EP2797731A2 - Utilisation de films plastiques biodégradables dans le cadre de procédés de fabrication de matières plastiques renforcées par des fibres par infusion sous vide - Google Patents

Utilisation de films plastiques biodégradables dans le cadre de procédés de fabrication de matières plastiques renforcées par des fibres par infusion sous vide

Info

Publication number
EP2797731A2
EP2797731A2 EP12815714.6A EP12815714A EP2797731A2 EP 2797731 A2 EP2797731 A2 EP 2797731A2 EP 12815714 A EP12815714 A EP 12815714A EP 2797731 A2 EP2797731 A2 EP 2797731A2
Authority
EP
European Patent Office
Prior art keywords
fiber
aliphatic
plastic film
vacuum
curing
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Withdrawn
Application number
EP12815714.6A
Other languages
German (de)
English (en)
Inventor
Martin Kaune
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
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 BASF Coatings GmbH filed Critical BASF Coatings GmbH
Priority to EP12815714.6A priority Critical patent/EP2797731A2/fr
Publication of EP2797731A2 publication Critical patent/EP2797731A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • B29C70/342—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation using isostatic pressure
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/40—Plastics, e.g. foam or rubber
    • 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
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0085—Copolymers
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • 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
    • B29K2867/00—Use of polyesters or derivatives thereof as mould material
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
    • 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
    • B29L2031/08—Blades for rotors, stators, fans, turbines or the like, e.g. screw propellers
    • B29L2031/082—Blades, e.g. for helicopters
    • 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
    • B29L2031/08—Blades for rotors, stators, fans, turbines or the like, e.g. screw propellers
    • B29L2031/082—Blades, e.g. for helicopters
    • B29L2031/085—Wind turbine blades

Definitions

  • the present invention relates to the use of plastic films in processes for producing fiber-reinforced plastics by means of vacuum infusion, and to corresponding processes using such plastic films.
  • Vacuum infusion processes are currently used in the manufacture of large composite fiber components such as in the manufacture of rotor blades for wind turbines.
  • the vacuum infusion process in so-called sandwich construction is now a very common production method of rotor blades.
  • the largest and most modern wings consist of glued glass and carbon fiber mats, into which epoxy resin is injected under vacuum.
  • the high-tech construction provides the required exceptional stability and flexibility, while keeping the wings thin and light at the same time.
  • the mold consisting of two heatable shells is subjected to release agent. Then, if necessary, the shell is covered with an inmould gelcoat and, after its hardening, laid out with glass fiber mats and other reinforcing material such as balsa wood and PU foams. Then special hoses are used, from which then flows the mixture of epoxy resin, hardeners and additives. This is followed by a plastic film that seals the whole thing airtight. This is laid double-layered to ensure airtightness. In the next step, all the air is drawn out between the tool and the film.
  • the resulting vacuum sucks the liquid resin and hardener mixture through the hoses into the mold and soaks the reinforcing material.
  • Advantage of this method is the uniform impregnation of the fibers and thus the high quality of the produced components and their reproducibility.
  • the half-shells are then heated to about 40 to 50 ° C in order to solidify the component so far that it can be transported safely.
  • the Vacuum foil, tnfusions bamboon and the like removed and then the rotor blade halves are cured at about 70 degrees Celsius. This is followed by the gluing of both halves of the sheet.
  • the coating Prior to the multi-level coating, the coating, the blade surface is ground to remove the release agent.
  • plastic film used before the application of the vacuum which serves the airtight sealing prior to the aspiration of the resin and hardener mixture can be used only once due to the method and must then be disposed of.
  • Such two-layer films used are usually made of polyamide,
  • the object of the present invention was inter alia to overcome the above-mentioned disadvantages associated with the use of the previously used films.
  • biodegradable plastic films that meet the stringent requirements of the binding European standard for biodegradable plastics (EN 13432) have proven to be suitable for replacing the previously used films based on polyamide. This was particularly surprising because such films usually tend to thermal decomposition at the elevated curing temperatures of about 50 ° C.
  • the Ecoflex® films from BASF SE, Ludwigshafen, Germany, have proved to be particularly suitable.
  • the main basic properties, in addition to the temperature resistance consist in the airtightness and elasticity of the films in order to compensate for possible stresses during vacuum drawing.
  • the films can also be additionally optimized by an appropriate surface treatment, such as a nanoscale dephase dephase plasma layer.
  • the present invention thus relates to the use of biodegradable plastic films as vacuum films in processes for the production of fiber-reinforced plastics by means of vacuum infusion.
  • Another object of the invention is a process for the production of fiber-reinforced plastics or plastic components by means of vacuum infusion, in which (a) a heated mold is optionally applied with a release agent, (b) fiber material and optionally further reinforcing material is introduced into the mold, (c) a or several tubes are inserted, which serve the subsequent supply of a liquid mixture comprising at least one resin and at least one resin-reactive hardener, (d) a plastic film is applied, which allows an airtight completion of the mold, and (e) the air between Tool mold and plastic film is pulled out, for example, by pumping, the resulting vacuum sucks the liquid mixture through the hoses in the mold and the fiber material and any other reinforcing materials are impregnated, and connect nd (f) a hardening of the liquid mixture to the fiber-reinforced plastic takes place, characterized in that the plastic film used in step (d) is a biodegradable plastic film.
  • This method is referred to below as the method according to the invention.
  • plastic films used in the inventive use or in the process according to the invention are preferably plastic films based on aliphatic-aromatic copolyesters.
  • Suitable copolyesters are those which are obtainable using short-chain aliphatic diols having 2 to 8 carbon atoms, in particular 4 carbon atoms such as 1,4-butanediol, aliphatic dicarboxylic acids having 3 to 8 carbon atoms, their anhydrides, esters or halides, such as adipic acid, and aromatic dicarboxylic acids, their anhydrides, esters or halides, such as terephthalic acid, terephthalic anhydride or terephthalic acid ester.
  • copolyesters are, for example, those in the journal Chemosphere 44 (2001) 289-299 by Witt et al. aliphatic-aromatic copolyester described. Such copolyesters are available, for example, under the trade name Ecoflex® from BASF SE (Ludwigshafen, DE).
  • biodegradable films can be used directly. However, it may also be advantageous, for example, to physically pretreat the film at higher infusion temperatures or higher temperatures during the first curing step, for example, by a low pressure plasma technique to facilitate containment from the workpiece after curing.
  • the liquid mixture drawn in process step (e), comprising resin and hardener, is preferably sucked in at a pre-tempered temperature.
  • this temperature is preferably 35-45 ° C.
  • the curing step (f) is preferably carried out in several stages, particularly preferably in two stages.
  • a pre-curing is preferably carried out at a temperature which is 5 to 15 ° C above the infusion temperature.
  • this temperature is typically in the range of 40 to 60 ° C, preferably 45 to 55 ° C.
  • the duration of which is usually several hours, for example 2 to 8 hours, preferably 4 to 6 hours, the plastic film applied in step (d) is removed. This is preferably done by peeling off the plastic film.
  • the pre-cured fiber-reinforced plastic is fully cured.
  • the complete cure is usually carried out at a temperature which is 20 to 40 ° C, preferably 25 to 35 ° C above the infusion temperature.
  • this temperature is typically in the range of 60 to 80 ° C, preferably 65 to 75 ° C.
  • the temperature of the second curing stage (also referred to as the temperature stage) is higher than that of the first stage.
  • the temperature is preferably at least 5 ° C when carrying out the second stage, more preferably at least 10 ° C and very particularly preferably at least 15 ° C higher than when carrying out the first stage.
  • the curing time in this step is preferably 5 to 15, more preferably 7 to 12 hours.
  • the molds for use in the process of the invention usually consist of glass fiber reinforced plastic, carbon fiber reinforced plastic or steel.
  • the release agents used in step (a) of the process according to the invention are, if necessary, usually silicone-containing, water-dilutable or solvent-containing release agents, such as Frekote NC 55 (containing solvents, Henkel KGaA, Dusseldorf, Germany) and Mono Coat 1001 W (water-dilutable; ChemTrend, Maisach, Germany).
  • the fiber materials used to make the fiber-reinforced plastics are preferably glass fibers or carbon fibers, for example in the form of individual fibers, but especially in the form of glass fiber mats or bundles and carbon fiber mats or bundles. Other suitable reinforcing materials are balsa wood and polyurethane foams, as well as metal mesh.
  • vacuum hoses for example, pressure- and vacuum-stable polyethylene hoses can be used.
  • the plastic component of the fiber-reinforced plastic usually comprises an epoxy resin or a polyester resin as well as the resins to suitable hardeners (crosslinkers), which react chemically with the resins.
  • Epoxy resins are preferably cured by means of amine curing agents.
  • epoxy resin-amine hardener systems which can be used in the vacuum infusion technique are described inter alia in WO 2010/010048 A1.
  • Particularly preferred epoxy resins have an epoxy equivalent weight of 150 to 200 » preferably 160 to 190 g / equivalent.
  • Particularly suitable amine hardeners for the abovementioned epoxy resins are those having an amine number of between 350 and 750 mg KOH / g, very particularly preferably an amine number of 400 to 700 mg KOH / g and in particular 450 to 650 mg KOH / g.
  • the ratio of the epoxy resin to the amine curing agent is preferably 100: 25 to 100: 35 (m / m) in the aforementioned cases.
  • Such resin-hardener systems may contain other additives such as flow agents, defoamers and deaerators, as well as surface additives.
  • the curing of the epoxy resin-amine hardener systems in step (f) of the process according to the invention is usually carried out at temperatures between 50 and 90 ° C, preferably between 60 and 80 ° C, particularly preferably at 65 to 75 ° C.
  • An epoxy resin system which is outstandingly suitable for use in the process according to the invention is obtainable under the name Baxxodur® (BASF SE, Ludwigshafen, DE). Polyester resins are usually cured by means of peroxidic polymerization initiators.
  • polyester resin systems that can be used in vacuum infusion technology are disclosed, inter alia, in the corresponding technical data sheets of BÜFA (Rastede, Germany). Such resin systems may contain other additives such as flow agents, antioxidants, as well as anti-foaming and surface additives.
  • the curing of the polyester resin systems in step (f) of the process according to the invention is usually carried out at temperatures between 50 and 90 ° C, preferably between 60 and 80 ° C, particularly preferably 65 to 75 ° C.
  • the process according to the invention is usually followed by a coating of the hardened and optionally tempered workpiece.
  • two workpieces are first produced by the method according to the invention in a mold consisting of two heatable half-shells or in two molds, which are then glued together before coating. Bonding usually takes place via connecting webs.
  • workpieces made of fiber-reinforced plastics of any desired shape and size can be produced in an efficient and environmentally friendly manner using the method according to the invention.
  • large and or complex shaped workpieces such as rotor blades, especially those for wind turbines, aircraft or helicopter parts or automotive components and serial components, such. Bonnet and fenders, can be prepared by the process of the invention.
  • GFRP plate glass-fiber-reinforced plastic plate
  • Infusion resin RIM 135 (Momentive) (100 parts by weight)
  • the Ecoflex® film is placed on top of the glass layer, the inlet and outlet channels are made and connected, and the infusion is started.
  • Hardening step 1 about 50 ° C (5h)
  • Hardening step 2 about 70 ° C (7-10 h)
  • the curing step 1 is aerated and the vacuum film from the 50 ° C warm surface removed by peeling. Subsequently, in the second curing step (also referred to as annealing step), the complete curing of the FRP plate.
  • Infusion resin RIM 135 (Momentive) (100 parts by weight)
  • the Ecovio® film is placed on top of the glass layer, the inlet and outlet channels are made and connected, and the infusion is started.
  • Hardening step 1 about 50 ° C (5h)
  • Hardening step 2 about 70 ° C (7-10 h)
  • the FRP plate produced in Example 1 by means of an Ecoflex® film can be freed of the vacuum infiltration film without residue.
  • the Ecovio® film withstands vacuum infusion but can not be removed from the GFRP surface without residue. This is without the use of a surface treatment by e.g. a release agent such as e.g. Frekote NC 55 of a nanoscale plasma layer not possible.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Moulding By Coating Moulds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne l'utilisation de films plastiques biodégradables en tant que films à vide dans le cadre de procédés de fabrication de matières plastiques renforcées par des fibres ou de pièces en matière plastique renforcées par des fibres par infusion sous vide. L'invention concerne également un procédé de fabrication de matières plastiques renforcées par des fibres ou de pièces en matière plastique renforcées par des fibres, notamment de pales de rotor renforcées par des fibres pour des éoliennes, par infusion sous vide, avec utilisation de films biodégradables.
EP12815714.6A 2011-12-29 2012-12-28 Utilisation de films plastiques biodégradables dans le cadre de procédés de fabrication de matières plastiques renforcées par des fibres par infusion sous vide Withdrawn EP2797731A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12815714.6A EP2797731A2 (fr) 2011-12-29 2012-12-28 Utilisation de films plastiques biodégradables dans le cadre de procédés de fabrication de matières plastiques renforcées par des fibres par infusion sous vide

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201161581140P 2011-12-29 2011-12-29
EP11196091 2011-12-29
EP12815714.6A EP2797731A2 (fr) 2011-12-29 2012-12-28 Utilisation de films plastiques biodégradables dans le cadre de procédés de fabrication de matières plastiques renforcées par des fibres par infusion sous vide
PCT/EP2012/077053 WO2013098392A2 (fr) 2011-12-29 2012-12-28 Utilisation de films plastiques biodégradables dans le cadre de procédés de fabrication de matières plastiques renforcées par des fibres par infusion sous vide

Publications (1)

Publication Number Publication Date
EP2797731A2 true EP2797731A2 (fr) 2014-11-05

Family

ID=48698720

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12815714.6A Withdrawn EP2797731A2 (fr) 2011-12-29 2012-12-28 Utilisation de films plastiques biodégradables dans le cadre de procédés de fabrication de matières plastiques renforcées par des fibres par infusion sous vide

Country Status (6)

Country Link
US (1) US20150021835A1 (fr)
EP (1) EP2797731A2 (fr)
CN (1) CN104039536A (fr)
BR (1) BR112014015772A8 (fr)
CA (1) CA2852377A1 (fr)
WO (1) WO2013098392A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2023011137A (es) * 2021-04-09 2023-10-05 Lm Wind Power As Un aspa de aerogenerador con carenado.

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5123985A (en) * 1986-09-02 1992-06-23 Patricia Evans Vacuum bagging apparatus and method including a thermoplastic elastomer film vacuum bag
US5227113A (en) * 1988-06-13 1993-07-13 Honda Giken Kogyo Kabushiki Kaisha Process for the high speed production of fiber reinforced plastic
WO1999063001A1 (fr) * 1998-05-30 1999-12-09 Daicel Chemical Industries, Ltd. Composition de resine de polyester biodegradable, composition de resine biodesintegrable et objets moules que ces compositions permettent de fabriquer
CN101234531B (zh) * 2008-02-15 2010-09-29 无锡天奇竹风科技有限公司 竹制复合材料风力发电机叶片叶根预成型灌输工艺
ES2379691T3 (es) * 2008-07-22 2012-04-30 Basf Se Preparados que contienen resina de epóxido y mezclas de aminas con derivados de guanidina

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013098392A2 *

Also Published As

Publication number Publication date
BR112014015772A8 (pt) 2017-07-04
WO2013098392A2 (fr) 2013-07-04
CA2852377A1 (fr) 2013-07-04
US20150021835A1 (en) 2015-01-22
CN104039536A (zh) 2014-09-10
WO2013098392A3 (fr) 2013-09-19
BR112014015772A2 (pt) 2017-06-13

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