
WO
WIPO (PCT)
Prior art keywords
casing
core
product
mass
plastic materials
Prior art date
Application number
PCT/IB2003/002975
Other languages
English (en)
Inventor
Dario Giacomo Tolio
Ippolito Caccamo
Original Assignee
Dario Giacomo Tolio
Ippolito Caccamo
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dario Giacomo Tolio, Ippolito Caccamo filed Critical Dario Giacomo Tolio
Priority to AU2003251080A priority Critical patent/AU2003251080A1/en
Priority to EP20030766521 priority patent/EP1556200A1/fr
Publication of WO2004012918A1 publication Critical patent/WO2004012918A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
    • B29B17/0042—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting for shaping parts, e.g. multilayered parts with at least one layer containing regenerated plastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/10—Building elements, e.g. bricks, blocks, tiles, panels, posts, beams
    • B29L2031/104—Tiles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • PROCESS FOR MANUFACTURING A COMPOSITE STRUCTURE OBJECT USING RECYCLABLE PLASTIC MATERIALS, AS WELL AS OBJECT OBTAINED WITH SUCH PROCESS
  • This invention generally addresses the field of plastic processing and particularly relates to a process for manufacturing composite products from recycled plastics.
  • Another aspect of the invention relates to a plant for carrying out the above process, by using synthetic materials recovered by various methods, for instance selective waste sorting in civil and industrial landfills, to minimize the environmental impact and promote waste recycling.
  • the invention relates to a product, particularly a tile, made of composite plastic, which is obtained by the above process and plant.
  • a general interest is known to minimize environmental pollution caused by non- biodegradable materials, particularly plastics, by recycling products made of such materials, which form a large percentage of ordinary objects of daily and industrial use.
  • plastics recycling methods are known. Most of these processes generally include the steps of selecting, shredding or comminuting, mixing and heating the starting synthetic materials, collected from public and private landfills, until they become at least partly plastic, and form an injectable, castable or otherwise formable mass, which is molded in suitable molds or extruded through suitable dies. From "Plastics engineering", Vol. 44, No. 6, June 1988, Brookfield, CT, USA, pp. 30-41 , a process is known for partly recycling synthetic wastes in a plastic state, and extruding to form products whose structure has a higher density at the edges than in the central portion or core. This differentiated structure is obtained by using materials having different consistencies in the extrusion area.
  • FR-A-2191984 discloses a process for forming a material in the plastic state, wherein products are formed by extrusion or injection. By using steam as a blowing agent, fibrous products are obtained.
  • EP-A-0862977 discloses a process for recycling plastic materials, including comminution, heating and homogenization of starting materials.
  • the resulting mass is injected into a mold such that the thinner component of the synthetic mass gathers at the edges, and a finer cover is formed, whereas polyethylene is injected as a binder in the inner portion, to form a rougher structure.
  • Synthetic recycled materials are previously shredded to obtain a maximum particle size of 6 mm, mixed and dried so as to have a residual moisture of 5% to 10%. Then, the mixture is heated to about 150°C and injected into a mold, where it expands due to the residual moisture which acts as a blowing agent.
  • US-A-4, 795,603 discloses a process for using plastic and synthetic rubber wastes, which are shredded and mixed with finely comminuted polyethylene or polypropylene to form a base material mixture.
  • the base material is heated until only the plastic material is molten, and is injected into a mold to obtain products having a wood-like surface finish, high lightness and water and weather resistance.
  • US-A-4,303,349 discloses a process for making products from recycled plastics containing considerable amounts of dirt, oils, sand and other foreign materials.
  • the products manufactured with prior art methods, by using the same starting materials have blowholes, inhomogeneities, internal cavities, hence they exhibit poor mechanical properties.
  • a semi-molten extruded object is prepared, and introduced in a press, in which it is subjected to high pressure to full stabilization, to provide low-cost products having good mechanical properties.
  • a drawback of the above mentioned prior art processes is that they are unable to provide a highly homogeneous surface finish, and to allow arbitrary change of colors and mechanical properties of surface layers, whereby they limit the field of application of the finished product.
  • a general object of this invention is to provide a process for manufacturing recycled plastics products, having high structural strength, durability, moisture and weather resistance, as well as a high-quality surface finish.
  • a particular object is to provide a process and a plant, allowing to use recycled plastics for manufacturing a product, particularly a covering or floor tile, having a differentiated structure, i.e. an outer protective casing made of a material with different characteristics from the inner core.
  • Another particular object is to conceive a process as described hereinbefore, wherein the protective casing has such a consistency and surface finish as to be suitable for the final application of the product made therewith.
  • Yet another object is to manufacture a composite product, whose central core is stably anchored to the outer casing.
  • a process for manufacturing a composite product particularly but not limited to a tile for wall and floor coverings, from recycled plastics
  • a process for manufacturing a composite product comprises the steps of withdrawing recycled plastic materials, dosing the plastic materials, comminuting them into granules, mixing the granules to form a substantially homogeneous mixture, at least partly drying the mixture, heating the mixture to at least a partial molten state to form a mass of injectable material, injecting said injectable mass into a female mold to form the core of the product, characterized in that it includes a previous step of preparing a relatively thin plastics casing, which is stably anchored to said core to define the outer surface layer of the finished product.
  • a plant for carrying out the above process, characterized in that it comprises means for withdrawing recycled plastic materials, means for dosing said materials, means for comminuting said materials into granules, means for mixing the granules to form a substantially homogeneous mixture, means for at least partly drying said mixture, means for heating the dry mixture to at least a partial molten state to form a mass of injectable material, means for injecting said injectable mass into a mold to form the core of the product to be manufactured, characterized in that it comprises means for preparing a relatively thin preformed plastics casing, as well as means for inserting said casing in said mold, in such a manner as to stably anchor said casing to said core and to define the outer surface layer of the finished product.
  • the invention also addresses a composite plastic product, manufactured by using a process and a plant as described above, which has a casing stably anchored to a core, said core being made from a mixture of recycled plastic materials, said casing being made from plastic materials different from or similar to said core, wherein the core has a plurality of projections in its inner surface, for stable anchorage to the core, upon injection of the mixture of recycled plastics.
  • Fig. 1 is a flowchart of a process according to the invention, for manufacturing a composite plastic product
  • Fig. 2 is a top view of a plant for carrying out the process of Fig. 1.
  • Fig. 3 is a perspective view of a covering or pavement formed by tiles made by the process of Fig. 1 ;
  • Fig. 4 is a top perspective view of the tile as shown in Fig. 3;
  • Fig. 5 is a bottom perspective view of the tile as shown in Fig. 3;
  • Fig. 6 is a top view of a tile as shown in Fig. 3;
  • Fig. 7 is a side sectional view of the tile as shown in Fig. 3, as taken along a vertical longitudinal plane VII-VII;
  • Fig. 8 is an enlarged cross sectional view of the tile as shown in Fig. 3, as taken along a vertical transverse plane VIII-VIII;
  • Fig. 9 is a further enlarged view of a detail of the sectional view as shown in
  • FIGs. 1 and 2 a process and a plant are shown for manufacturing composite products from recycled plastics.
  • recycled materials may consist of plastic materials recovered from household wastes, carpet wastes, glues, rubbers and foam, cellulose, polyethylene, polyacrylates.
  • plastic materials recovered from household wastes, carpet wastes, glues, rubbers and foam, cellulose, polyethylene, polyacrylates.
  • natural or synthetic materials may be further used, such as fibers, metals, dyes, for the purpose of providing the finished product with particular mechanical or aesthetic characteristics.
  • a process according to the invention is schematically shown, particularly for manufacturing a wall or floor covering tile M, which provides high tear, moisture and weather resistance and a considerable durability, besides having a high quality surface finish and aesthetic aspect.
  • the process includes the following steps.
  • the various recycled plastic materials may be mechanically withdrawn from special containers in a withdrawing step A.
  • Such materials are further dosed B to obtain a mixture having a predetermined composition.
  • Such dosed materials are comminuted into granules having a substantially uniform particle size.
  • the resulting granular material may be further mixed D to form a substantially homogeneous granular mixture, and the homogenized mixture is at least partly dehumidified E and heated F to an at least partial molten state, to form a mass of injectable material.
  • the partly molten mass is used in the injection step G, wherein it is injected into a female mold to form the core N of the product M to be manufactured.
  • a preliminary step H is provided for preparing a relatively thin plastics casing W, stably anchored to the core to define the outer surface layer of the finished product.
  • the casing W may be preformed separately by injection L of plastic materials different from or similar to those of the core N.
  • the preformed casing W is inserted in the inner cavity of the mold before injection G of the mass of injectable material.
  • the casing W may be preformed to have a plurality of substantially radial at least partly inward projections S on its inner surface.
  • the casing W may be stably anchored to the core N by injection of the injectable mass in the intermediate spaces.
  • an adhesive layer may be interposed between the inner surface of the casing W and the outer surface of the core N.
  • the outer casing W may be made from thermoplastic materials, such as High Density Polyethylene (HDPE) or Low Density Polyethylene (LDPE), to provide a stable anchorage to the core upon injection of molten plastics into the mold.
  • HDPE High Density Polyethylene
  • LDPE Low Density Polyethylene
  • the plant for carrying out the above process includes a storage station 2, composed of a number of containers denoted as C1 , C2, C3 respectively, which contain plastic materials of various natures and origins, as mentioned above.
  • a doser 3 Downstream from the storage station, a doser 3 is provided, which is fed with controlled amounts of plastic materials from the storage station, through suitable automatic conveyors, known per se.
  • the dosed material is conveyed by a belt conveyor 4 to a mill 5 to be crushed and reduced into granules having a particle size of a few millimeters and, by a belt conveyor 6, to a mixer 7 to form a homogeneous mixture.
  • the resulting mixed granular mixture is conveyed, by a belt conveyor 8, or equivalent conveyor, to the dryer 9, where it is at least partly dried, while retaining a residual moisture, to be used as a blowing agent during injection.
  • the homogenized and dried granular mixture is fed by a belt conveyor 10 to an injection molding machine, generally designated by reference numeral 11 , which essentially comprises a heater device 12 for at least partly melting the plastics mixture, to form a mass of injectable material, and a screw conveyor 13 for feeding and compressing the injectable mass toward an injection nozzle 14.
  • the cycle may start from the drying step by using a special molding machine, not shown, which is designed to plasticize the mixed mass, while removing moisture.
  • the nozzle 14 is located in a molding station to be selectively coupled with one mold 15 at a time, which mold is supported with other equally spaced molds on a carousel or rotary table 16 or another similar device.
  • the carousel 16 rotates intermittently in steps whose angular width corresponds to the distance between two adjacent molds, to carry one mold at a time in front of the nozzle 14.
  • the carousel 16 rotates about a central axis, step by step, in the direction of arrow R until the mold 15 is carried from the start position 15' in front of the nozzle 14, to an end position 15" in front of an ejection station.
  • the carousel rotational speed is selected such that the time required to carry each mold from the position 15' to the position 15" is sufficient to cool and solidify the finished product M, so that it can be ejected from the mold when the latter is opened.
  • Each finished piece M may be discharged by means of a chute or a belt conveyor 17 and collected in a container of finished products 18.
  • a loading station 19 is provided for inserting in each mold 15 a preformed plastic casing W, having a relatively small thickness t, and generally shaped like an upwardly open container, with the bottom wall U being designed to form the upper surface of the finished product M.
  • the casings may be preformed in a special molding station, schematically designated as 20, and may be fed by a loader 21 , e.g. of the linear type, having a mechanical and/or pneumatic feeding device.
  • a loader 21 e.g. of the linear type, having a mechanical and/or pneumatic feeding device.
  • the inner cavity of the mold 15 will hold the casing W, and the rest of the cavity will be filled with the plastic mass injected by the nozzle 14, to create a substantially uniform core N, stably anchored to the casing W.
  • the casing W will be preformed in such a manner as to have a plurality of radial inward projections S on its inner surface.
  • the mass injected from the nozzle 14 will fill the remaining space left by the casing W in the mold cavity and, when it is cooled, it will be stably anchored to the core N of the finished product M thanks to the projections S.
  • a composite tile M is shown as a product manufactured by the process and plant as described hereinbefore.
  • the tile M has such a plan shape that it can be placed next to other tiles of the same type, as schematically shown in Fig. 3, preferably on the ground or a horizontal or inclined wall, to provide a covering with a high tear, moisture and weather resistance.
  • the tile essentially comprises a core N made of recycled plastics of various natures and origins, at least partly covered by a casing W, also made of virgin or selected recycled plastic materials. More particularly, the casing covers the upper face U and the side walls of the tile and has a relatively small thickness t, of at least 1 mm and not exceeding 1/3 of the largest thickness of the finished tile M.
  • the outer upper face U of the casing W has an approximately continuous aspect, whereas its inner concave surface has a plurality of inward radial projections S, which are designed to provide an excellent anchorage to the core N.
  • the mutual anchorage between the casing W, possibly without projections S, and the core N may be provided by the presence of an interposed structural adhesive layer, not shown.
  • the tile M will have a plurality of through holes F across its thickness, for water and moisture drainage.
  • the bottom face D of the tile M may have longitudinal and transverse grooves G, intersecting at the holes F, to improve moisture drainage and anchorage to the walls to be covered with the help of mastic or cement.
  • the plastic material that forms the casing W may be uncolored or uniformly colored with suitable pigments to provide the finished product with the desired aspect.
  • the composition and density of the plastic material or the mixture of plastic materials that form the casing W may be provided with the desired compliance, as requested by its final application.
  • a relatively soft and rubbery plastic material such as Low Density Polyethylene
  • the resulting tiles may be suitable for paving environments like gymnasiums, schools, nursery schools, playgrounds, waiting rooms.
  • a relatively rigid material such as High Density Polypropylene or PVC, for the casing W, produces tiles that are more suitable for paving garages, alleys, machine shops, hangars, yards, sidewalks, parking places, waiting rooms for bus, subway, train stations, harbors and airports.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un procédé permettant de produire un produit composite (M), essentiellement, mais de façon non limitative, un carreau de sol ou de pavage, à partir de matières plastiques recyclées. Ce procédé comprend les étapes consistant à : (A) récupérer des matières plastiques recyclées ; (B) doser ces matières plastiques ; (C) les réduire en granulés ; (D) mélanger les granulés obtenus pour former un mélange sensiblement homogène ; (E) sécher au moins partiellement le mélange ; (F) chauffer ce mélange jusqu'à ce qu'il soit au moins partiellement fondu pour obtenir une masse de matière injectable ; (G) injecter cette masse injectable dans un moule femelle pour former le noyau (N) du produit (M) ; (H) préparer un réceptacle plastique (W) préformé relativement fin, ce réceptacle (W) étant introduit (L) dans la cavité du moule avant l'injection de la masse de matière injectable, de façon à être ancré de manière stable dans le noyau (N) et de manière à définir la couche superficielle extérieure du produit fini (M).
PCT/IB2003/002975 2002-07-26 2003-07-28 Procede de production d'un objet a structure composite a partir de matieres plastiques recyclables et objet produit au moyen de ce procede WO2004012918A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003251080A AU2003251080A1 (en) 2002-07-26 2003-07-28 Process for manufacturing a composite product from recycled plastic materials, as well as product obtained with by such process
EP20030766521 EP1556200A1 (fr) 2002-07-26 2003-07-28 Procede de production d'un objet a structure composite a partir de matieres plastiques recyclables et objet produit au moyen de ce procede

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITVI20020169 ITVI20020169A1 (it) 2002-07-26 2002-07-26 Procedimento per la realizzazione di un oggetto a struttura compositacon materiali plastici di riciclaggio, nonche' oggetto ottenuto con ta
ITVI2002A000169 2002-07-26

Publications (1)

Publication Number Publication Date
WO2004012918A1 true WO2004012918A1 (fr) 2004-02-12

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2003/002975 WO2004012918A1 (fr) 2002-07-26 2003-07-28 Procede de production d'un objet a structure composite a partir de matieres plastiques recyclables et objet produit au moyen de ce procede

Country Status (4)

Country Link
EP (1) EP1556200A1 (fr)
AU (1) AU2003251080A1 (fr)
IT (1) ITVI20020169A1 (fr)
WO (1) WO2004012918A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2180116A2 (fr) * 2008-10-22 2010-04-28 Nicocyl-GmbH Procédé de fabrication des panneaux de revêtement de sol en matière plastique élastique
EP2921643A1 (fr) * 2014-03-21 2015-09-23 Herrenknecht AG Élément de protection, élément en béton et procédé de fabrication d'un élément en béton

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303349A (en) * 1978-07-12 1981-12-01 Upton Albert E Method of manufacturing articles
DE4020417A1 (de) * 1990-06-27 1992-01-02 Zimmermann Wolfgang Verfahren zur wiederverwendung von recycling-kunststoff
DE4141023A1 (de) * 1991-12-12 1993-06-17 Alletto Rothhaar Verfahren zur herstellung von dekorativen und technisch nutzbaren fussbodenbelaegen, matten und bahnen, sowie wand-, boden- und deckenplatten aus recyclinggranulat oder regenerat
US5741454A (en) * 1992-07-13 1998-04-21 Maloney Contractors Ltd. Method of making composite tiles containing waste plastic

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303349A (en) * 1978-07-12 1981-12-01 Upton Albert E Method of manufacturing articles
DE4020417A1 (de) * 1990-06-27 1992-01-02 Zimmermann Wolfgang Verfahren zur wiederverwendung von recycling-kunststoff
DE4141023A1 (de) * 1991-12-12 1993-06-17 Alletto Rothhaar Verfahren zur herstellung von dekorativen und technisch nutzbaren fussbodenbelaegen, matten und bahnen, sowie wand-, boden- und deckenplatten aus recyclinggranulat oder regenerat
US5741454A (en) * 1992-07-13 1998-04-21 Maloney Contractors Ltd. Method of making composite tiles containing waste plastic

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2180116A2 (fr) * 2008-10-22 2010-04-28 Nicocyl-GmbH Procédé de fabrication des panneaux de revêtement de sol en matière plastique élastique
EP2180116A3 (fr) * 2008-10-22 2011-04-13 Nicocyl-GmbH Procédé de fabrication des panneaux de revêtement de sol en matière plastique élastique
EP2727708A3 (fr) * 2008-10-22 2014-10-01 Nicocyl-GmbH Procédé de fabrication de panneaux pour le sol constitués de matière plastique élastique
EP2921643A1 (fr) * 2014-03-21 2015-09-23 Herrenknecht AG Élément de protection, élément en béton et procédé de fabrication d'un élément en béton
WO2015139807A3 (fr) * 2014-03-21 2015-12-10 Herrenknecht Ag Élément de protection, élément en béton et procédé de fabrication d'un élément en béton
CN106103894A (zh) * 2014-03-21 2016-11-09 海瑞克股份公司 保护元件、混凝土元件以及用于制造混凝土元件的方法
AU2015233840B2 (en) * 2014-03-21 2017-11-09 Herrenknecht Ag Protective element, concrete element, and method for producing a concrete element
CN106103894B (zh) * 2014-03-21 2019-09-10 海瑞克股份公司 保护元件、混凝土元件以及用于制造混凝土元件的方法

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Publication number Publication date
ITVI20020169A1 (it) 2004-01-26
EP1556200A1 (fr) 2005-07-27
AU2003251080A1 (en) 2004-02-23

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