CN103042702B - Method capable of reducing the surface defects of fiber reinforced thermoplastic composite products - Google Patents
Method capable of reducing the surface defects of fiber reinforced thermoplastic composite products Download PDFInfo
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Abstract
The invention relates to a method capable of reducing the surface defects of fiber reinforced thermoplastic composite products, a fiber reinforced thermoplastic composite material formed by the method and products made by the composite material. The method comprises the following steps of: (1) providing a mold with a female mold and a male mold which are matched with each other; (b) laying more than one layer of fiber woven fabric and more than one layer of elastic fiber on the mold in a stacked way, or laying a stacked body containing more than one layer of the fiber woven fabric and more than one layer of the elastic fiber on the mold, wherein the elastic fiber products are one or more than two kinds of fabrics selected from fiber felts and three-dimensional fiber woven fabrics; (c) matching the female mold with the male mold and heating the mold; (d) injecting a thermoplastic resin composite into the mold; and (e) demolding the thermoplastic resin composite injected mold to obtain the products after the thermoplastic resin composite is solidified and the mold is cooled. The appearance of the obtained products does not have obvious dry spots or cracks.
Description
Technical field
The invention belongs to thermoplastic resin based composite material field, be specifically related to a kind of method reducing fiber reinforced thermolplastic composite material product surface defect.The invention still further relates to a kind of fiber reinforced thermolplastic composite material of being obtained by described method and a kind of goods be made up of described composite.
Background technology
Thermoplastic resin based composite material comparatively thermosetting resin based composites has shock resistance better, and the process-cycle is short, easy to be recycled, weldability and the advantage such as resistance to chemical corrosion is good.It all has a wide range of applications in fields such as space flight and aviation, automobile, chemical industry, electronics, electrical equipment.
The thermoplastic resin based composite material system being applicable to resin transfer moulding (RTM) in recent years shaping is developed.Such as in the 18th the international composite exhibition of China, win fiber reinforced nylon used for electric vehicle 6 composite floor of " the multiple material exhibition-JEC of China " outstanding innovative product prize.The fiber-reinforced PC BT composite (number of patent application 201110412006.6) mentioned in a such as patent again.The batch micro operations of this complex structural member being fiber-reinforced thermoplastic resin based composites provides good start and guarantee.
But due to the complex structure of complex structural member, in the process that RTM mold manufactures, the precision of mould matched molds can vary widely.Overall single piece type lay can not be adopted during lay down fibre fabric, need its territory, rationalization partition, piecemeal lay.Will cause the finished parts of structural member in some region, occur the phenomenon that fiber infiltrates not exclusively or resin is too much like this, obvious resin-rich area is there is at turning or fiber lap-joint, cause the rich resin of obtained structural member surface easily in use to crack or dry spot, thus the outward appearance of the mechanical property of structural member, serviceability and structural member can be affected.Particularly for the exterior appearance of fibre-reinforced opaque or translucent thermoplas tic resin composite.For some fiber reinforced thermolplastic composite material, due to its resin easy reasons such as the comparatively large and mobility of ratio of viscosities is poor after high-temperature oxydation, melting in atmosphere, also there is no now corresponding defect mending technology.
Therefore still need in this area provides a kind of method reducing fiber reinforced thermolplastic composite material product surface defect, makes the exterior appearance of the fiber reinforced thermolplastic composite material goods of acquisition without obvious dry spot or crackle.
Summary of the invention
The first object of the present invention is to provide a kind of method reducing fiber reinforced thermolplastic composite material product surface defect, it is characterized in that, comprises following steps:
A () provides one have each other can a former of matched moulds and the mould of a formpiston;
(b) by fibre knitting cloth more than one deck and elastomer goods more than one deck with stacking mode lay in described mould, or by a stacking thing lay containing fibre knitting cloth more than one deck and elastomer goods more than one deck in described mould, described elastomer goods are one or more in fibrofelt, three-dimensional fiber woven fabric;
C (), by described former and formpiston matched moulds, heats described mould;
D one thermoplastic resin composition is injected described mould by (); With
E () treats that described thermoplastic resin composition is solidified, after mold cools down, the demoulding obtains goods.
The second object of the present invention is to provide a kind of fiber reinforced thermolplastic composite material, it is characterized in that, described composite comprises thermoplastic, polymeric materials body and is arranged in the stacking thing of the fibre knitting cloth of more than one deck of described body and elastomer goods formation more than one deck, and described stacking thing is integrated with described polymeric material body, described elastomer goods are one or more in fibrofelt, three-dimensional fiber woven fabric.
The third object of the present invention is to provide a kind of fiber reinforced thermolplastic composite material goods, it is characterized in that, described goods are made up of described fiber reinforced thermolplastic composite material.
Usefulness of the present invention is: the inventive method enforcement is simple and easy to operate, Bing and the good results are evident to reducing the resin-rich area defect on fiber-reinforced thermoplastic resin base composite-material product surface and dryspot, the qualification rate of goods can be increased substantially, accelerate the bulk industrial production process of fiber-reinforced thermoplastic resin based composites.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the preference that the inventive method is described;
Fig. 2 is the photo that fibre knitting cloth and the ply stacking-sequence of fibrofelt lay in mould in this preference are described;
Fig. 3 is the photo of the automotive floor panel mould that embodiment 1 and comparative example 1 are described;
Fig. 4 is the photo that the automotive floor panel goods that embodiment 1 is obtained are described;
Fig. 5 is the photo that the automotive floor panel goods that comparative example 1 is obtained are described
Fig. 6 is the photo that the deck goods that embodiment 2 is obtained are described;
Fig. 7 is the photo that the deck goods that comparative example 2 is obtained are described.
Detailed description of the invention
The present inventor finds through extensive and deep research, due to three-dimensional fiber woven fabric or fibrofelt high resilience, during by their interlayers in fibre knitting cloth, fibre knitting cloth can be made to be adjacent to the chamber wall of mould mould, the fiber cloth that the precision problem due to die cavity causes can be improved and can not be adjacent to die cavity wall and the resin-rich area caused, or the dry spot that the too closely knit of fibre knitting cloth pressure causes by die cavity wall.Three-dimensional fiber woven fabric or fibrofelt can form elastomer in the corner of structural member, be obedient to the angle at turning, fibre knitting cloth can be made after matched moulds to be close to the corner surface of female mould, reduce the rich surface resin of corner, also play the effect of reinforcing turning intensity and improving structural member serviceability simultaneously.Complete the present invention on this basis.
Elastomer goods
Preferably, the unit are grammes per square metre of described elastomer goods is 100 to 900g/m
2.
Preferably, the thickness of every one deck of described elastomer goods is not more than 2mm.
As used herein, term " fibrofelt (fiber mats) " refers to by the monofilament of staple fibre, continuous fiber or precursor, the lamellar product shortly cut or not shortly to cut, combine directed or non-directional and make.
Preferably, described fibrofelt is one or more in glass mat, carbon fiber felt, the kind be suitable for comprise short cut in felt, continuous felt, surperficial felt, Nomex, stitching felt one or more.Preferably, described fibrofelt is alkali-free glass fibre felt.
As used herein, term " three-dimensional fiber woven fabric (three-dimensional woven fabric) " refers to one group of warp thread and one group of weft yarn, according to the fabric with 3-D solid structure that certain rule is interwoven on loom.
Preferably, described three-dimensional fiber woven fabric is one or more in three-dimensional glass woven fabric, three-dimensional carbon fibre fabric, and the woven mode of three-dimensional fiber woven fabric can be four step rule woven endless, or multistep processes braiding, as two step method, Six Steps braiding.
Preferably, described fibre knitting cloth is glass fabric, carbon cloth, comprises one or more in plain weave, twill, satin.Preferably, described fibre knitting cloth is glass fabric.
Method for making, composite and goods
The present invention reduces the method for fiber reinforced thermolplastic composite material product surface defect, it is characterized in that, comprises following steps:
A () provides one have each other can a former of matched moulds and the mould of a formpiston;
(b) by fibre knitting cloth more than one deck and elastomer goods more than one deck with stacking mode lay in described mould, or by a stacking thing lay containing fibre knitting cloth more than one deck and elastomer goods more than one deck in described mould, described elastomer goods are one or more in fibrofelt, three-dimensional fiber woven fabric;
C (), by described former and formpiston matched moulds, heats described mould;
D one thermoplastic resin composition is injected described mould by (); With
E () treats that described thermoplastic resin composition is solidified, after mold cools down, the demoulding obtains goods.
Preferably, described (c) step is that mold integral is heated to 150-200 DEG C.
Preferably, the thermoplastic resin composition of described (d) step comprises a monomer component and a catalyst component, described monomer component contains caprolactam (Caprolactam, be called for short CPL), and the goods that (e) step obtains are fibre-reinforced nylon 6 (Nylon 6 is called for short PA6) composite products.Preferably, described nylon 6 is anion polyamide-6 (Anionic polyamide-6 is called for short APA-6).
Preferably, described catalyst component contains a major catalyst and a co-catalyst.Described major catalyst is the alkali metal salt of lactam monomers, one or more in caprolactam magnesium bromide, sodium caprolactam.Described co-catalyst is hexa-methylene-1,6-bis-formyl caprolactam, one or more in toluene di-isocyanate(TDI) (be called for short TDI), hexamethylene diisocyanate (being called for short HDI), vinylcaprolactam.
Preferably, described (b) step be also included in the turning of mould, fiber lap-joint one or more add elastomer goods described in one deck, and then cover upper fibre knitting cloth.
Preferably, described (b) step be in the outermost of the pattern tool mode that is fibre knitting cloth by fibre knitting cloth and elastomer goods lay in described mould.
Preferably, the mould of described (a) step is the mould for the manufacture of automobile floor or car back box lid.
Preferably, the described fibre knitting cloth of (b) step use and the number of plies of elastomer goods are 5-10 layer and 4-8 layer respectively.
Preferably, the inventive method also comprises a cutting fibre knitting cloth before (a) step and fibrofelt or three-dimensional fiber woven fabric, dries the steps such as the fibre knitting cloth and fibrofelt that cut or three-dimensional fiber woven fabric, cleaning mould, coating releasing agent.
Preferably, the inventive method also comprises the step of a preparation thermoplastic resin composition before (d) step.Preferably, this preparation process first heats this monomer component and in the monomer component of melting, adds major catalyst and co-catalyst and obtain thermoplastic resin composition.
Below coordinate Fig. 1 schematic flow sheet that one of the inventive method preference is described:
Step 301: according to the size cutting fibre knitting cloth of goods and fibrofelt or three-dimensional fiber woven fabric;
Step 302: the fibre knitting cloth cut and fibrofelt or three-dimensional fiber woven fabric are put into baking oven and dries.
Step 303: cleaned out by die surface, polishes smooth.
Step 304: apply releasing agent equably at die surface.
Step 305: the ply stacking-sequence according to Fig. 2, in former, then carries out matched moulds to mould by the fibre knitting cloth cut (in Fig. 2, label is 1) and fibrofelt or three-dimensional fiber woven fabric (in Fig. 2, label is 2) lay.
Step 306: by mold heated to 150-190 DEG C.
Step 307: molten monomer component (as caprolactam), adds major catalyst and co-catalyst and obtains a Composite Melt (thermoplastic resin composition) in the monomer component of melting.
Step 308: pressure is applied to the Composite Melt of step 307, is filled in mould,
Step 309: Composite Melt wetting fibre woven cloth and fibrofelt or three-dimensional fiber woven fabric, Bing is polymerized and crystallization in a mold.To be polymerized and crystallization completes.
Step 310: to cool mould, the demoulding, obtains goods after carrying out deburring to goods.
Composite of the present invention comprises thermoplastic, polymeric materials body and is arranged in the stacking thing of the fiber cloth of more than one deck of described body and elastomer goods formation more than one deck, and described stacking thing is integrated with described polymeric material body, described elastomer goods are one or more in fibrofelt, three-dimensional fiber woven fabric.
Preferably, described thermoplastic polymer comprises nylon 6.
Preferably, described composite is obtained by aforementioned method preparation of the present invention.
Fiber reinforced thermolplastic composite material goods of the present invention are made up of described fiber reinforced thermolplastic composite material.
Preferably, described fiber reinforced thermolplastic composite material goods comprise automobile floor and car back box lid.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.
< material source >
1. glass fibre plain: purchased from Jiuding New Materials Co., Ltd., Jiangsu, specification is EWR 400g/m
2.
2. alkali-free glass fibre felt: purchased from Jiuding New Materials Co., Ltd., Jiangsu, specification is EWC 200g/m
2.
3. caprolactam: purchased from BASF Aktiengesellschaft.
4. caprolactam magnesium bromide: purchased from German Br ü ggemann Chemical company.
5. hexa-methylene-1,6-bis-formyl caprolactam: purchased from German Br ü ggemann Chemical company.
6. releasing agent: purchased from Lars composite Co., Ltd of Shanghai section, model is X807.
Embodiment 1:
The implementation step of the present embodiment method is as follows:
1. according to size cutting glass fibre plain and the glass mat of automotive floor panel mould.
2. dry 3 hours at cutting glass fibre plain and glass mat being put into 120 DEG C, baking oven.
3. automotive floor panel die surface is as shown in Figure 3 cleaned out, polish smooth, apply releasing agent equably at die surface.
4. by 6 layers of glass fibre plain (abbreviation cloth) of cutting and 8 layers of glass mat (abbreviation felt) with following stacking mode lay from top to bottom in former: cloth/felt/cloth/felt/felt/cloth/felt/felt/cloth/felt/felt/cloth/felt/cloth, and as shown in table 1 below, the unit are grammes per square metre of the stacking thing that described plain and fibre felt layer poststack are formed is 4000 (g/m
2).
5. former and formpiston are given matched moulds.
6. by mold heated to 150 DEG C.
7. by caprolactam melting, caprolactam after melting adds caprolactam magnesium bromide (major catalyst) and hexa-methylene-1,6-bis-formyl caprolactam (co-catalyst) and obtain preparing glue needed for composite (i.e. thermoplastic resin composition, wherein the content ratio of above-mentioned three kinds of components take molar basis as caprolactam: major catalyst: co-catalyst=98:1:1).。
8. the glue of step 7 is transferred in glue-injection machine, 0.2Mpa pressure is applied to it, is filled in mould, until after having glue to flow out from the gum outlet of mould, stop its perfusion glue.
9. prepare the glue wetting fibre cloth needed for composite and glass mat, Bing is polymerized and crystallization in a mold.
10., after to be polymerized and crystallization completes, mould is cooled, the demoulding, obtain automotive floor panel goods as shown in Figure 4 after deburring is carried out to goods.
Table 1
Comparative example 1:
The implementation step of the present embodiment method is with embodiment 1, and difference is in and uses 10 layers of glass fibre plain in: step 2, and does not use glass mat, and as shown in table 1, the unit are grammes per square metre of the stacking thing of the stacked rear formation of plain is also 4000 (g/m
2); The goods that step 10 obtains are the automotive floor panel goods as Fig. 5.
Embodiment 2:
The implementation step of the present embodiment method is with embodiment 1, difference is in the glass fibre plain used in: step 2 and is only of five storeys, glass mat only has 4 layers, and with following overlapped way lay from top to bottom in former: cloth/felt/cloth/felt/cloth felt/cloth/felt/cloth, as shown in table 1, the unit are grammes per square metre of the stacking thing that described plain and fibre felt layer poststack are formed is 2800 (g/m
2); Step 1 and 3 mould be automobile rear cabinet box cover die; The goods that step 10 obtains are the deck goods as Fig. 6.
Comparative example 2:
The implementation step of the present embodiment method is with embodiment 2, and difference is in and uses 7 layers of glass fibre plain in: step 2, and does not use glass mat, and as shown in table 1, the unit are grammes per square metre of the stacking thing of the stacked rear formation of plain is also 2800 (g/m
2); The goods that step 10 obtains are the automotive floor panel goods as Fig. 7.
Embodiment and comparative example's effect illustrate:
As seen from Figure 5, the automotive floor panel goods not using the comparative example 1 of glass mat to obtain have obvious dry spot and resin-rich area defect, and these defects disappear in the automotive floor panel goods of the embodiment 1 of Fig. 4 display.Moreover, because the corner part of mould is few in comparative example 2, thus Fig. 7 to show the defect that resin-rich area causes not obvious, but Fig. 7 still can see the defect of dry spot, and dryspot also disappears in the goods of the embodiment 2 of Fig. 6 display.So the effects of surface defects that the present invention is applicable to the shaping fiber-reinforced thermoplastic resin base composite-material product of resin transfer moulding (RTM) to minimizing is fairly obvious.
In sum, the inventive method enforcement is simple and easy to operate, Bing and the good results are evident to minimizing fiber-reinforced thermoplastic resin base composite-material product blemish, the qualification rate of goods can be increased substantially, accelerate the bulk industrial production process of fiber-reinforced thermoplastic resin based composites.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read above-mentioned instruction content of the present invention.
Claims (14)
1. reduce a method for fiber reinforced thermolplastic composite material product surface defect, it is characterized in that, comprise following steps:
A () provides one have each other can a former of matched moulds and the mould of a formpiston;
(b) by fibre knitting cloth more than one deck and elastomer goods more than one deck with stacking mode lay in described mould, or by a stacking thing lay containing fibre knitting cloth more than one deck and elastomer goods more than one deck in described mould, described elastomer goods are one or more in fibrofelt, three-dimensional fiber woven fabric;
C (), by described former and formpiston matched moulds, heats described mould;
D one thermoplastic resin composition is injected described mould by (); With
E () treats that described thermoplastic resin composition is solidified, after mold cools down, the demoulding obtains goods.
2. the method for claim 1, is characterized in that, the fibrofelt of described (b) step is one or more in glass mat, carbon fiber felt.
3. the method for claim 1, is characterized in that, the three-dimensional fiber woven fabric of described (b) step is one or more in three-dimensional glass woven fabric, three-dimensional carbon woven cloth.
4. the method for claim 1, is characterized in that, the unit are grammes per square metre of the elastomer goods of described (b) step is 100 to 900g/m
2.
5. the method for claim 1, it is characterized in that, the thermoplastic resin composition of described (d) step comprises a monomer component and a catalyst component, described monomer component contains caprolactam, and the goods that (e) step obtains are fibre-reinforced nylon 6 composite material goods.
6. method as claimed in claim 5; it is characterized in that; described catalyst component contains a major catalyst and a co-catalyst; described major catalyst is the alkali metal salt of lactam monomers; one or more in caprolactam magnesium bromide, sodium caprolactam; described co-catalyst is one or more in hexa-methylene-1,6-bis-formyl caprolactam, toluene di-isocyanate(TDI), hexamethylene diisocyanate, vinylcaprolactam.
7. the method for claim 1, is characterized in that, described (b) step be also included in the turning of mould, fiber lap-joint one or more add elastomer goods described in one deck, and then cover upper fibre knitting cloth.
8. the method for claim 1, is characterized in that, described (b) step be in the outermost of the pattern tool mode that is fibre knitting cloth by fibre knitting cloth and elastomer goods lay in described mould.
9. the method for claim 1, is characterized in that, the mould of described (a) step is the mould for the manufacture of automobile floor or car back box lid.
10. a fiber reinforced thermolplastic composite material, it is characterized in that, described composite comprises thermoplastic, polymeric materials body and is arranged in the stacking thing of the fibre knitting cloth of more than one deck of described body and elastomer goods formation more than one deck, and described stacking thing is integrated with described polymeric material body, described elastomer goods are one or more in fibrofelt, three-dimensional fiber woven fabric.
11. composites as claimed in claim 10, it is characterized in that, described thermoplastic polymer comprises nylon 6.
12. composites as claimed in claim 10, it is characterized in that, described composite is prepared by method according to claim 1 and obtains.
13. 1 kinds of fiber reinforced thermolplastic composite material goods, is characterized in that, described goods are made up of fiber reinforced thermolplastic composite material according to claim 10.
14. goods as claimed in claim 13, it is characterized in that, described goods comprise automobile floor and car back box lid.
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| CN105619841A (en) * | 2015-12-29 | 2016-06-01 | 东华大学 | Forming method for thermoplastic composite material |
| CN106113811A (en) * | 2016-06-21 | 2016-11-16 | 郑州大学 | Thermoplastic continuous fibers's composite and preparation method thereof and process units |
| CN108407333B (en) * | 2018-03-14 | 2020-05-01 | 天津爱思达航天科技有限公司 | Composite material mold female die and manufacturing method and application thereof |
| CN108527732B (en) * | 2018-03-14 | 2019-10-11 | 天津爱思达航天科技有限公司 | A kind of composite material mould and its manufacturing method |
| CN112406133A (en) * | 2020-09-22 | 2021-02-26 | 合肥兴海元能源科技有限公司 | High-temperature high-pressure RTM (resin transfer molding) method for new energy automobile battery upper cover |
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