CN104029401A - Method for preparing phenolic resin system Z-pin by using twisted carbon fibers - Google Patents

Method for preparing phenolic resin system Z-pin by using twisted carbon fibers Download PDF

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Publication number
CN104029401A
CN104029401A CN201410236717.6A CN201410236717A CN104029401A CN 104029401 A CN104029401 A CN 104029401A CN 201410236717 A CN201410236717 A CN 201410236717A CN 104029401 A CN104029401 A CN 104029401A
Authority
CN
China
Prior art keywords
pin
phenolic resin
resin system
carbon fiber
operation
Prior art date
Application number
CN201410236717.6A
Other languages
Chinese (zh)
Inventor
李勇
张向阳
还大军
文立伟
肖军
褚奇奕
Original Assignee
南京航空航天大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 南京航空航天大学 filed Critical 南京航空航天大学
Priority to CN201410236717.6A priority Critical patent/CN104029401A/en
Publication of CN104029401A publication Critical patent/CN104029401A/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/40Shaping or impregnating by compression not applied
    • B29C70/50Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/54Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing

Abstract

The invention discloses a method for preparing phenolic resin system Z-pin by using twisted carbon fibers, wherein reinforcing materials for extruding and forming the Z-pin are the twisted carbon fibers with twist degree of 80-100 t/m. The method uses the twisted fibers to generate pressure on a resin matrix to restrain the growth of bubbles in phenolic resin, and modifies the defect of generation of air holes in the Z-pin products due to volatilization of phenolic resin curing products. The obtained Z-pin products can be used for reinforcing ablation-resisting and heat-preventing composite materials of a carbon fiber/phenolic resin system, and prominently modify the stripping resistance and the scouring resistance.

Description

Utilize twisting carbon fiber to prepare the method for phenolic resin system Z-pin

 

Technical field

The present invention relates to carbon fiber the preparation method of phenolic resin system Z-pin, belong to method for composite material technical field.

Background technology

Phenolic resin-base composite is current conventional thermally protective materials, be widely used in return capsule, rocket and the guided missile termination of various manned spaceships, but composite interlayer causes MULTILAYER COMPOSITE thermally protective materials interlayer antistripping, erosion resistibility to be difficult to the instructions for use that reaches higher in conjunction with weakness.In order to address this problem, Li Ning (Li Ning. Z-pin strengthens phenolic aldehyde laminate preparation technology and performance study [D]. Nanjing Aero-Space University, 2012.) publish thesis, utilize quartzy phenolic system Z-pin can improve quartzy the interfacial bonding strength of phenolic resin system composite.But for the resistance to ablative composite material of carbon fiber system, because the material properties such as modulus, thermal coefficient of expansion and temperature tolerance do not mate, quartz fibre strengthens Z-pin cannot meet use, must exploitation carbon fiber reinforced phenol formaldehyde resin system Z-pin.The volatilization of thermosetting phenolic resin cured product leaves a large amount of gas hole defects in carbon fiber/phenolic system Z-pin pultrusion product, and the existence of pore causes Z-pin to be implanted in composite blank as reinforcement, thereby cannot realize interlaminar improvement effect.

Summary of the invention

The object of the present invention is to provide a kind of carbon fiber the manufacture method of phenolic resin system Z-pin, utilize carbon fiber twist to the air blister defect of processing so that phenolic resin curing volatile matter causes in solution Z-pin preparation process, for carbon fiber the resistance to ablation thermal protection composite material of phenolic resin system reinforcement is provided.

A kind of method of utilizing twisting carbon fiber to prepare phenolic resin system Z-pin, adopt pultrude process moulding, fiber is twisted operation, impregnation operation, die forming operation, rear curing process, traction operation and winding process online successively, it is characterized in that: before impregnation operation, add online twisting operation, realize carbon fiber twisting and process.

Described utilization twisting carbon fiber is prepared the method for phenolic resin system Z-pin, it is characterized in that: the twist of twisting operation is 80 ~ 100 twists/m.

The principle that utilization twisting carbon fiber improves Z-pin internal porosity defect is as follows, the helix that twisted fibers monofilament forms is along yarn bundle circle distribution, under extrusion traction effect, fibre single thread deforms, apart from distance of shaft centers from away from more, be out of shape larger, adjacent two-layer fibre single thread, due to distortion difference, the resin between them produced to squeezing action.Utilize this extruding force effect to offset the volatilization of phenolic resin curing product to the hole driving force providing of grow, thereby produce air blister defect in inhibition Z-pin goods, improve fiber and resin boundary surface bonding state.

The advantage of utilizing twisting carbon fiber to prepare phenolic resin system Z-pin is: (1) has got rid of the air blister defect in Z-pin, can realize carbon fiber phenolic resins Z-pin continuously, steady production; (2) in Z-pin, fiber and resin-bonded are in good condition, have avoided in follow-up implantation process Z-pin that end occurs and have pulverized or unstability, improved maximum implantation depth, thus improved can reinforced composite maximum ga(u)ge.

Brief description of the drawings

Fig. 1 be carbon fiber phenolic resins Z-pin pultrusion process schematic diagram;

Fig. 2 is the ultrasonic implantation schematic diagram of Z-pin;

Number in the figure title: 1, the online twister 2 of fiber, fibre guide device, 3, gumming device, 4, pultrusion die, 5, rear solidification equipment, 6, draw-gear, 7, wrap-up, 8, ultrasonic implanting gun, 9, Z-pin implants precast body, 10 prepreg blanks.

Specific embodiment

This embodiment illustrates the preparation method of twisting carbon fiber reinforced phenol formaldehyde resin system Z-pin provided by the invention.

1. select T300 carbon fiber to be placed on the online twister of Fig. 1, fiber is passed to fibre guide device 2, gumming device 3, pultrusion die 4, rear solidification equipment 5, draw-gear 6 and the wrap-up 7 in Fig. 1 successively, the pultrusion speed that the online twister 1 shaft rotating speed of fiber and pultrusion die 4 are set, obtaining the fiber twist is 80 twists/m.

2. B30 phenolic resins being placed in to vacuum drying oven carries out after 60 DEG C, 1h deaeration process, pouring in glue groove to be used.

3. mold temperature is set is 90 DEG C, and rear solidification equipment temperature is 180 DEG C.

4., after waiting system is stablized, open draw-gear.

5. detecting Z-pin diameter is 0.5 ± 0.01mm, and obviously bubble of inner nothing, carries out ultrasonic implantation experiment by ultrasonic method for implantation shown in Fig. 2, and obtaining the maximum implantation depth of Z-pin is 10mm.

Claims (2)

1. utilize twisting carbon fiber to prepare a method of phenolic resin system Z-pin, adopt pultrude process moulding, fiber is twisted operation, impregnation operation, die forming operation, rear curing process, traction operation and winding process online successively, it is characterized in that:
Before impregnation operation, add online twisting operation, realize carbon fiber twisting and process.
2. utilization twisting carbon fiber according to claim 1 is prepared the method for phenolic resin system Z-pin, it is characterized in that: the twist of twisting operation is 80 ~ 100 twists/m.
CN201410236717.6A 2014-05-30 2014-05-30 Method for preparing phenolic resin system Z-pin by using twisted carbon fibers CN104029401A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410236717.6A CN104029401A (en) 2014-05-30 2014-05-30 Method for preparing phenolic resin system Z-pin by using twisted carbon fibers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410236717.6A CN104029401A (en) 2014-05-30 2014-05-30 Method for preparing phenolic resin system Z-pin by using twisted carbon fibers

Publications (1)

Publication Number Publication Date
CN104029401A true CN104029401A (en) 2014-09-10

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CN (1) CN104029401A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104552989A (en) * 2015-01-23 2015-04-29 南京航空航天大学 Equipment and method for preparing glass fiber composite material Z-Pin by virtue of microwave heating and quick pull-extrusion
CN104723583A (en) * 2015-03-30 2015-06-24 南京航空航天大学 Equipment and method for preparing composite material, Z-pin, by using electronic beam curing technology
CN104760304A (en) * 2015-03-19 2015-07-08 南京航空航天大学 Device for preparing glass fiber composite material Z-pin through ultraviolet curing quick pultrusion and preparation method of the glass fiber composite material
CN104875397A (en) * 2015-05-11 2015-09-02 上海复合材料科技有限公司 Method for molding fiber composite material spray pipe perform connected by Z-pin
CN106393741A (en) * 2016-10-21 2017-02-15 天津工业大学 Coating method of composite toughened slender rod

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1671539A (en) * 2002-05-22 2005-09-21 格勒普史蒂文斯国际股份公司 Tufted composite laminate
DE102008017381A1 (en) * 2008-04-05 2009-10-08 Deutsches Zentrum für Luft- und Raumfahrt e.V. Method for producing e.g. preform, from fiber-reinforced composite in molding tool, involves pressing vacuum foil against fiber scrim by pressure distribution applied by support structure, during evacuation of mold cavity
CN102198730A (en) * 2011-04-21 2011-09-28 北京玻钢院复合材料有限公司 Pultrusion process and pultrusion device of phenolic resin composite
CN102431180A (en) * 2011-09-13 2012-05-02 南京航空航天大学 Manufacturing method of partially cured Z-pin
CN102777708A (en) * 2012-07-25 2012-11-14 广东宝通玻璃钢有限公司 Fiber-woven pultrusion pipeline and production method
CN103302906A (en) * 2013-06-01 2013-09-18 山东爱地高分子材料有限公司 Ultra-high-modulus polyethylene fiber reinforced plastic rod and manufacturing method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1671539A (en) * 2002-05-22 2005-09-21 格勒普史蒂文斯国际股份公司 Tufted composite laminate
DE102008017381A1 (en) * 2008-04-05 2009-10-08 Deutsches Zentrum für Luft- und Raumfahrt e.V. Method for producing e.g. preform, from fiber-reinforced composite in molding tool, involves pressing vacuum foil against fiber scrim by pressure distribution applied by support structure, during evacuation of mold cavity
CN102198730A (en) * 2011-04-21 2011-09-28 北京玻钢院复合材料有限公司 Pultrusion process and pultrusion device of phenolic resin composite
CN102431180A (en) * 2011-09-13 2012-05-02 南京航空航天大学 Manufacturing method of partially cured Z-pin
CN102777708A (en) * 2012-07-25 2012-11-14 广东宝通玻璃钢有限公司 Fiber-woven pultrusion pipeline and production method
CN103302906A (en) * 2013-06-01 2013-09-18 山东爱地高分子材料有限公司 Ultra-high-modulus polyethylene fiber reinforced plastic rod and manufacturing method thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104552989A (en) * 2015-01-23 2015-04-29 南京航空航天大学 Equipment and method for preparing glass fiber composite material Z-Pin by virtue of microwave heating and quick pull-extrusion
CN104760304A (en) * 2015-03-19 2015-07-08 南京航空航天大学 Device for preparing glass fiber composite material Z-pin through ultraviolet curing quick pultrusion and preparation method of the glass fiber composite material
CN104723583A (en) * 2015-03-30 2015-06-24 南京航空航天大学 Equipment and method for preparing composite material, Z-pin, by using electronic beam curing technology
CN104875397A (en) * 2015-05-11 2015-09-02 上海复合材料科技有限公司 Method for molding fiber composite material spray pipe perform connected by Z-pin
CN106393741A (en) * 2016-10-21 2017-02-15 天津工业大学 Coating method of composite toughened slender rod
CN106393741B (en) * 2016-10-21 2018-09-18 天津工业大学 A kind of coating process of the thin stick of composite material toughening

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Application publication date: 20140910