EP0571586A1 - Materiau en composes carbones - Google Patents
Materiau en composes carbonesInfo
- Publication number
- EP0571586A1 EP0571586A1 EP92924605A EP92924605A EP0571586A1 EP 0571586 A1 EP0571586 A1 EP 0571586A1 EP 92924605 A EP92924605 A EP 92924605A EP 92924605 A EP92924605 A EP 92924605A EP 0571586 A1 EP0571586 A1 EP 0571586A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- material according
- carbon
- disintegrated
- anthracite
- polymers
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/405—Intermeshing co-rotating screws
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2503/00—Use of resin-bonded materials as filler
- B29K2503/04—Inorganic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2503/00—Use of resin-bonded materials as filler
- B29K2503/04—Inorganic materials
- B29K2503/08—Mineral aggregates, e.g. sand, clay or the like
Definitions
- the invention relates to a material consisting of carbon compounds, which can be processed with all known plastics processing machines into shaped bodies, plates, tubes, foils or the like.
- plastic-filler combinations in the market have become particularly important.
- Combinations of finely grained carbon powders, coke powders and petroleum coke powders embedded in a matrix of thermoplastic polymers have also become known to cover special market requirements, although in some cases the finely grained powders made of coal, coke or petroleum coke were not considered to be fillers in the usual sense , but more or less also as an integral part of the thermoplastic polymer, which significantly influences the properties of this plastic.
- the coal or coke powders in the plastically deformable masses did not have the often material-worsening properties of the mostly used fillers, but surprisingly led to improved physical properties of the molding compositions (improved tensile strength, flexural tensile strength, tensile elongation and cold break stability); the molding compounds were easily deformable.
- - Hard coal, petroleum or pitch coke have proven to be particularly suitable for filling the polyethylene matrix. Especially from low-ash hard coal coke, good elastic plates could be formed with the same parts of polyethylene.
- the bending test in contrast to the filling of the polyethylene matrix with other fillers, e.g. B. slate flour, showed good stability. With the same mixing ratio of slate flour and polyethylene, the panels broke after only a few bending stresses.
- the coke powders are produced in the usual way by grinding. Not only can powders with a high fineness (6,400 mesh cm 2 ) but also with a coarser structure (900 mesh cm 2 ) be used for high-quality molding compounds.
- Crosslinking agents can also be added to the mixture of polyethylenes and coke powders.
- Molding compositions with a content of finely divided coke with a diameter of less than 60 ⁇ m made of polyethylene, polypropylene, polybutylene, ethylene-propylene, ethylene-butylene or propylene-butylene in copolymers are also known, these containing 200 to 400 parts of finely divided petroleum coke per 100 parts of polymers, which has at least 80% an average particle size between 0.75 and 50 ⁇ m (DE-AS 1 259 095).
- These molding compositions were based on the knowledge that the size distribution of the petroleum coke particles was critical for achieving a high structure is in the end product. It was practically impossible to add more than 150 to 200 parts of petroleum coke sticks to these polymers, the average diameter of which was greater than 50 ⁇ m.
- Any commercially available polyolefin or mixed polyolefin with a melting coefficient between about 10 and 0.2 and a molecular weight between about 50,000 and 700,000 can be used to produce the known molding compositions.
- the crushing and calibration of the petroleum coke before it is used in the known molding materials can be achieved by grinding in a ball mill, rod mill, hammer mill, spinning the coke parts by blowing with steam or air against a surface, by centrifugal centrifugal action of rotor blades (Pallmann pulverizing device) by supersonic vibration or by using opposing steel rollers at a distance of 0.0254 cm or less.
- the influence of oxygen is prevented during comminution by an inert gas atmosphere, while classification, however, by spraying with zinc stearate at approximately 0.1 or 1%, based on the weight of the product, the particles being coated individually with the zinc stearate until a relatively uniform coating has been obtained.
- the coating melts when the coke powder thus protected is added to the natural rubber to vulcanize it.
- coal processed by the known method can also be used as a filler for conventional plastics.
- plastics or plastic-filler combinations can only be recycled to a greater or lesser extent. Rather, with the previously known plastic-filler combinations there is usually a considerable loss of quality, with the result that already recycled plastics can often only be used in conjunction with primary plastics or can only be used to produce inferior molded parts without mixing with them.
- plastic such as plastic.
- plastics are not recycled (polyethylene, polypropylene, polystyrene, polycarbonate, polyester, polyamide etc.) or primary plastics and secondary plastics, or if plastics contain color pigments, stabilizers, plasticizers or other additives, especially when used for the first time, there is an additional loss of quality that prohibit the reuse of such plastics for economic reasons. As a result, only a small proportion of plastics are recycled. Recycling without significant loss of quality is only possible with pure plastics. However, these also largely differ according to the type of fillers or color pigments used, so that a loss of quality is inevitable.
- the invention has for its object to provide inexpensively producible, processable on almost all existing plastics processing machines and systems, consisting of carbon compounds, which not only have at least comparably good mechanical, physical and processing, technical properties such as known materials consisting of carbon compounds have, but can also be reused without devaluing quality and can be disposed of easily and environmentally friendly.
- the carbon compounds in addition to very high impact velocities to fine-grained carbon powders, disintegrated low-pollutant and low-ash hard coal, hard coal coke or petroleum coke also contain thermoplastic polymers of the hydrocarbon group which contain the very fine particles of the carbon powder the binding energies released during their high-speed impact crushing in a closed system of material processing systems are chemically combined without additional additives to form a material that can be recycled several times without devaluing quality and with a calorific value of over 37,500 kJ / kg.
- this energy reserve can be converted into thermal energy even after repeated recycling, in an environmentally friendly and almost cost-neutral manner, without using landfills or waste incineration plants.
- the fuels can in principle be shredded in shredders suitable for high-speed impact crushing.
- eddy current disintegrators according to the German patent DE 3802260 D2.
- Such vortex flow disintegrators work with counter-rotating, radially successive blade rings in such a way that vortex zones are formed in the annular spaces between the blade rings, in which the fuel particles collide at high speeds without any disturbing metal abrasion taking place.
- each fuel particle experiences eight collisions with other particles as it passes through the radially successive vortex zones, with impingement velocities close to the speed of sound occurring especially in the last vortex zone between the penultimate and the outer blade ring, but also beyond.
- the comminution time within a vortex flow disintegrator is extremely short at 0.5 seconds, measured on a comminution time of the fuels, for example in a ball mill or other comminution devices, which not only results in less expensive processing than in other mills, but also a significant procedural advantage, since released binding energies (primarily ions or electrons) are not so quickly dissipated into the ground via the metal construction of the processing plant.
- the material comminution in an eddy current disintegrator of the type mentioned thus has another important value over other types of comminution advantage.
- high impact speeds during comminution but above all because the fuel particles themselves collide with one another and are not hurled against a wall or the like by centrifugal forces or even surface-compacted by the balls in a ball mill, high binding energies can be released and largely obtained, which during Bringing together the fuel parts with the hydrocarbon of the polymers in the extruder are almost completely available to improve the material quality of the material according to the invention.
- the weakest binding energies disintegrate first, unlike in the case of shear or tear crushing, e.g. B.
- the high-speed impact crushing provides excitation energy for the hydrogen ions / electrons and the carbon electrons, which can occupy free orbitals, even of a higher energy level. This process depends on the temperature. According to the invention, therefore, the high-speed impact crushing and also the mixing of the activated carbon powder with the polymers in the extruder is carried out with the supply of heat and partly under an inert gas atmosphere, in order to prevent released binding energies from reacting with the oxygen in the air. In addition, the reactivity of the carbon powder is increased by supplying heat energy before and in the extruder. It has been found that the best processing temperature of the carbon powder with the polymers into a bonded material in the extruder is between 240 and 300 ° C. If this temperature is lowered too much, the high quality properties of the new materials, including the good electrical conductivity, will not be achieved.
- the above-described preparation process with high-speed impact crushing at almost the speed of sound leads to a change in the surface of anthracite with the formation of pores with diameters below 3.6 ⁇ m in the particle structure, with the result that the surface of the particle particles is 10 times larger than in spheres - or vibrating mills prepared anthracite.
- the surface for high-speed impact crushing was 28 m 2 / g instead of 2.6 m 2 / g and 2.8 m 2 / g when processed with a ball or vibrating mill.
- the pores arise from the fact that the Velocity impact crushing near the sound limit briefly temperatures up to 300oC arise during the impact processes and thereby volatile components of the anthracite are released.
- the purest possible polymers or polypropylenes are used as polymers, which are melted at 240.degree. C. to 300.degree. C., for example in a twin-screw extruder with screws rotating in the same direction, and the processed carbon powder, preferably the finely divided disintegrated anthracite heated to 200 to 300.degree.
- the anthracite content varies from granule type to granule type between 40 - 80 M%.
- the resulting extrudate is granulated so that it remains storable without quality devaluation and can be processed into marketable products on almost all known plastic processing machines or systems (e.g. molded articles, plates, tubes, foils and, because of its chemical and UV resistance, also to containers, tanks, drums and canisters for the disposal of chemical waste and special waste).
- Low-ash and low-sulfur anthracite is particularly suitable as a finely grained carbon powder with approximately the following analysis values:
- This material consists of 70% by weight powdered anthracite and 30% by weight polyethylene.
- this finely grained anthracite powder chemically combines with the polyethylene to form a new material.
- this has the following performance values:
- E-module 53 457 840 N / mm 2 2460 N / mm 2
- the fine-grained carbon memevers are disintegrated and sized to grain sizes between 10 ⁇ m and 90 ⁇ m. Their weight shares in the new material make up between 20 to 70%, whereby the difference to 100% of the weight parts consists of polymers.
- the new material can be disposed of without difficulty even after repeated recycling by incineration in power plants, cement plants, lime plants, etc. or in waste incineration plants to obtain environmentally friendly thermal energy.
- an amount of up to DM 400 per ton had to be paid for the burning of plastics in special waste incineration plants.
- a delivery to power plants, cement plants, lime distilleries, etc. can pay the high calorific value to the supplier! Because of the high carbon content of over 90%, such material waste is also interesting for the steel industry to improve the steel quality! Contamination of the combustion systems or pollution of the flue gases beyond the permissible level of pollutants does not occur.
- Processable special qualities of material granules or material powders with high strength, high temperature resistance and high electrical conductivity result if the materials are processed in a treatment system that is completely sealed off from the ambient air in an inert gas atmosphere or an inert gas atmosphere with a residual oxygen content of up to 3% and without further processing Contacts with the air atmosphere are stored in gas-tight packaging.
- thermoplastic polymers added in each case as additives, stabilizers, electrical conductors or pigments, contain only those substances which, when the material or the products produced therefrom are burned, do not contain the flue gas with toxic substances or beyond the permissible level pollute with pollutants.
- a comparison basis with 100% serves pure polyethylene (PE).
- PE polyethylene
- the analysis values of the anthracite correspond to those which are characterized in claim 2. As the grain size of the anthracite powder becomes smaller, the tensile strength increases only slightly.
- Figure 2 shows the increase in strength of the new materials as a function of the anthracite mass.
- Pure PE with 25.2 N / mm 2 and pure PP with 32.5 N / mm 2 serve as the basis.
- the anthracite again has a grain size of 50 ⁇ m. It is interesting that a material with PE as a polymer component has significantly higher tensile strength than a material that contains PP as a polymer component.
- the anthracite prepared according to the invention reacts more stable with PE than with PP. With both materials, the tensile strength increases differently with increasing amounts of anthracite.
- Figure 3 shows the impact strength of the new materials depending on the different fineness of the anthracite in the material.
- the impact strength is fully retained with a grain size of the anthracite powder from 90 ⁇ m to 30% by weight of anthracite. With increasing anthracite masses, it then drops and reaches a lower value of 20% with a mass fraction of anthracite of 60%. They behave similarly in the case of materials in which the anthracite powder have grain sizes of 60 ⁇ m, 30 ⁇ m or 10 ⁇ m. If the impact strength with a high proportion of anthracite in the new material is more important, it is advisable to choose a smaller grain size.
- the impact resistance of the materials according to the invention does not change due to the assessment.
- PE on the other hand, becomes brittle after only 250 hours.
- this disadvantage of PE is usually compensated for by the addition of stabilizers.
- the material according to the invention does not need these additives.
- the mass fraction of anthracite also has an influence on the electrical conductivity.
- the conductivity reaches a maximum at 80% mass fraction of anthracite (which corresponds to a minimum of the surface resistance).
- the mass fraction of anthracite also influences the softening temperature of the new materials.
- the softening temperature of the material with 70% by mass of anthracite with a grain size of 60 ⁇ m is almost 137%, that is about 107oC.
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Processing Of Solid Wastes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4140025A DE4140025C2 (de) | 1991-12-04 | 1991-12-04 | Aus Kohlenstoffverbindungen bestehender Werkstoff |
DE4140025 | 1991-12-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0571586A1 true EP0571586A1 (fr) | 1993-12-01 |
Family
ID=6446277
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92924605A Withdrawn EP0571586A1 (fr) | 1991-12-04 | 1992-11-26 | Materiau en composes carbones |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0571586A1 (fr) |
JP (1) | JPH06505527A (fr) |
CN (1) | CN1076433A (fr) |
AU (1) | AU666898B2 (fr) |
CA (1) | CA2101650A1 (fr) |
DE (1) | DE4140025C2 (fr) |
FI (1) | FI933456A (fr) |
HU (1) | HUT76624A (fr) |
NO (1) | NO932776L (fr) |
PL (1) | PL170735B1 (fr) |
RU (1) | RU2089566C1 (fr) |
TW (1) | TW235305B (fr) |
WO (1) | WO1993012169A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10152189B4 (de) * | 2001-10-23 | 2006-03-23 | Hubert Rosing | Verfahren zur Herstellung von Halbzeugen aus ultrahochmolekularem Polyethylen mit Anthrazit, derart hergestellte Halbzeuge und deren Verwendung |
RU2491302C2 (ru) * | 2008-10-13 | 2013-08-27 | Закрытое акционерное общество "Макполимер" | Электропроводный композиционный материал на основе полипропилена и глобулярного углеродного нанонаполнителя |
CN110603286A (zh) * | 2017-04-05 | 2019-12-20 | 俄亥俄大学 | 煤塑复合材料 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE550668A (fr) * | 1955-08-29 | |||
NL285994A (fr) * | 1961-11-30 | |||
GB1115973A (en) * | 1965-02-12 | 1968-06-06 | Exxon Research Engineering Co | Coke fillers |
US3404120A (en) * | 1965-08-02 | 1968-10-01 | Marathon Oil Co | Polymer compositions containing coal which has been ground in a non-oxidizing atmosphre |
US3846523A (en) * | 1967-12-12 | 1974-11-05 | American Mfg Co Inc | Method of forming expanded composite materials in the absence of recognized blowing agents |
DE2017410A1 (de) * | 1970-04-11 | 1971-10-28 | Conradty Fa C | Kunststoff zur Herstellung von Rohren, Platten, Scheiben und anderen Formkörpern durch Extrusion und Spritzgießen |
DE3802260A1 (de) * | 1988-01-27 | 1989-08-10 | Kasa Technoplan | Rotierende desintegrationsvorrichtung |
-
1991
- 1991-12-04 DE DE4140025A patent/DE4140025C2/de not_active Expired - Fee Related
-
1992
- 1992-11-26 PL PL92300205A patent/PL170735B1/pl unknown
- 1992-11-26 HU HU9302106A patent/HUT76624A/hu unknown
- 1992-11-26 AU AU30827/92A patent/AU666898B2/en not_active Ceased
- 1992-11-26 WO PCT/EP1992/002724 patent/WO1993012169A1/fr not_active Application Discontinuation
- 1992-11-26 EP EP92924605A patent/EP0571586A1/fr not_active Withdrawn
- 1992-11-26 RU RU9293053626A patent/RU2089566C1/ru active
- 1992-11-26 CA CA002101650A patent/CA2101650A1/fr not_active Abandoned
- 1992-11-26 JP JP5510546A patent/JPH06505527A/ja active Pending
- 1992-12-03 TW TW081109710A patent/TW235305B/zh active
- 1992-12-04 CN CN92114941A patent/CN1076433A/zh active Pending
-
1993
- 1993-08-03 FI FI933456A patent/FI933456A/fi not_active Application Discontinuation
- 1993-08-03 NO NO93932776A patent/NO932776L/no unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9312169A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU3082792A (en) | 1993-07-19 |
NO932776D0 (no) | 1993-08-03 |
CN1076433A (zh) | 1993-09-22 |
NO932776L (no) | 1993-08-03 |
PL300205A1 (en) | 1994-02-21 |
TW235305B (fr) | 1994-12-01 |
HUT76624A (en) | 1997-10-28 |
JPH06505527A (ja) | 1994-06-23 |
FI933456A0 (fi) | 1993-08-03 |
FI933456A (fi) | 1993-08-03 |
HU9302106D0 (en) | 1994-03-28 |
CA2101650A1 (fr) | 1993-06-05 |
WO1993012169A1 (fr) | 1993-06-24 |
AU666898B2 (en) | 1996-02-29 |
DE4140025A1 (de) | 1993-06-09 |
RU2089566C1 (ru) | 1997-09-10 |
DE4140025C2 (de) | 1994-06-30 |
PL170735B1 (pl) | 1997-01-31 |
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