CN102941722A - Flame-retardant corrosion-resistant case material, resin transfer molding (RTM) technique thereof and injection molding system - Google Patents
Flame-retardant corrosion-resistant case material, resin transfer molding (RTM) technique thereof and injection molding system Download PDFInfo
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Abstract
The invention discloses a flame-retardant corrosion-resistant case material which is mainly composed of inner and outer layer composite materials. The inner layer takes low-pressure barium phenolic resin as the substrate, the outer layer takes a bisphenol A (BPA) epoxy vinyl ester resin and dibenzoyl peroxide system as the substrate, and transition between the inner layer and the outer layer is achieved through a dibenzoyl peroxide; the case material is prepared through an RTM technique for simultaneous injection and synchronous curing, in detail, the preparing method includes preparing an injection molding system first and preparing overlying fiber preforms; then preheating resin and performing simultaneous injection and synchronous curing in two sets of the injection molding systems; and finally demolding and trimming to obtain the case material. The injection molding system comprises a die, first and second injection units and first and second vacuum-pumping units, wherein a polysulfone membrane is arranged in the die cavity and divides the die cavity into an inner layer die cavity and an outer layer die cavity. The material, the technique and the system have the advantages that the technique steps are few, the equipment investment is small, the cost is low, the efficiency is high, once integral molding is facilitated, and the like.
Description
Technical field
The present invention relates to a kind of fibre reinforced composites and forming preparation process thereof, relate in particular to a kind of composite and RTM moulding process thereof with Multifunctional layered.
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 refers to liquid polymer is injected the closed mould cavity that is covered with perform manufacturing, or heat fused puts into the resin molding of die cavity in advance, and liquid polymer is finished the infiltration of resin/fiber and sent out a technology through the class preparation that curing molding becomes goods 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 with 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 development direction of now composite low-cost manufacturing technique.
RTM technique is a kind of technology that adopts the rigidity close die to make composite, and technological principle as shown in Figure 1.RTM technique is to place in advance reinforcing material preform 13 in the mold cavity of formpiston 12 and former 11 compositions, after matched moulds clamps, under certain temperature and pressure, will be injected in the mold cavity through the gum-injecting port 14 of injecting systems 15 through the resin system that static mixer mixes, vacuumize by pumped vacuum systems 17, the unnecessary resin of resin system lay-up preform 13(is extracted out from gum outlet 16), obtain goods finally by curing, the demoulding.RTM technique has become one of main development direction of advanced composite material low-cost manufacturing technique because of advantages such as it have product's dimensional precision height, even thickness, porosity is low, fugitive constituent is few.
For some composite element, such as the glass fiber hull case material, the hull housing generally is comprised of inside and outside two parts, and the housing internal layer requires to have the fire-retardant fireproof function to guarantee the safety of passenger in the cabin, and the outer energy resisting sea water erosion that requires of housing is to guarantee the hull durability.
Yet, traditional RTM technique can only be injected single resin, for above-mentioned glass fiber hull housing composite element with inside and outside dual functional layer, common preparation method adopts RTM technique to prepare respectively each functional layer, again it is bonded together, so not only increase difficulty and the complexity of technique, and reduced integrally-built reliability.If adopt simultaneously injected mode disposable integral to prepare such composite element, at first because injection technique characteristic and the curing process characteristic of dissimilar resins differ greatly, two kinds of dissimilar resins are difficult to realize simultaneously injection and solidify synchronously; Secondly because two kinds of resins enter die cavity simultaneously, do not have separation layer between the enhancing body of difference in functionality layer, two kinds of dissimilar resin adhesive liquid can produce mixed flow.As seen, for the moulding of the composite element with Multifunctional layered, can't effectively solve in the existing RTM forming technique always.
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 cost is low, good integrity, mechanical property is good and the case material of good flame resistance, good corrosion resistance, provide also that a kind of processing step is few, process equipment drop into little, cost is low, efficient is high, be conducive to the RTM moulding process of Integratively formed aforementioned case material, also provide a kind of simple in structure, easy to assembly, cost is low, can be used for the injection molding apparatus that the RTM moulding process of RTM disposal integral molding Multifunctional layered composite is used.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind ofly to have fire-retardant and case material decay resistance, mainly formed by inner layer composite material and outer layer of composite material, described inner layer composite material is as the internal layer matrix take the low pressure ba phenolic resin, described outer layer of composite material is as outer matrix take bisphenol type epoxy vinyl ester resin and curing agent dibenzoyl peroxide system, (thickness is preferably 0.02mm～0.03mm by a polysulfones rete in the middle of described inner layer composite material and the outer layer of composite material, for example about 0.025mm) realize transition and fusion, described case material is to inject simultaneously by RTM technique, solidify synchronously and Integratively formed after prepare.In fact, case material of the present invention is specially adapted to glass fiber hull, and for the various functional materials that requirement beyond the glass fiber hull has fire-retardant and corrosion-resistant inside and outside two kinds of functional layers, the present invention all can be equal to applicable.
In the above-mentioned case material with fire-retardant and decay resistance, preferred, described low pressure ba phenolic resin viscosity in 55 ℃～80 ℃ temperature range is lower than 800mPas, and the retention time of viscosity below 800mPas is greater than 20min.
In the above-mentioned case material with fire-retardant and decay resistance, preferred, described bisphenol type epoxy vinyl ester resin viscosity in 30 ℃～75 ℃ temperature range is lower than 800mPas, and the retention time of viscosity below 800mPas is greater than 20min.
Above-mentioned has fire-retardant and case material decay resistance, and in the resin system of described outer matrix adopting, the consumption of described dibenzoyl peroxide is preferably 1%～5% of bisphenol type epoxy vinyl ester resin quality.
As a total technical conceive, the present invention also provides a kind of above-mentioned RTM moulding process with case material of fire-retardant and decay resistance, may further comprise the steps:
(1) prepare injection molding apparatus: the physical dimension according to the case material that designs in advance, be ready to the injection molding apparatus that the RTM moulding process is used, described injection molding apparatus comprises mould, the first injecting systems, the second injecting systems and pumped vacuum systems;
(2) preparation preform: reinforcing material and PS membrane are covered in the inner surface shop at described mould, make its final superimposed type perform manufacturing that forms inner fiber preform-PS membrane-outer layer fiber preform; Form the internal layer die cavity that comprises the inner fiber preform of being kept apart by PS membrane and the outer die cavity that comprises the outer layer fiber preform behind the mould matched moulds;
(3) prepare resin system: the low pressure ba phenolic resin of in described the first injecting systems, purchasing, in described the second injecting systems, purchase bisphenol type epoxy vinyl ester resin and curing agent dibenzoyl peroxide system, and resin in first and second injecting systems carried out preheating;
(4) injection: described first and second injecting systems is connected with described internal layer die cavity and outer die cavity respectively, open described pumped vacuum systems, make the low pressure ba phenolic resin in described the first injecting systems be expelled in the internal layer die cavity and abundant dipping inner fiber preform wherein, meanwhile, make bisphenol type epoxy vinyl ester resin and curing agent dibenzoyl peroxide system in described the second injecting systems be expelled in the outer die cavity and the abundant outer layer fiber preform that floods wherein;
(5) solidify: the mould after injection is finished solidifies processing synchronously, through the demoulding, finishing, obtains having fire-retardant and case material decay resistance after curing is finished.
Above-mentioned RTM moulding process, the curing cycle during described curing is preferably: be incubated 2h～4h first under 70 ℃～80 ℃ temperature, then be incubated 2h～4h under 110 ℃～120 ℃ temperature, be incubated 2h～4h at last under 150 ℃～160 ℃ temperature.
Above-mentioned RTM moulding process, the injection temperature during described injection preferably are controlled at 55 ℃～70 ℃.By adjusting the injection pressure of two kinds of resin adhesive liquid, can realize that two kinds of resin adhesive liquid are to the synchronous dipping of perform manufacturing separately.
Above-mentioned RTM moulding process, preferably, mould in the described injection molding apparatus comprises former and formpiston, PS membrane in described formpiston and the die cavity is encircled into described internal layer die cavity, PS membrane in described former and the die cavity is encircled into described outer die cavity, described the first injecting systems is communicated to the internal layer die cavity by the first gum-injecting port, and described the second injecting systems is communicated to outer die cavity by the second gum-injecting port; Described pumped vacuum systems comprises the first pumped vacuum systems and the second pumped vacuum systems, and described the first pumped vacuum systems is communicated to the internal layer die cavity by the first gum outlet, and described the second pumped vacuum systems is communicated to outer die cavity by the second gum outlet.
As a total technical conceive, the present invention also provides a kind of injection molding apparatus fire-retardant and that case material RTM moulding process decay resistance is used that has, comprise mould, the first injecting systems, the second injecting systems, the first pumped vacuum systems and the second pumped vacuum systems, described mould comprises former and formpiston, be provided with a PS membrane in the die cavity that described former and formpiston form, described polysulfones rete is separated into internal layer die cavity and outer die cavity with described die cavity, described the first injecting systems is communicated to the internal layer die cavity by the first gum-injecting port, and described the second injecting systems is communicated to outer die cavity by the second gum-injecting port; Described the first pumped vacuum systems is communicated to the internal layer die cavity by the first gum outlet, and described the second pumped vacuum systems is communicated to outer die cavity by the second gum outlet.
Technique scheme is based on following technical thought, at first be based in the reality demand to the case material with inside and outside difference in functionality layer, this its inside part of shells material General Requirements has the fire protection flame retarding function to guarantee the safety of personnel in the body of cabin, Outboard Sections is owing to be immersed in the water for a long time, housing outer surface can suffer erosion easily, so housing outer surface should have anticorrosion, moisture-proof function.For the RTM moulding process that this shells material can application of advanced is prepared, then at first need to select respectively suitable resin combination product for internal layer and the skin of this shells material, and the resin combination product of selecting must meet two basic conditions, that is: the first, two kinds of resins of inside and outside layer should satisfy RTM technique to simultaneously injection, the integrated molding requirement of solidifying synchronously; The second, these two kinds of resins inject at the same time, can not react to each other in the curing molding process synchronously and miscible.Certainly, except aforementioned two fundamentals, the resin of selecting also should keep higher level and relative advantage at the aspects such as superiority of raw material availability, economy, function.Therefore, the selection of RTM resin raw material, that is be the selection of resin matrix in the glass fiber hull case material, become one of key element of the present invention.
At first, with regard to the outer matrix of case material of the present invention, in order to optimize the resin as the corrosion proof function layer of can be used in the case material of the present invention that obtains to be applicable to the RTM injection, we are take the strongest vinyl ester resin of resistance to chemical attack function as the basis, yet the kind that vinyl ester resin comprises is very abundant, and the curing agent kind that is applicable to various vinyl ester resins is also quite a lot of, after repeatedly testing, optimize and obtain the bisphenol type epoxy vinyl ester resin, phenol formaldehyde epoxy vinyl ester resin/, flexible ethylene base ester resin, the PU modified epoxy vinyl ester resin, the acrylic type vinyl ester resin is as the resin matrix tested object, methyl ethyl ketone peroxide with optimization from numerous curing agent, isopropyl benzene hydroperoxide, dibenzoyl peroxide is as the curing agent tested object, and the viscosity-temperature characteristics of testing respectively the resin system that aforementioned differing ethylene base ester resin and curing agent consist of, characteristic when sticking, DSC, the mechanical property of resin cured matter, and the indexs such as decay resistance of the composite take aforementioned resin as matrix, through our contrast repeatedly, observation and analysis has determined that finally the bisphenol type epoxy vinyl ester resin of combination property the best and curing agent dibenzoyl peroxide system are as the base stock of case material ectomesoderm resin matrix of the present invention.This resin system is carried out the Chemical Kinetics analysis as can be known, and the curing cycle of this resin system is at 50 ℃～80 ℃ lower insulation 2h～4h, at 100 ℃～120 ℃ lower insulation 2h～4h, then at 140 ℃～160 ℃ lower insulation 2h～4h.
Under the prerequisite as the outer anticorrosion moisture-proof function of case material of the present invention layer matrix, we further determine selecting of inner layer resin matrix material at selected bisphenol type epoxy vinyl ester resin and curing agent dibenzoyl peroxide system.With regard to the internal layer matrix of case material of the present invention, general preferred employing phenolic resins carries out fire-retardant as internal layer, yet, the resin kind that comprises in the phenolic resins is very abundant, by our repeatedly experiment, observation and analysis, we are with the ammonia phenolic resins after optimizing, Phenolic Resin Modified By Bismaleimide benzoxazine colophony, poly-aryl ethane resin, common ba phenolic resin, the low pressure ba phenolic resin, Novolac Cyanate Ester Resins is concrete tested object, the viscosity-temperature characteristics that the process system repeatedly is tested various phenolic resins, characteristic when sticking, DSC, the mechanical property of resin cured matter, and the composite oxygen index (OI) take aforementioned phenolic resins as matrix, finally we have determined that the resin that the internal layer matrix is selected in the case material of the present invention is the low pressure ba phenolic resin, by the low pressure ba phenolic resin is carried out the Chemical Kinetics analysis as can be known, the curing cycle of low pressure ba phenolic resin is: at 70 ℃～90 ℃ lower insulation 2h～4h, at 110 ℃～130 ℃ lower insulation 2h～4h, then at 150 ℃～170 ℃ lower insulation 2h～4h.This resin can not only mate aforementioned definite bisphenol type epoxy vinyl ester resin and the process window of curing agent dibenzoyl peroxide system, and combination property reaches best.
Therefore, disclose in the prior art under a great selection of prerequisite of selecting the resin kind, under the Protean background of the combination of different resins and curing agent thereof, the present invention has finally determined can jointly be applicable to the RTM injection molding technique and inject simultaneously, the resin combination mode of solidifying synchronously, this is not only the present application people contrast experiment repeatedly and the technical scheme that proposes after optimizing, and decay resistance and the mechanical property of outermost resin have been taken into full account, mechanical property and the fire resistance of inner layer resin have also been taken into full account, also taken into full account two kinds of resins inject simultaneously and synchronously admittedly the time to the applicability of technological requirement, also fully verified effect and the feasibility of various resin formulas, technique scheme of the present invention finally shows very significant technique effect and advantage.
In the case material of the present invention, after the selection of outermost resin matrix and collocation mode are determined, need also further to solve that two kinds of resins may dissolve each other in the RTM technique, mixed flow and the problem that reacts to each other, because only have a die cavity in traditional RTM injection molding apparatus, if multilayer materials is moulding in same die cavity all, then can make inevitably resin matrix generation mixed flow, thereby the purpose that makes preparation have inside and outside double-deck functional layer composite can not realize, although once have the cured resin matrix was prepared the Multifunctional layered composite as the intermediate isolating layer with the process program of realizing the die cavity subregion, but this technique also is only applicable to the composite more than three layers, and owing to increased the setting of intermediate isolating layer, its process costs improves greatly.And in dissimilar for fear of two kinds among the present invention, mixed flow occurs after entering simultaneously die cavity in the outermost resin glue, the present invention has adopted and PS membrane has been set as two kinds of functional layer separation interface, the optimal material that obtains behind inventor's process systematic comparison and the Optimum Experiment is not only in the selection of PS membrane material, and its thickness little (only having about 0.02mm), technological operation is good, and (it is convenient to lay, two kinds of glues can be isolated fully), interfacial bonding property excellent (in the resin adhesive liquid solidification process of both sides, can form good interface combination), in behind co-curing, can really realizing, the perfect adaptation of outer layer of composite material and one-body molded can not look like such as bonding, the physical bond mode such as cementing affects the globality of case material.
In sum, compared with prior art, the invention has the advantages that: the resin combination collocation mode that the present invention proposes, the injection molding apparatus of RTM moulding process and resin adhesive liquid, injection and synchronously curing when can really realize two kinds of different resins, but its effective application has the preparation of fire-retardant and corrosion-resistant two kinds of functional layer composite elements in glass fiber hull housing etc., can realize the Integratively formed of this Multifunctional layered (particularly two one functional layer) composite element, reduce processing step, improve the integrally-built reliability of RTM moulded products, the multifunctionality of RTM moulded products is strengthened, reduce preparation cost.
Description of drawings
Fig. 1 is the structural representation that RTM technique is used injection molding apparatus in the prior art.
Fig. 2 is the structural representation that RTM technique is used injection molding apparatus among the present invention.
Fig. 3 is the Cross Section Morphology photo of the glass fiber hull case material that makes in the embodiment of the invention.
Marginal data:
11. former; 12. formpiston; 13. reinforcing material preform; 14. gum-injecting port; 15. injecting systems; 16. gum outlet; 17. pumped vacuum systems; 21. inner fiber preform; 22. PS membrane; 23. outer layer fiber preform; 31. the first injecting systems; 32. the second injecting systems; 41. the first gum-injecting port; 42. the second gum-injecting port; 51. the first pumped vacuum systems; 52. the second pumped vacuum systems; 61. the first gum outlet; 62. the second gum outlet; 71. inner layer composite material; 72. polysulfones rete; 73. outer layer of composite material.
The specific embodiment
The invention will be further described below in conjunction with Figure of description and specific embodiment.
Embodiment: glass fiber hull housing and RTM moulding thereof.
A kind of glass fiber hull housing of the present invention as shown in Figure 3, the skin of this glass fiber hull case material will contact the seawater face, need to have the functions such as protection against the tide, anticorrosion, internal layer is mainly used in carrying and guarantees personal security in the cabin, need have good mechanical property and fire resistance.Case material in the present embodiment mainly is comprised of inner layer composite material 71 and outer layer of composite material 73, inner layer composite material 71 is that (trade mark is as B30 take the low pressure ba phenolic resin, available from brass hill chemical plant, Gaobeidian City, Hebei) be the internal layer matrix, low pressure ba phenolic resin viscosity in 55 ℃～80 ℃ temperature range is lower than 800mPas, and the retention time of viscosity below 800mPas is greater than 20min; Outer layer of composite material 73 is with the bisphenol type epoxy vinyl ester resin (trade mark 922, available from Ya Shilan company) and curing agent dibenzoyl peroxide (available from permanent Tonghua, Laiwu in Shandong province city worker Co., Ltd) resin system be outer matrix, the consumption of dibenzoyl peroxide is 2% of bisphenol type epoxy vinyl ester resin quality, wherein, outer matrix is lower than 800mPas with bisphenol type epoxy vinyl ester resin viscosity in 30 ℃～75 ℃ temperature range, and the retention time of viscosity below 800mPas is greater than 20min; Realize transition and fusions by polysulfones retes 72 in the middle of inner layer composite material 71 and the outer layer of composite material 73, the case material of present embodiment be by RTM technique inject simultaneously, solidify synchronously and Integratively formed after prepare.
The glass fiber hull case material of present embodiment is prepared by the RTM moulding process, this process using injection molding apparatus as shown in Figure 2, this injection molding apparatus comprises mould, the first injecting systems 31, the second injecting systems 32, the first pumped vacuum systems 51 and the second pumped vacuum systems 52, mould comprises former 11 and formpiston 12, be provided with a PS membrane 22 in the die cavity that former 11 and formpiston 12 form, PS membrane 22 is separated into die cavity for the internal layer die cavity of putting inner fiber preform 21 with for the outer die cavity of putting outer layer fiber preform 23, the first injecting systems 31 is communicated to the internal layer die cavity by the first gum-injecting port 41, and the second injecting systems 32 is communicated to outer die cavity by the second gum-injecting port 42; The first pumped vacuum systems 51 is communicated to the internal layer die cavity by the first gum outlet 61, and the second pumped vacuum systems 52 is communicated to outer die cavity by the second gum outlet 62.
The RTM moulding process of present embodiment glass fiber hull case material may further comprise the steps:
1. preparation injection molding apparatus:
Physical dimension according to the glass fiber hull case material that designs in advance is ready to the injection molding apparatus that RTM moulding process is as shown in Figure 2 used; And with mould and die preheating to 60 ℃.
2. preparation preform:
2.1 spread and cover the internal layer reinforcing material: cutting is for the preparation of the internal layer reinforcing material of inner layer composite material in the present embodiment housing, this internal layer reinforcing material is alkali-free glass fibre 04 plain (available from Jiangsu Danyang Zhongya Glass Fiber Co., Ltd.), according to ten layers of aforesaid alkali-free glass fibre 04 plain of shape and size cutting of formpiston 12, the shop that then superposes successively as shown in Figure 2 overlays on formpiston 12 surfaces and obtains inner fiber preform 21.
Cover the isolation PS membrane 2.2 spread: cutting is used for the insolated layer materials of isolation surfaces externally and internally functional layer, this material is that PS membrane (available from company of Bert Filters Co., Ltd of Hangzhou section) is made, external surface shape and size cutting one deck PS membrane 22 according to inner fiber preform 21 get final product (thickness is 0.02mm), then as shown in Figure 2 PS membrane 22 are spread and overlay on inner fiber preform 21 surfaces.
2.3 spread and cover outer reinforcing material: cutting is for the preparation of the outer reinforcing material of present embodiment housing ectomesoderm composite, this skin reinforcing material is alkali-free glass fibre 04 plain (available from Jiangsu Danyang Zhongya Glass Fiber Co., Ltd.), according to PS membrane 22 external surface shape and eight layers of alkali-free glass fibre 04 plain of size cutting, then superposeing successively to spread as shown in Figure 2 overlays on PS membrane 22 surfaces, obtains outer layer fiber preform 23; The final superimposed type perform manufacturing that forms inner fiber preform 21-PS membrane 22-outer layer fiber preform 23 in the die cavity behind the matched moulds; Die cavity then forms the internal layer die cavity that comprises inner fiber preform 21 of being kept apart by PS membrane 22 and comprises the outer die cavity of outer layer fiber preform 23.
3. preparation resin system:
The low pressure ba phenolic resin of purchasing in the first injecting systems 31 of present embodiment injection molding apparatus is preheated to it 60 ℃ equally.
In the second injecting systems 32 of present embodiment injection molding apparatus, purchase bisphenol type epoxy vinyl ester resin and dibenzoyl peroxide system, and the measuring equipment of regulating the second injecting systems 31, make the mass ratio of bisphenol type epoxy vinyl ester resin and dibenzoyl peroxide in the injecting glue process satisfy 100 ︰ 2, and the resin system in the second injecting systems 32 is preheated to 60 ℃.
4. injection:
The first injecting systems 31 is used for injection present embodiment housing inner layer composite material matrix, it is communicated with the internal layer die cavity by the first gum-injecting port 41, the second injecting systems 32 is for injection present embodiment housing covering ectomesoderm matrices of composite material, and it is communicated with outer die cavity by the second gum-injecting port 42.Then open simultaneously the first pumped vacuum systems 51 and the second pumped vacuum systems 52, respectively internal layer die cavity and outer die cavity are vacuumized processing, and in keeping, the vacuum of outer die cavity reaches-more than the 0.095MPa, open again the first injecting systems 31 and the second injecting systems 32, the low pressure ba phenolic resin is injected in the internal layer die cavity with dipping inner fiber preform 21 wherein through the first gum-injecting port 41, meanwhile, bisphenol type epoxy vinyl ester resin and dibenzoyl peroxide system are injected in the outer die cavity with dipping outer layer fiber preform 23 wherein through the second gum-injecting port 42, owing between two-layer perform manufacturing, be provided with the PS membrane 22 of isolation usefulness, thereby after effectively having avoided two kinds of dissimilar resin adhesive liquid systems to enter die cavity mixed flow occur; When finding that the first gum outlet 61 and the second gum outlet 62 places have resin adhesive liquid to overflow, stop injection; Close pumped vacuum systems, stop to vacuumize.
5. solidify:
After injection is finished, the first injecting systems 31, the second injecting systems 32, the first pumped vacuum systems 51 and the second pumped vacuum systems 52 are removed from mould, then mould is solidified processing synchronously, curing cycle when solidifying synchronously is: be incubated 2h first under 80 ℃ of temperature, then under 120 ℃ of temperature, be incubated 2h, under 160 ℃ of temperature, be incubated 4h at last; After finishing, curing through the demoulding, finishing, cleaning, obtains the glass fiber hull case material of present embodiment.
Claims (9)
1. one kind has fire-retardant and case material decay resistance, mainly formed by inner layer composite material and outer layer of composite material, it is characterized in that: described inner layer composite material is as the internal layer matrix take the low pressure ba phenolic resin, described outer layer of composite material is as outer matrix take bisphenol type epoxy vinyl ester resin and curing agent dibenzoyl peroxide system, realize transition and fusion by a polysulfones rete in the middle of described inner layer composite material and the outer layer of composite material, described case material is to inject simultaneously by RTM technique, solidify synchronously and Integratively formed after prepare.
2. according to claim 1 have fire-retardant and case material decay resistance, it is characterized in that: described low pressure ba phenolic resin viscosity in 55 ℃～80 ℃ temperature range is lower than 800mPas, and the retention time of viscosity below 800mPas is greater than 20min.
3. according to claim 1 and 2 have fire-retardant and case material decay resistance, it is characterized in that: described bisphenol type epoxy vinyl ester resin viscosity in 30 ℃～75 ℃ temperature range is lower than 800mPas, and the retention time of viscosity below 800mPas is greater than 20min.
4. according to claim 1 and 2 have fire-retardant and case material decay resistance, and it is characterized in that: in the resin system of described outer matrix adopting, the consumption of described dibenzoyl peroxide is 1%～5% of bisphenol type epoxy vinyl ester resin quality.
5. one kind such as each described RTM moulding process with case material of fire-retardant and decay resistance in the claim 1～4, may further comprise the steps:
(1) prepare injection molding apparatus: the physical dimension according to the case material that designs in advance, be ready to the injection molding apparatus that the RTM moulding process is used, described injection molding apparatus comprises mould, the first injecting systems, the second injecting systems and pumped vacuum systems;
(2) preparation preform: reinforcing material and PS membrane are covered in the inner surface shop at described mould, make its final superimposed type perform manufacturing that forms inner fiber preform-PS membrane-outer layer fiber preform; Form the internal layer die cavity that comprises the inner fiber preform of being kept apart by PS membrane and the outer die cavity that comprises the outer layer fiber preform behind the mould matched moulds;
(3) prepare resin system: the low pressure ba phenolic resin of in described the first injecting systems, purchasing, in described the second injecting systems, purchase bisphenol type epoxy vinyl ester resin and curing agent dibenzoyl peroxide system, and resin in first and second injecting systems carried out preheating;
(4) injection: described first and second injecting systems is connected with described internal layer die cavity and outer die cavity respectively, open described pumped vacuum systems, make the low pressure ba phenolic resin in described the first injecting systems be expelled in the internal layer die cavity and abundant dipping inner fiber preform wherein, meanwhile, make bisphenol type epoxy vinyl ester resin and curing agent dibenzoyl peroxide system in described the second injecting systems be expelled in the outer die cavity and the abundant outer layer fiber preform that floods wherein;
(5) solidify: the mould after injection is finished solidifies processing synchronously, through the demoulding, finishing, obtains having fire-retardant and case material decay resistance after curing is finished.
6. RTM moulding process according to claim 5, it is characterized in that, curing cycle during described curing is: be incubated 2h～4h first under 70 ℃～80 ℃ temperature, then be incubated 2h～4h under 110 ℃～120 ℃ temperature, be incubated 2h～4h at last under 150 ℃～160 ℃ temperature.
7. according to claim 5 or 6 described RTM moulding process, it is characterized in that the injection temperature during described injection is controlled at 55 ℃～70 ℃.
8. according to claim 5 or 6 described RTM moulding process, it is characterized in that, mould in the described injection molding apparatus comprises former and formpiston, PS membrane in described formpiston and the die cavity is encircled into described internal layer die cavity, PS membrane in described former and the die cavity is encircled into described outer die cavity, described the first injecting systems is communicated to the internal layer die cavity by the first gum-injecting port, and described the second injecting systems is communicated to outer die cavity by the second gum-injecting port; Described pumped vacuum systems comprises the first pumped vacuum systems and the second pumped vacuum systems, and described the first pumped vacuum systems is communicated to the internal layer die cavity by the first gum outlet, and described the second pumped vacuum systems is communicated to outer die cavity by the second gum outlet.
9. one kind has injection molding apparatus fire-retardant and that case material RTM moulding process decay resistance is used, comprise mould, the first injecting systems, the second injecting systems, the first pumped vacuum systems and the second pumped vacuum systems, described mould comprises former and formpiston, it is characterized in that: be provided with a PS membrane in the die cavity that described former and formpiston form, described polysulfones rete is separated into internal layer die cavity and outer die cavity with described die cavity, described the first injecting systems is communicated to the internal layer die cavity by the first gum-injecting port, and described the second injecting systems is communicated to outer die cavity by the second gum-injecting port; Described the first pumped vacuum systems is communicated to the internal layer die cavity by the first gum outlet, and described the second pumped vacuum systems is communicated to outer die cavity by the second gum outlet.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103847072A (en) * | 2014-02-14 | 2014-06-11 | 江苏恒神纤维材料有限公司 | Resin transfer molding (RTM) mold with resin heating runner |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103847072A (en) * | 2014-02-14 | 2014-06-11 | 江苏恒神纤维材料有限公司 | Resin transfer molding (RTM) mold with resin heating runner |
| EP3162547A1 (en) * | 2015-10-09 | 2017-05-03 | United Technologies Corporation | Improved laminate resin transfer molding of fibrous preforms using particle filed resin systems |
| US10086544B2 (en) | 2015-10-09 | 2018-10-02 | United Technologies Corporation | Laminate resin transfer molding of fibrous preforms using particle filled resin systems |
| CN108602289A (en) * | 2016-02-03 | 2018-09-28 | 乐金华奥斯有限公司 | Prepreg preparation facilities and utilize its preimpregnation preparation method for material |
| US10946554B2 (en) | 2016-02-03 | 2021-03-16 | Lg Hausys, Ltd. | Prepreg manufacturing device and prepreg manufacturing method using same |
| CN111098523A (en) * | 2019-11-13 | 2020-05-05 | 北京玻钢院复合材料有限公司 | Composite material light cabin and preparation method thereof |
| CN114248467A (en) * | 2021-12-29 | 2022-03-29 | 安徽玄离智能科技股份有限公司 | Robot shell grease injection process |
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