WO2015084933A1 - Resin transfer molding with rapid cycle time - Google Patents
Resin transfer molding with rapid cycle time Download PDFInfo
- Publication number
- WO2015084933A1 WO2015084933A1 PCT/US2014/068326 US2014068326W WO2015084933A1 WO 2015084933 A1 WO2015084933 A1 WO 2015084933A1 US 2014068326 W US2014068326 W US 2014068326W WO 2015084933 A1 WO2015084933 A1 WO 2015084933A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- injection ports
- fibers
- mold
- injection
- Prior art date
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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
- B29C45/78—Measuring, controlling or regulating of temperature
-
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
-
- 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
- B29C45/02—Transfer moulding, i.e. transferring the required volume of moulding material by a plunger from a "shot" cavity into a mould cavity
-
- 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
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
- B29C45/77—Measuring, controlling or regulating of velocity or pressure of moulding 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
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76498—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
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76531—Temperature
-
- 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
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76551—Time
- B29C2945/76561—Time duration
-
- 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
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76655—Location of control
- B29C2945/76732—Mould
-
- 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
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76655—Location of control
- B29C2945/76765—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
- 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
- B29K2311/00—Use of natural products or their composites, not provided for in groups B29K2201/00 - B29K2309/00, as reinforcement
- B29K2311/10—Natural fibres, e.g. wool or cotton
Definitions
- the present invention in general relates to resin transfer molding and in particular to an improved resin transfer molding process with a staggered injection of resin by time and position in a multipoint injection system.
- Resin transfer molding is a method of fabricating composite structures with high strength, complex geometries, tight dimensional tolerances, and part quality typically required for automotive and aerospace applications.
- RTM uses a closed mold commonly made of aluminum with a fiber "lay-up" such as graphite placed into the mold. The mold is closed, sealed, heated, and placed under vacuum. A room temperature (20°C) or heated resin is then injected into the mold to impregnate the fiber layup. Having the mold heated and under vacuum assists the resin flow. The mold is then held at a temperature sufficient to cure the resin.
- a resin experiences three distinct states during the RTM process; a viscous state during injection, a jelling state during which the viscosity of the resin changes to a higher viscosity, and a cure time when the resin materials chemically crosslink and the resin hardens.
- Molds used for RTM have one or more injection ports for introducing the resin, and at least one exhaust port for gas and excess resin to leave the mold.
- Multiport injection molds are typically used for larger parts that have an increased processing time.
- a common problem encountered during the RTM process is a non-uniform flow of the resin, where the resin experiences a change in viscosity as the resin travels away from the injection point. Furthermore, as shown in the graph of FIG. 1 as the time of processing progresses the pressure and temperature experienced by the resin decreases as a function of time. The aforementioned problems experienced during the RTM process contribute to defects in formed parts.
- a process for resin transfer molding (RTM) with staggered injection of a resin is provided that injects resin into a plurality of injection ports of a mold.
- the temperature and pressure applied to the mold are controlled during injection to limit promote rapid filling of the mold cavity.
- the injection ports are activated for injecting the resin in any order of individually, in groups, or pairings. Fibers are readily added to the mold separately or within the resin. Cycle times of from 1 to 5 minutes are provided for the process.
- FIG. 1 is a graph showing the typical response curve as the time of processing progresses the pressure and temperature experienced by the resin decreases as a function of time;
- FIG. 2 is a graph showing the response curve of pressure and temperature as a function of time for resin with staggered injection in a multiport RTM mold according to an embodiment of the inventive process;
- FIG. 3 is a plan view of a multiport RTM mold with four injection ports for staggered resin injection according to embodiments of the invention
- FIG. 4 is a plan view of a multiport RTM mold with six injection ports for staggered resin injection according to embodiments of the invention.
- FIG. 5 is a flowchart of a production process of the staggered multiport RTM process according to embodiments of the invention.
- the present invention has utility as an improved resin transfer molding (RTM) process with a staggered injection of resin by time and position in a multipoint injection system.
- RTM resin transfer molding
- the staggered introduction of resin in a mold provides for an improved pressure and temperature profile versus time for the resin used for forming parts versus existing RTM processes that simultaneously inject resin.
- the staggered introduction of resin in embodiments of the inventive process provide for improved product yields with fewer formed part defects resulting from non- impregnated portions, thereby improving the quality of the molded product.
- product cycle time is also reduced by staggering the injection of resin in a multiport mold versus the existing process of simultaneous injection of resin in a multiport mold.
- Resins used in embodiments of the inventive staggered RTM process include thermosetting resins such as epoxy; urethanes; polyesters, and vinylesters; that are low in viscosity and easy to be impregnated into reinforcing fibers.
- These resins illustratively include epoxy resin, an unsaturated polyester resin, a polyvinylester resin, a phenolic resin, a guanamine resin, a polyimide resin such as bismaleimide triazine resin, a furan resin, a polyurethane resin, a polydiarylphthalate resin, a melamine resin, a urea resin, an amino resin, etc.
- Fibers may be introduced to the resin used in certain embodiments of the inventive staggered RTM process to strengthen formed parts including glass, carbon, and other synthetic fibers, as well as natural fibers. Natural fibers may include coconut fibers, bamboo fibers, sugar cane fibers, banana skin fibers, etc.
- FIG. 2 a graph 20 showing the response curve of pressure and temperature as a function of time for resin with staggered injection in a multiport RTM mold according to an embodiment of the inventive process.
- the rapid decline of pressure and temperature during the processing of a molded part in the mold is avoided compared to conventional RTM process, and the temperature and pressure is maintained during the RTM process of embodiments of the invention to increase cycle time of molding a part.
- FIG. 3 is a plan view of a multiport RTM system 30 with a mold 32 with four injection ports 34A-34C for staggered resin injection and an exhaust port 36 according to embodiments of the invention.
- the injection ports may be activated in any order both individually, and in groups, or pairings.
- injection ports 34A and 34B may be turned on as a pair and alternated with injection ports 34C and 34D as a second pair, where the adjacent pairings (34A-34B, 34C-34D) inject resin at alternating times.
- cross-pairings of injection ports (34A-34D) and (34B-34C) may inject resin at alternating times.
- the injection ports 34A, 34B, 34C, and 34D are each individually turned on and off in sequential clockwise or counter clockwise order. While four such ports 34A-34D are shown it is appreciated that the number of injection ports ranges from 1 to 10 in various inventive embodiments, while in other embodiments, from 2 to 6 ports and in still other embodiments 2 or 3 ports are used.
- FIG. 4 is a plan view of a multiport RTM system 40 with a mold 42 with six injection ports 44A-44F for staggered resin injection and an exhaust port 46 according to embodiments of the invention.
- the injection ports 44A-44F may be activated in any order both individually, and in groups, or pairings.
- the number possible combinations and configurations for activating and injecting resin through the various injection ports increases as the number of available injection ports increases for a given mold.
- FIG. 5 is a flowchart of a production process 50 of the staggered multiport RTM process according to embodiments of the invention.
- the process starts with an operator programing a production controller (step 52) with process parameters for a particular molded part to be formed with the RTM process using a multi resin injection port mold.
- Process parameters including pressure, temperature, and firing sequence of the resin injectors are set by the operator based on the resin material and part to be formed in the RTM process.
- the operator loads the resin for forming the part into the reservoirs of the resin injectors, as well as the layup into the mold (step 54).
- the multiport mold fixture resin input lines are hooked up to the resin injectors (step 56).
- the RTM process is started (step 58), and the completed part is removed from the mold (step 60).
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/035,163 US20160288394A1 (en) | 2013-12-03 | 2014-12-03 | Resin transfer molding with rapid cycle time |
EP14868247.9A EP3077175B1 (en) | 2013-12-03 | 2014-12-03 | Resin transfer molding with rapid cycle time |
MX2016007289A MX2016007289A (en) | 2013-12-03 | 2014-12-03 | Resin transfer molding with rapid cycle time. |
CA2931030A CA2931030C (en) | 2013-12-03 | 2014-12-03 | Resin transfer molding with rapid cycle time |
US16/720,575 US11247415B2 (en) | 2013-12-03 | 2019-12-19 | Resin transfer molding with rapid cycle time |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361910974P | 2013-12-03 | 2013-12-03 | |
US61/910,974 | 2013-12-03 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/035,163 A-371-Of-International US20160288394A1 (en) | 2013-12-03 | 2014-12-03 | Resin transfer molding with rapid cycle time |
US16/720,575 Continuation-In-Part US11247415B2 (en) | 2013-12-03 | 2019-12-19 | Resin transfer molding with rapid cycle time |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015084933A1 true WO2015084933A1 (en) | 2015-06-11 |
Family
ID=53274061
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2014/068326 WO2015084933A1 (en) | 2013-12-03 | 2014-12-03 | Resin transfer molding with rapid cycle time |
Country Status (7)
Country | Link |
---|---|
US (1) | US20160288394A1 (en) |
EP (1) | EP3077175B1 (en) |
CN (2) | CN104690876A (en) |
CA (1) | CA2931030C (en) |
MX (1) | MX2016007289A (en) |
PT (1) | PT3077175T (en) |
WO (1) | WO2015084933A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018125711A1 (en) * | 2016-12-27 | 2018-07-05 | Continental Structural Plastics, Inc. | Continuous channel resin transfer molding with rapid cycle time |
EP3766676A1 (en) * | 2019-07-18 | 2021-01-20 | Covestro Deutschland AG | Method for preparing a polyurethane composite by a vacuum infusion process |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6831662B2 (en) * | 2016-09-12 | 2021-02-17 | 川崎重工業株式会社 | Manufacturing method of fiber reinforced plastic molded product |
CN107984562B (en) * | 2017-12-31 | 2023-11-28 | 浙江省林业科学研究院 | Manufacturing method of RTM (resin transfer molding) bamboo bundle composite board |
FR3085298B1 (en) * | 2018-08-31 | 2021-11-26 | Safran | RESIN INJECTION MODULATOR, RESIN INJECTION CIRCUIT AND RELATED METHODS |
CN109666264A (en) * | 2019-01-09 | 2019-04-23 | 东北林业大学 | A kind of RTM molding bamboo fiber felt enhancing thermosetting resin based composites and preparation method |
CN114074438A (en) * | 2021-03-19 | 2022-02-22 | 亨弗劳恩(江苏)复合材料研发有限公司 | Method for improving injection molding defects of thermosetting composite material |
Citations (5)
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US5518388A (en) * | 1993-12-14 | 1996-05-21 | United Technologies Corporation | Automated apparatus and method for resin transfer molding |
EP1157810A1 (en) * | 1999-12-28 | 2001-11-28 | Universidad Politecnica De Madrid | Production system, device and process for manufacturing structural parts made of composite material by resin transfer molding |
US20030122285A1 (en) * | 2000-06-23 | 2003-07-03 | Steve Crane | Method of resin transfer molding and components for use therewith |
EP1721719A1 (en) | 2004-02-17 | 2006-11-15 | Toray Industries, Inc. | Rtm molding method and device |
JP2011168010A (en) * | 2010-02-22 | 2011-09-01 | Toray Ind Inc | Rtm molding method |
Family Cites Families (8)
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TW243424B (en) * | 1992-09-28 | 1995-03-21 | Takeda Pharm Industry Co Ltd | |
DE29720598U1 (en) * | 1997-11-20 | 1998-02-05 | Christian Heinrich Sandler GmbH & Co. KG, 95126 Schwarzenbach a d Saale | Non-woven fabric made from natural fibers and synthetic fibers |
US7081219B2 (en) * | 1999-03-18 | 2006-07-25 | Stewart David H | Method and machine for manufacturing molded structures using zoned pressure molding |
CA2517806A1 (en) * | 2003-03-13 | 2004-09-23 | Toho Tenax Co., Ltd. | Method of resin transfer molding |
US7829637B2 (en) * | 2004-02-17 | 2010-11-09 | Continental Structural Plastics | Polymeric thickener for molding compounds |
JP5440049B2 (en) * | 2008-09-11 | 2014-03-12 | 東レ株式会社 | RTM molding method |
WO2011022459A2 (en) * | 2009-08-18 | 2011-02-24 | University Of Delaware | Computer controlled flow manipulation for vacuum infusion processes |
EP2322713A1 (en) * | 2009-11-11 | 2011-05-18 | Aarsen Holding B.V. | Method for producing bamboo fibres as well as plastics containing same |
-
2014
- 2014-12-03 EP EP14868247.9A patent/EP3077175B1/en active Active
- 2014-12-03 CN CN201410723649.6A patent/CN104690876A/en active Pending
- 2014-12-03 US US15/035,163 patent/US20160288394A1/en not_active Abandoned
- 2014-12-03 PT PT148682479T patent/PT3077175T/en unknown
- 2014-12-03 WO PCT/US2014/068326 patent/WO2015084933A1/en active Application Filing
- 2014-12-03 MX MX2016007289A patent/MX2016007289A/en unknown
- 2014-12-03 CA CA2931030A patent/CA2931030C/en active Active
- 2014-12-03 CN CN202010446359.7A patent/CN111571914A/en active Pending
Patent Citations (6)
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US5518388A (en) * | 1993-12-14 | 1996-05-21 | United Technologies Corporation | Automated apparatus and method for resin transfer molding |
EP1157810A1 (en) * | 1999-12-28 | 2001-11-28 | Universidad Politecnica De Madrid | Production system, device and process for manufacturing structural parts made of composite material by resin transfer molding |
US20030122285A1 (en) * | 2000-06-23 | 2003-07-03 | Steve Crane | Method of resin transfer molding and components for use therewith |
EP1721719A1 (en) | 2004-02-17 | 2006-11-15 | Toray Industries, Inc. | Rtm molding method and device |
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JP2011168010A (en) * | 2010-02-22 | 2011-09-01 | Toray Ind Inc | Rtm molding method |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018125711A1 (en) * | 2016-12-27 | 2018-07-05 | Continental Structural Plastics, Inc. | Continuous channel resin transfer molding with rapid cycle time |
EP3562654A4 (en) * | 2016-12-27 | 2020-07-29 | Continental Structural Plastics, Inc. | Continuous channel resin transfer molding with rapid cycle time |
US11407187B2 (en) | 2016-12-27 | 2022-08-09 | Teijin Automotive Technologies, Inc. | Continuous channel resin transfer molding with rapid cycle time |
EP3766676A1 (en) * | 2019-07-18 | 2021-01-20 | Covestro Deutschland AG | Method for preparing a polyurethane composite by a vacuum infusion process |
Also Published As
Publication number | Publication date |
---|---|
US20160288394A1 (en) | 2016-10-06 |
EP3077175B1 (en) | 2023-02-22 |
CN104690876A (en) | 2015-06-10 |
CA2931030A1 (en) | 2015-06-11 |
EP3077175A4 (en) | 2017-07-12 |
CN111571914A (en) | 2020-08-25 |
PT3077175T (en) | 2023-05-09 |
CA2931030C (en) | 2022-02-15 |
EP3077175A1 (en) | 2016-10-12 |
MX2016007289A (en) | 2016-09-07 |
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