CN101804714B - Composite material member with surface functional layer and RTM preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of composite material members with multilayer structures and preparation methods thereof, and in particular discloses an RTM preparation method of a composite material member with a surface functional layer. The composite material member comprises an upper surface layer, a lower surface layer and a sandwich layer; the upper and lower surface layers are the first composite material systems in which epoxy resin, phenolic resin and the like are taken as matrixes; the sandwich layer is the second composite material system in which unsaturated polyester resin is taken as a matrix; and fiber cloth made of carbon fiber or glass fiber is taken as reinforcement in each system. The RTM preparation method comprises the following steps: preparing a reinforced resin film on the surface of a forming mold by a resin transfer molding process by adopting a resin film infiltration process; and preparing the composite material member with the forming mold covered with the reinforced resin film by the resin transfer molding process. The TRM process combines dual advantages of an RFI process and an RTM process; and the prepared composite material member has the advantages of better surface quality, better integration and excellent comprehensive performance.

Description

RTM preparation method with composite element of surface functional layer

Technical field

The present invention relates to a kind of composite element and preparation method thereof, relate in particular to composite element of a kind of sandwich construction and preparation method thereof.

Background technology

Low pressure liquid molding technology (Liquid Composite Molding, be called for short LCM) be the moulding process that is widely used in the preparation of large-sized composite material member, it is meant liquid polymer is injected the closed mould cavity that is covered with the fiber preform, or heat fused puts into the resin molding of die cavity in advance, and liquid polymer is finished the infiltration of resin/fiber and become a class technology of preparing of goods through curing molding in the mold filling that flows.Resin transfer moulding (Resin Transfer Molding is hereinafter to be referred as RTM), resin molding infiltration (Resin Film Infusion is hereinafter to be referred as RFI) are modal advanced LCM technologies.The LCM technology can one the step dip forming have the large-scale component of sandwich, reinforcement, built-in fitting, can have high-performance, make advantage cheaply by the structural requirement lay down fibre, be the main developing direction of composite low-cost manufacturing technique now.

The RFI technological principle as shown in Figure 1, RFI technology is that the resin of pre-catalysis (having added curing agent and other auxiliary agents) is made resin molding 81 in advance, this resin molding 81 is placed in the bottom of RFI mould 8, cover fibre reinforcement 82 on it, with vacuum bag 83 8 encapsulation of RFI mould are formed die cavity 84, by heating, vacuumize and make the liquid resin that forms after resin molding 81 fusings under the negative pressure of vacuum effect, upwards infiltrate behind the fibre reinforcement 82, and fill up space, whole fibre reinforcement 82 place, reaching resin evenly distributes, be cured according to corresponding curing system at last, obtain required composite element.A key factor of RFI technology is exactly a resin molding, and one of them the most basic requirement is exactly that resin molding at room temperature can be crooked arbitrarily and not broken, and tack-free.Because do not have wild phase in the existing resin molding, film strength and rigidity are relatively poor, technological operation is not good.

RTM technology is a kind of technology that adopts the rigidity close die to make composite, and technological principle as shown in Figure 2.RTM technology is to place reinforcing material preform 7 in advance in the mold cavity of former 1 and formpiston 2 compositions, after matched moulds clamps, under certain temperature and pressure, will be injected in the mold cavity through the gum-injecting port 31 of injecting glue system 3 through the resin system that static mixer mixes, vacuumize by pumped vacuum systems 4, make resin system lay-up preform 7 (unnecessary resin from gum outlet 41 extract out), after solidify, the demoulding obtains goods.RTM technology has become one of main developing direction of advanced composite material low-cost manufacturing technique because of it has advantages such as product's dimensional precision height, thickness is even, porosity is low, fugitive constituent is few.But traditional RTM technology just is put in fibre reinforcement in the die cavity, after with resin injection progressive die chamber, impregnation of fibers strengthens the moulding that is heating and curing again behind the body, generally only uses a kind of resin matrix with a moulding process, does not give goods top layer specific function.

Summary of the invention

The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide that a kind of surface quality is better, globality is better, the composite element with surface functional layer of excellent combination property, also provide a kind of operability better, be fit to the large-scale component moulding and be combined with RFI technology and the RTM preparation method of this composite element of RTM technology two-fold advantage.

For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of composite element with surface functional layer, and described composite element comprises upper epidermis, following top layer and intermediate core layer; Described upper epidermis, following top layer are first composite system, and described intermediate core layer is second composite system; Described first composite system is to be matrix with epoxy resin, phenolic resins, vinylite or unsaturated polyester resin, described second composite system is to be matrix with the unsaturated polyester resin, and described first composite system and second composite system all are that no latitude cloth, plain, twill or the satin with carbon fiber or glass fibre serves as to strengthen body.

In the above-mentioned composite element, also preferably contain fire retardant, antistatic additive or wave absorbing agent functional additives such as (lossy mediums) in described first composite system with surface functional layer; Wherein, the content of described fire retardant generally is no more than 10% of substrate quality in first composite system, be preferably 1%～10%, the content of described antistatic additive generally is no more than 20% of substrate quality in first composite system, be preferably 2%～20%, the content of described wave absorbing agent generally is no more than 20% of substrate quality in first composite system, is preferably 2%～20%; Also contain polymerization inhibitor in described second composite system, the content of described polymerization inhibitor generally is no more than 5% of substrate quality in second composite system, is preferably 0.5%～5%.

In the above-mentioned composite element with surface functional layer, the thickness proportion of described upper epidermis, following top layer and intermediate core layer preferably is controlled at 1: (1～2): (4～20).

As a total technical conceive, the present invention also provides a kind of RTM preparation method with composite element of surface functional layer, described RTM preparation method adopts earlier RFI technology to strengthen resin molding at a RTM technological forming with the die surface preparation, then with being coated with the described mold for forming of this enhancing resin molding and preparing the composite element with surface functional layer by RTM technology.This preparation method is the comprehensive improvement to traditional RTM technology and traditional RFI technology, the enhancing resin molding that wherein utilizes RFI technology to prepare is generated as the upper and lower top layer of composite element (being manufactured goods) at last, RTM technology then is mainly used in the intermediate core layer of forming composite member, simultaneously through making upper and lower top layer and intermediate core layer be shaped to an integral body behind the curing schedule in the RTM technology.

Preferably, above-mentioned RTM preparation method specifically can may further comprise the steps:

(1) preparation strengthens resin molding: the reinforcing material shop that cuts is overlayed on described mold for forming surface, this mold for forming comprises formpiston and former, use the even dip-coating of first resin system of preparation in advance on described reinforcing material surface then, and described first resin system carried out precuring, obtain upper and lower top layer respectively and strengthen resin molding;

(2) preparation composite element: the reinforcing material preform shop that will prepare separately is layed onto described upper epidermis or following top layer strengthens surface resin film, then described formpiston and former are carried out matched moulds, on the mould behind the matched moulds, connect simultaneously injecting glue system and the pumped vacuum systems that resin transfer molding (RTM) process is used, then the die cavity behind the matched moulds is vacuumized processing and carries out the injection of second resin system, finish until the second resin system filling; Remove described injecting glue system and pumped vacuum systems at last and carry out the co-curing processing, obtain having the composite element of surface functional layer after the demoulding, the finishing;

Described first resin system is epoxy resin, phenolic resins, vinylite or unsaturated polyester resin; Described second resin system is a unsaturated polyester resin; Described reinforcing material is no latitude cloth, plain, twill or the satin of carbon fiber or glass fibre.

Among the above-mentioned preparation method, the temperature during described precuring preferably is controlled at 30 ℃～60 ℃, and the time of precuring is preferably 1～6h; Described vacuumizing when handling makes the vacuum of described die cavity preferably reach 0.085MPa above (ideal value is 0.1MPa); Curing system when described co-curing is handled is preferably earlier and is incubated 2～4h down at 30 ℃～60 ℃, then insulation 2～4h under 60 ℃～150 ℃.

Among the above-mentioned preparation method, the system of described precuring determines it is to decide according to the curing characteristics of actual first resin system of selecting in the concrete practice, this preferred precuring system can allow described first resin system suitably harden, and does not make the first resin system completion of cure simultaneously again.

Among the above-mentioned preparation method, it is exactly to make the described upper and lower top layer enhancing resin molding and second resin system carry out co-curing, bond altogether, to form an integral body that described co-curing is handled; Wherein the definite of co-curing system is to decide according to the curing characteristics of described first resin system and second resin system equally, is exactly the co-curing system of two kinds of resin systems specifically.

Compared with prior art, the invention has the advantages that: the present invention in conjunction with RFI technology Z fast advantage of impregnating speed in dipping distance weak point and RTM technical face, need not prefabricated a large amount of large-area RFI resin molding simultaneously by traditional RFI and RTM technology are improved.Problem in view of the technological operation difference of traditional RFI resin molding, the present invention improves traditional RFI resin molding, introduced wild phase and obtain RFI enhancing resin molding of the present invention (be called for short and strengthen resin molding) in the RFI resin molding, this wild phase is to be applied by the multi-layer fiber cloth shop to form.Than traditional RTM technology, owing to prepared the enhancing resin molding in RTM technology with die surface among the preparation method of the present invention, this makes composite element goods of the present invention have better surface quality; And be preset at the enhancing resin molding of this die surface owing to be precuring, so also increased the rigidity of this mould, be beneficial to the injection pressure that increases RTM technology, so that prepare large-sized composite element; And because to strengthen first resin system of resin molding be precuring, can to carry out co-curing bonding altogether with second resin system that injects die cavity thereafter, the therefore good integrity of the composite element finished product of preparation.In addition, because the otherness of composite element of the present invention material therefor system in superficial layer, intermediate core layer makes the present invention can give some specific function of superficial layer (for example adding fire retardant makes extexine have flame retardant effect).

Description of drawings

Fig. 1 is the process principle figure of traditional RFI technology;

Fig. 2 is the process principle figure of traditional RTM technology;

Fig. 3 prepares the state of the art figure of top layer enhancing resin molding down in the embodiment of the invention 1;

Fig. 4 covers the state of the art figure of reinforcing material preform for the embodiment of the invention 1 middle berth;

Fig. 5 is the state of the art figure during the vacuum injecting glue in the embodiment of the invention 1;

The composite element structural representation of Fig. 6 for preparing in the embodiment of the invention 1.

Marginal data:

1, former 2, formpiston

3, injecting glue system 31, gum-injecting port

4, pumped vacuum systems 41, gum outlet

5, the top layer strengthens resin molding 51, resin adhesive liquid down

52, surface fibre preform 53, glue scraping plate

6, upper epidermis strengthens resin molding 7, reinforcing material preform

8, RFI mould 81, resin molding

82, fibre reinforcement 83, vacuum bag

84, die cavity 9, composite element

91, upper epidermis 92, following top layer

93, intermediate core layer

The specific embodiment

Embodiment 1:

Preparation scenic spot tourist coach roof

Adopt preparation method of the present invention to prepare a kind of composite element, specifically may further comprise the steps as scenic spot tourist coach roof:

1. preparation mould

Physical dimension preparation formpiston 2 and former 1 as shown in Figure 5 according to pre-designed scenic spot tourist coach roof.

2.RFI the technology preparation strengthens resin molding

2.1 reinforcing material is covered in the cutting shop: cutting is used to prepare the reinforcing material that strengthens resin molding, this reinforcing material is that alkali-free glass fibre 02 plain (available from Jiangsu Danyang Zhongya Glass Fiber Co., Ltd.) is made, according to four layers of alkali-free glass fibre 02 plain of shape and size cutting of former 1, the shop that superposes successively as shown in Figure 3 then overlays on former 1 surface and obtains surface fibre preform 52;

2.2 dip-coating first resin system: (this resin is a kind of unsaturated polyester resin to prepare a certain amount of 191# matrix resin, available from U.S. Ya Shilan Co., Ltd), add curing agent methyl ethyl ketone peroxide (available from chemical reagent work of Guangdong Ba Ling petro-chemical corporation) according to 1% of matrix resin quality, consider that the scenic spot tourist coach requires very high to security performance (flame retardant effect), need emphasis to consider the anti-flammability of resin system, therefore in aforementioned 191# matrix resin, add the talcum powder of quality 4% as fire retardant; After the even mixing of matrix resin, curing agent and fire retardant, obtain resin adhesive liquid 51 (i.e. first resin system), good surface fibre preform 52 surfaces (as shown in Figure 3) are covered in its dip-coating in the shop, and with glue scraping plate 53 that resin adhesive liquid 51 is evenly floating on surface fibre preform 52 surfaces, make resin adhesive liquid 51 abundant lay-up;

2.3 precuring: the precuring operation of carrying out resin adhesive liquid 51 hardening time according to 30 ℃ solidification temperatures, 2h obtains down the top layer and strengthens resin molding 5;

According to the operation of above-mentioned steps 2.1～2.3, strengthen resin molding 6 at formpiston 2 surface preparation upper epidermis.

3.RTM technology prepares composite element

3.1 the reinforcing material preform is covered in the cutting shop: cutting is used to prepare the reinforcing material preform 7 of intermediate core layer composite, used reinforcing material is alkali-free glass fibre 04 plain (available from Jiangsu Danyang Zhongya Glass Fiber Co., Ltd.), according to ten layers of alkali-free glass fibre 04 plain of shape cutting of former 1, the shop that superposes successively as shown in Figure 4 then overlays on and is coated with down former 1 surface that the top layer strengthens resin molding 5;

3.2 matched moulds: formpiston 2 and former 1 matched moulds are formed die cavity, and check the air-tightness of die cavity;

3.3 vacuum injecting glue: prepare Palatal1777-G-4 unsaturated polyester (UP) (available from Nanjing DSM company), methyl ethyl ketone peroxide (available from chemical reagent work of Guangdong Ba Ling petro-chemical corporation) and F-2 polymerization inhibitor (available from Korea S CRAY VALLEY company), prepare RTM technology injecting glue system 3 and pumped vacuum systems 4, injecting glue system 3 is connected to gum-injecting port 31 places that are provided with on the mould by structure shown in Figure 5, pumped vacuum systems 4 is connected to gum outlet 41 places that are provided with on the mould, regulate the measuring equipment in the injecting glue system 3, make Palatal1777-G-4 unsaturated polyester (UP) in the injecting glue process, the mass ratio of methyl ethyl ketone peroxide and F-2 polymerization inhibitor is 100: 1: 2, obtains second kind of resin adhesive liquid (i.e. second resin system) after mixing; Open 4 pairs of die cavitys of pumped vacuum systems and vacuumize processing, and maintenance die cavity vacuum is more than the 0.09MPa; Open injecting glue system 3 then, second kind of resin adhesive liquid preparing in this step is expelled in the die cavity, when gum outlet 41 places have second kind of resin adhesive liquid to overflow, stop injection; Close pumped vacuum systems 4, stop to vacuumize;

3.4 co-curing is handled: pumped vacuum systems 4 and injecting glue system 3 are removed from mould respectively, solidified 2h earlier according to 30 ℃ solidification temperature then, according to behind 60 ℃ the solidification temperature curing 2h, finish co-curing and handle operation again;

3.5 post processing: the demoulding, finishing, cleaning obtains scenic spot tourist coach roof finished product.

The scenic spot tourist coach roof finished product of present embodiment preparation is as shown in Figure 6 a composite element 9, comprises upper epidermis 91, top layer 92 and intermediate core layer 93 down; Upper epidermis 91, following top layer 92 are first composite system, and intermediate core layer 93 is second composite system; First composite system is to be matrix with the 191# unsaturated polyester resin, with alkali-free glass fibre 02 plain (four layers) serves as to strengthen body, also contain fire retardant in first composite system, the fire retardant quality be in first composite system matrix resin quality 4%; Second composite system is to be matrix with the Palatal1777-G-4 unsaturated polyester resin, with alkali-free glass fibre 04 plain (ten layers) serves as to strengthen body, also contain the F-2 polymerization inhibitor in second composite system, F-2 polymerization inhibitor quality be in second composite system matrix resin quality 2%.The thickness proportion of upper epidermis 91, following top layer 92 and intermediate core layer 93 is 1: 1: 5 in this composite element 9.

Embodiment 2:

Preparation large glass steel composite material hull housing

Adopt preparation method of the present invention to prepare a kind of large glass steel composite material member, specifically may further comprise the steps as the hull housing:

1. preparation mould

Physical dimension according to pre-designed hull housing prepares formpiston and former.

2.RFI the technology preparation strengthens resin molding

2.1 reinforcing material is covered in the cutting shop: cutting is used to prepare the reinforcing material that strengthens resin molding, this reinforcing material is medium-alkali glass fibre 02 plain (available from Jiangsu Danyang Zhongya Glass Fiber Co., Ltd.), according to four layers of medium-alkali glass fibre 02 plain of shape and size cutting of former, the stack shop overlays on female mold surfaces successively then;

2.2 dip-coating first resin system: prepare a certain amount of 992 vinylites as matrix resin (available from U.S. Ya Shilan Co., Ltd), after the even mixing of matrix resin, obtain resin adhesive liquid, good reinforcing material surface is covered in its dip-coating in the shop, and with glue scraping plate that resin adhesive liquid is evenly floating on the reinforcing material surface, make the abundant lay-up of resin adhesive liquid;

2.3 precuring: the precuring operation of carrying out resin adhesive liquid hardening time according to 30 ℃ solidification temperatures, 2h obtains down the top layer and strengthens resin molding;

2.4 the preparation upper epidermis strengthens resin molding: cover reinforcing material according to the male mold surfaces cutting shop that operates in of step 2.1 equally, prepare a certain amount of 191# matrix resin (a kind of unsaturated polyester resin then, available from U.S. Ya Shilan Co., Ltd), add curing agent methyl ethyl ketone peroxide (available from chemical reagent work of Guangdong Ba Ling petro-chemical corporation) according to 1% of this 191# matrix resin quality, add talcum powder as fire retardant by 6% of this 191# matrix resin quality; After the even mixing of matrix resin, curing agent and fire retardant, obtain resin adhesive liquid (all belonging to first resin system) with the resin adhesive liquid in the step 2.2, good reinforcing material surface is covered in its dip-coating in the shop, and with glue scraping plate that resin adhesive liquid is evenly floating on the reinforcing material surface, make the abundant lay-up of resin adhesive liquid; The precuring operation of carrying out resin adhesive liquid hardening time according to 30 ℃ solidification temperatures, 2h obtains upper epidermis and strengthens resin molding.

3.RTM technology prepares composite element

3.1 the reinforcing material preform is covered in the cutting shop: cutting is used to prepare the reinforcing material preform of intermediate core layer composite, used reinforcing material is alkali-free glass fibre 04 plain (available from Jiangsu Danyang Zhongya Glass Fiber Co., Ltd.), according to 15 layers of alkali-free glass fibre 04 plain of shape cutting of former, the stack shop overlays on and is coated with down the female mold surfaces that the top layer strengthens resin molding successively then;

3.2 matched moulds: formpiston and former matched moulds are formed die cavity, and check the air-tightness of die cavity;

3.3 vacuum injecting glue: prepare 196 unsaturated polyester (UP)s (available from Wenzhou Zhongqiao Resin Chemical Industrial Corporation), methyl ethyl ketone peroxide (available from chemical reagent work of Guangdong Ba Ling petro-chemical corporation) and F-2 polymerization inhibitor (available from Korea S CRAY VALLEY company), prepare RTM technology injecting glue system and pumped vacuum systems, the injecting glue system is connected to the gum-injecting port place that is provided with on the mould, pumped vacuum systems is connected to the gum outlet place that is provided with on the mould, regulate the measuring equipment in the injecting glue system, make 196 unsaturated polyester (UP)s in the injecting glue process, the mass ratio of methyl ethyl ketone peroxide and F-2 polymerization inhibitor is 100: 1: 1.5, obtains resin adhesive liquid (i.e. second resin system) after mixing; Open pumped vacuum systems die cavity is vacuumized processing, and maintenance die cavity vacuum is more than the 0.09MPa; Open the injecting glue system simultaneously, the resin adhesive liquid of preparing in this step is expelled in the die cavity, when the gum outlet place has resin adhesive liquid to overflow, stop injection; Close pumped vacuum systems, stop to vacuumize;

3.4 co-curing is handled: pumped vacuum systems and injecting glue system are removed from mould respectively, solidified 2h earlier according to 40 ℃ solidification temperature then, according to behind 60 ℃ the solidification temperature curing 2h, finish co-curing and handle operation again;

3.5 post processing: the demoulding, finishing, cleaning obtains glass fiber reinforced plastics composite material hull housing finished product.

The glass fiber reinforced plastics composite material hull housing finished product of present embodiment preparation is a sandwich type composite element, comprises upper epidermis, following top layer and intermediate core layer; Upper epidermis, following top layer are first composite system, and intermediate core layer is second composite system; First composite system on following top layer is to be matrix with 992 vinylites, serves as to strengthen body with medium-alkali glass fibre 02 plain (four layers); First composite system of upper epidermis is to be matrix with the 191# unsaturated polyester resin, with alkali-free glass fibre 02 plain (four layers) serves as to strengthen body, also contain fire retardant in the upper epidermis, the fire retardant quality be in first composite system matrix resin quality 6%; Second composite system is to be matrix with 196 unsaturated polyester (UP)s, with alkali-free glass fibre 04 plain (15 layers) serves as to strengthen body, also contain the F-2 polymerization inhibitor in second composite system, F-2 polymerization inhibitor quality be in second composite system matrix resin quality 1.5%.The thickness proportion of upper epidermis, following top layer and intermediate core layer is 1: 1: 7 in this composite element.

Product of the present invention and technology are suitable for the global formation of various types of large-scale composite material members such as large scale wind power machine composite material blade housing, large ship housing, train composite casing fully.What need to adjust in concrete the application mainly is mould, reinforcing material and resin system.The composite element good integrity of the present invention's preparation; can be widely used in high efficiency, high-quality moulding, conceive the various process programs of no substantial differences all in the protection domain of claim of the present invention with the present invention such as large-scale composite material members such as blades of large-scale wind driven generator, large ship housing, rail traffic vehicles casings.

Claims (1)

1. RTM preparation method with composite element of surface functional layer, it is characterized in that: described RTM preparation method adopts earlier the resin molding infiltration process to strengthen resin molding in a resin transfer molding (RTM) process mold for forming surface preparation, then with being coated with the described mold for forming of this enhancing resin molding and preparing the composite element with surface functional layer by resin transfer molding (RTM) process;

Described preparation method specifically may further comprise the steps:

(1) preparation strengthens resin molding: the reinforcing material shop that cuts is overlayed on described mold for forming surface, this mold for forming comprises formpiston and former, use the even dip-coating of first resin system of preparation in advance on described reinforcing material surface then, and described first resin system carried out precuring, obtain upper and lower top layer respectively and strengthen resin molding; Temperature during described precuring is controlled at 30 ℃～60 ℃, and the time of precuring is 1～6 h;

(2) preparation composite element: the reinforcing material preform shop that will prepare separately is layed onto described upper epidermis or following top layer strengthens surface resin film, then described formpiston and former are carried out matched moulds, on the mould behind the matched moulds, connect simultaneously injecting glue system and the pumped vacuum systems that resin transfer molding (RTM) process is used, then the die cavity behind the matched moulds is vacuumized processing and carries out the injection of second resin system, vacuumize when handling, the vacuum of described die cavity is reached more than the 0.085MPa, finish until the second resin system filling; Remove described injecting glue system and pumped vacuum systems at last and carry out the co-curing processing, the curing system when described co-curing is handled is earlier at 30 ℃ ～60 ℃ of insulations 2 down ～4 h are then at 60 ℃ ～150 ℃ of insulations 2 down ～4 h obtain having the composite element of surface functional layer after the demoulding, the finishing;

Described first resin system is epoxy resin, phenolic resins, vinylite or unsaturated polyester resin; Described second resin system is a unsaturated polyester resin; Described reinforcing material is no latitude cloth, plain, twill or the satin of carbon fiber or glass fibre.

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