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CN106003753B - A method of preparing complicated inner cavity product - Google Patents

A method of preparing complicated inner cavity product Download PDF

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Publication number
CN106003753B
CN106003753B CN201610313430.8A CN201610313430A CN106003753B CN 106003753 B CN106003753 B CN 106003753B CN 201610313430 A CN201610313430 A CN 201610313430A CN 106003753 B CN106003753 B CN 106003753B
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Prior art keywords
core
resin
liquid
continuous fiber
temperature
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Expired - Fee Related
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CN201610313430.8A
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Chinese (zh)
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CN106003753A (en
Inventor
冯跃飞
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Beijing Honghu Xiongshi Technology Development Co Ltd
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Beijing Honghu Xiongshi Technology Development Co Ltd
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Priority to CN201610313430.8A priority Critical patent/CN106003753B/en
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    • 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
    • B29C70/30Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • 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
    • B29C67/00Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

The invention discloses a kind of methods preparing complicated inner cavity product, which is characterized in that this method includes:A, the continuous fiber of pre-soaked resin is wrapped in the whose surfaces for being enclosed with isolation film at room temperature, or continuous fiber resin prepreg material is coated with to the core for obtaining being enclosed with precast body in the whose surfaces for being enclosed with isolation film;B, the core for being enclosed with precast body is put into mold, so that core and precast body is sealed against each other isolation using fluid sealant and isolation film;C, in cured condition by precast body curing molding;D, it is warming up to after core constituent material is fused into liquid, applies the core as liquid of compressed air discharge composite product intracavitary, cooling and demolding removes the remaining core of intracavitary and isolation film, obtains complicated inner cavity product.The method of the present invention can prepare the composite product of the various continuous lods with complicated cavity structure.

Description

A method of preparing complicated inner cavity product
Technical field
The present invention relates to technical fields prepared by complicated inner cavity product, and in particular to a kind of side preparing complicated inner cavity product Method.
Background technology
The polymer matrix composites product of continuous lod have higher specific strength and specific stiffness, aerospace, The fields such as oil pipeline, high-pressure bottle, civilian sports equipment, which have, to be more and more widely used.The resin base of continuous lod Composite product preparation method mainly has:It is lay-up molding, Wrapping formed, the also 3D printing technique etc. of newly-developed.Winding Forming method is mainly used for the preparation of pipeline, container or the complicated part containing cored structure, such as oil pipeline, gas cylinder, ship or straight Blade, the civilian light hollow equipment such as crutch, club, bicycle rack etc. of the machine of liter, usually by twining by design after fiber prepreg It is wrapped on a core or center material (such as foam) around direction and technique, core or center material imparting winding are fiber solidifying Final shape afterwards is subsequently cured to obtain composite product, then demoulds removing core and obtain heartwood in hollow product, or reservation Material and continuous fiber reinforced composite materials product become product jointly.Lay-up molding is then to spread continuous-filament woven fabric or prepreg It is overlying on a model face and pre-manufactured model (core or center-fill material), obtains precast body, recycle RTM techniques or preimpregnation Material technique obtains composite product.
But it prepares the product with complicated inner cavity structure and encounters insoluble problem, the mainly type of labyrinth Core can cause the problem of can not demoulding, and therefore, it is difficult to prepare inner cavity complexity such as inner cavity with long pipeline configuration or with lobster back The composite product of road structure.A kind of existing technology is to apply water-soluble core, and this core can be in composite molding It is removed afterwards using water-soluble method, but inevitable to bring that solution rate is slow, core material is unable to Reusability, environment dirty Dye, dissolution process influence the problems such as composite product performance.
To sum up, it in order to avoid problem above, needs to develop novel core removal methods, and prepare and have using the technology There is the composite product of complicated inner cavity structure.
Invention content
The purpose of the present invention is to provide a kind of methods preparing complicated inner cavity product, that is, use a kind of in composite material It is on-deformable hard solid under heat curing temperature, and the material for becoming liquid after beyond 30 DEG C~100 DEG C of the temperature is made For core material, it can be wound on core at room temperature or paving is at the composite preform of preformed shape, be molded temperature Precast construction shape, solidification can be well kept to complete to heat up again 30 DEG C~100 DEG C to be heated into upper core under degree and pressure For liquid, inner cavity can be discharged, so prepare the composite product with complicated inner cavity.
To achieve the above object, the present invention provides a kind of method preparing complicated inner cavity product, which is characterized in that this method Including:A, the continuous fiber of pre-soaked resin is wrapped in the whose surfaces for being enclosed with isolation film at room temperature, or by continuous fiber tree Fat prepreg is coated with the core for obtaining being enclosed with precast body in the whose surfaces for being enclosed with isolation film;B, precast body will be enclosed with Core be put into mold, so that core and precast body is sealed against each other isolation using fluid sealant and isolation film;C, at curing temperatures By precast body curing molding, curing molding product is obtained;D, it is warming up to after core constituent material is fused into liquid, it is empty to apply compression The core as liquid of curing molding product intracavitary, cooling and demolding, the remaining core of removal intracavitary and isolation film is discharged in gas, obtains To complicated inner cavity product.
Preferably, step d is replaced with:D ', cooling and demolding are warming up to after core constituent material is fused into liquid, pour out Core or the core as liquid for applying compressed air discharge curing molding product intracavitary, remove the remaining core of intracavitary and every From film, complicated inner cavity product is obtained.
Preferably, continuous fiber described in the continuous fiber of the pre-soaked resin and/or continuous fiber resin is selected from carbon At least one of fiber, glass fibre, aramid fiber and polyimide fiber, the resin are selected from epoxy resin, insatiable hunger At least one of with polyester, benzoxazine resin and bimaleimide resin.
Preferably, the isolation film is polytetrafluoroethylene (PTFE) nonporous film, and the fluid sealant is silicon rubber.
Preferably, the operation pressure is 0.4-1 megapascal, and the solidification temperature is 100-200 DEG C.
Preferably, the core constituent material is hard solid under the solidification temperature, higher than the solidification temperature 30 ~100 DEG C or more become flowable liquid, and the viscosity of the liquid is less than 1000Pa.s.The composition of core of the present invention Material includes that (such as glass state material is higher than glass transition temperature for low melting point (crystalline fusion of such as small molecule) and low flow temperature Become flowable liquid after spending certain value).
Preferably, the resin in the continuous fiber of the pre-soaked resin and/or continuous fiber resin is bismaleimide Resin, core constituent material are hard solid at 180 DEG C or 200 DEG C or less, higher than 30~100 DEG C of this 180 DEG C or 200 DEG C with Become flowable liquid when above and no more than precast body heat distortion temperature, viscosity is less than 1000Pa.s.
Preferably, the resin in the continuous fiber of the pre-soaked resin and/or continuous fiber resin is epoxy resin, core Constituent material is hard solid at 120 DEG C or less, more than a certain temperature in 150~200 DEG C becomes flowable liquid, and The viscosity of the liquid is less than 1000Pa.s.
Preferably, the resin in the continuous fiber of the pre-soaked resin and/or continuous fiber resin is epoxy resin, core Constituent material is hard solid at 180 DEG C or less, more than a certain temperature in 210~250 DEG C becomes flowable liquid, and The viscosity of the liquid is less than 1000Pa.s.
Preferably, the core constituent material is polyether-ether-ketone, the crystalline melt temperature of the core constituent material is 140~ Viscosity is less than 1000Pa.s at 145 DEG C, 160 DEG C or 180 DEG C;Alternatively, the core constituent material is copolymerized for modified polyarylether ketone Object, crystalline melt temperature are flowable liquid when being 200 DEG C, 250 DEG C;Alternatively, the core constituent material, which is fusing point, is less than 220 DEG C low-melting-point metal blend.
The method of the present invention has the following advantages that:
The core of technical scheme of the present invention is that have certain mechanics at a temperature of applying a kind of composite material curing molding Intensity and the core material easily removed after heating up, composite material can be kept at a temperature of curing molding well with this core material Inner-cavity structure, and core material can be discharged from inner cavity after heating up, therefore can be used for preparing the composite wood of complicated cavity structure Expect product, avoids the problem of complex core cannot demould, make up the deficiency of Conventional processing methods.
The tired of the composite product with tortuous or irregular shape complicated cavity structure is prepared for traditional handicraft Difficulty, proposition core fusible after being heated up using rigidity at a temperature of bonded composite curing molding prepare this kind of composite material The method of product, prepreg laying or winding on this core obtain precast body, can at a temperature of composite material curing molding It can simply be removed when well keeping its shape and inner-cavity structure, and further increasing to no more than composite material heat distortion temperature Core is removed, with quickly and easily preparing the composite material system with the various continuous lods with complicated cavity structure The advantages of part.
The advantages and features of the present invention is, first, the various continuous fibers with complicated cavity structure can be prepared and increased Strong composite product;Second, decoring speed is fast, and production efficiency is high;Third, coremaking is easy and speed is fast, can use cast side It is prepared by method;4th, inner-cavity structure keeps good.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1:
The implementation process of the present embodiment technical solution is as follows:
(1-1) is blocking by core material die casting, then is machined into method processing helically;Or directly by core material Material high temperature extrusion is injected into the mold with spiral shape cavity, and spiral-shaped core is obtained after cooling and demolding.Again in core The nonporous film of one strata tetrafluoroethene of outer wrapping, sealing.
The continuous carbon fibre for presoaking intermediate temperature setting epoxy resin is wrapped in the polytetrafluoroethyl-ne of above-mentioned core by (1-2) at room temperature The nonporous film surface of alkene, obtains composite preform, places into mold;The polytetrafluoroethylene (PTFE) at core both ends is non-porous thin Film seals on the mould wall, and molding is warming up to 120 DEG C and makes precast body curing molding under defined pressure and time;Then 160 DEG C or 180 DEG C are warming up to, compressed air is squeezed into from fluid injection/gas injection valve of mold, going out liquid/outlet valve from another releases The core material squeezed out by compressed air is released, liquid/outlet valve is finally closed out;60 DEG C or 40 DEG C or 70 DEG C are cooled to, are taken off Mould pulls the nonporous film of polytetrafluoroethylene (PTFE), along with the core for pulling out composite product internal residual, obtains the tool of forming There is the continuous carbon fibre reinforced epoxy based composites product of spiraled cavity.
Core material used in (1-3) is the polyether-ether-ketone of crystallization, and crystalline melt temperature is 140~145 DEG C, 160 DEG C or 180 Viscosity is less than 1000Pa.s at DEG C.
The present embodiment has obtained the continuous carbon fibre reinforced epoxy based composites product with spiraled cavity, core Material good mechanical properties when less than crystalline melt temperature, and melt after can be discharged, and can Reusability, after demoulding only need Remaining core can be removed completely by pulling out the nonporous film of polytetrafluoroethylene (PTFE), not need extra process, convenient and efficient, and core Material can directly recycle Reusability, be not required to complex process and without waste.
Embodiment 2:
The implementation process of the present embodiment technical solution is as follows:
Core material is warming up to 280 DEG C by (2-1), and it is sub- that injection enters the polyamides that a prefabricated hollow shape is zigzag In amine hermetic bag, overcoating polyimide seal bag, the interior core for core material are obtained.Again in one strata tetrafluoro of core outer wrapping The nonporous film of ethylene, sealing.
(2-2) will presoak the unidirectional continuous carbon fibre or glass fibre of High Temperature Curing Epoxy Resin System or benzoxazine at room temperature Prepreg is coated on the nonporous film surface of the polytetrafluoroethylene (PTFE) of above-mentioned core, is placed into mold, by the polyamides at core both ends The outlet of imines hermetic bag is fixed and sealed on connection gas nozzle, ensures air insulated between core and composite preform, together When composite preform side reserved bleeding point vacuumize, be warming up to 180 DEG C, heat carried out under defined pressure and temperature Press jug forming;After the completion of solidification, temperature is increased to 250 DEG C, and core becomes flowable viscous liquid at this time, and viscosity is 500Pa.s is passed through compressed air toward composite product inner cavity, the liquid core in inner cavity is discharged;It is cooled within 100 DEG C and takes Go out composite product and take out the isolation film and core of internal residual, obtains the continuous carbon with zigzag cavity of forming The continuous carbon fibre or glass fiber compound material system of fiber reinforced epoxy resin based composites product or benzoxazinyl Part.
Core material used in (2-3) is modified polyarylether ketone copolymers, and crystalline melt temperature is when being 200 DEG C, 250 DEG C Flowable liquid, non-toxic and tasteless, good mechanical properties.
Embodiment 3:
The implementation process of the present embodiment technical solution is as follows:
(3-1) prepares the high-temperature nylon hermetic bag that a prefabricated hollow shape is U-shaped;Core material is warming up to 260 DEG C, injection enters in the cavity of the high-temperature nylon hermetic bag, obtains the core of overcoating high-temperature nylon hermetic bag;Again outside core The nonporous film of a strata tetrafluoroethene is wrapped up, is sealed;
(3-2) at room temperature by unidirectional continuous carbon fibre or glass fiber winding above-mentioned core polytetrafluoroethylene (PTFE) it is non-porous Film surface, sizing obtain composite preform, place into mold, and the sealed nylon bag outlet at core both ends is fixed simultaneously It is tightly connected on gas nozzle, and ensures air insulated between core and composite preform, while composite preform side Reserved bleeding point vacuumizes, and is warming up to 110 DEG C, and High Temperature Curing Epoxy Resin System (highest solidification temperature 180 is injected by RTM techniques DEG C) or bimaleimide resin, cured after having injected and by program curing;The composite wood with core is taken out after cooling Expect product, then raise temperature to 230 DEG C or 250 DEG C, wherein bismaleimide resin based composites can be warming up to 280 DEG C will not thermal deformation, Core becomes liquid at this time, and from composite material inner cavity, one side outlet squeezes into compressed air, releases and is compressed from another outlet The core material that air squeezes out, until no liquid flows out;It is cooled to again less than 60 DEG C, the non-porous of polytetrafluoroethylene (PTFE) is pullled in demoulding Film or sealed nylon bag, along with the core for pulling out composite product internal residual.Obtain forming has U-shaped cavity Continuous carbon fibre reinforced epoxy base or bismaleimide resin based composites product, or corresponding glass fiber compound material system Part;
(3-3) above step, which is suitable for all 180 DEG C when choosing corresponding core material, has higher force intensity, and The 230 DEG C or 250 DEG C core materials for becoming liquid, such as a kind of low-melting-point metal blend, can be melted at 220 DEG C can flow Hydrodynamic body.
Embodiment 4:
The implementation process of the present embodiment technical solution is as follows:
Core material is poured into a mould blocking, then is machined into method and is processed into ellipsoid by (4-1);Or directly by core material It is injected into the mold with elliposoidal cavity, the core of elliposoidal is obtained after cooling and demolding.Again in one strata of core outer wrapping The nonporous film of tetrafluoroethene, sealing.
The continuous carbon fibre for presoaking intermediate temperature setting (120 DEG C) epoxy resin is wrapped in above-mentioned core by (4-2) at room temperature The nonporous film surface of polytetrafluoroethylene (PTFE), then it is cladded with the materials such as isolation film, airfelt, vacuum bag by autoclave forming process method Material is placed in autoclave and technique curing molding is cured as specified, and is then cooled to 60 DEG C and is carried hereinafter, removing auxiliary material taking-up The composite product of core;Composite product with core is warming up to 150 DEG C or 170 DEG C, core becomes viscous at this time Most of core materials of intracavitary are discharged using compressed air for thick liquid;It is cooled to 60 DEG C or 45 DEG C again, pulls polytetrafluoroethylene (PTFE) Nonporous film, along band pull out composite product internal residual core, or slightly cool down 10~20 DEG C when core composition Material is that viscous liquid is easy to pull out film when pulling out.Obtain the continuous carbon fibre enhancing ring with elliposoidal cavity of forming Epoxy resin-based composite product.
(4-3) the method is also applied for the continuous carbon fibre of preimpregnation bimaleimide resin, only cure process Temperature is 200 DEG C, needs to be warming up to 270 DEG C or 300 DEG C when core is discharged, and is hard solid when needing to select 200 DEG C accordingly, I.e. crystalline melt temperature higher than 20 DEG C of this temperature or more or glass transition temperature higher than 30 DEG C of this temperature or more, and 270 DEG C or The material of liquid at 300 DEG C for viscosity less than 1000Pa.s is as the material for preparing core.
Embodiment 5:
The implementation process of the present embodiment technical solution is as follows:
Core material is warming up to 280 DEG C by (5-1), and it is sub- that injection enters the polyamides that a prefabricated hollow shape is zigzag In amine hermetic bag, overcoating polyimide seal bag, the interior core for meltable core material are obtained.Again in one strata of core outer wrapping The nonporous film of tetrafluoroethene, sealing.
(5-2) at room temperature presoaks the unidirectional continuous polyimide fiber for presoaking High Temperature Curing Epoxy Resin System or aramid fiber Material is coated on the nonporous film surface of the polytetrafluoroethylene (PTFE) of above-mentioned core, is placed into mold, by the sealed nylon at core both ends Bag outlet is fixed and is tightly connected on gas nozzle, ensures air insulated between core and composite preform, while composite material The reserved bleeding point in precast body side vacuumizes, and is warming up to the required temperature of solidification and cures to obtain by regulation technique molding Composite product;260 DEG C are warming up to, compressed air is squeezed into from the gas valve of the connection core of mold, from another outlet Valve releases the core material squeezed out by compressed air, until closing outlet valve after the outflow of no liquid.Then it is cooled to 55 DEG C or less or 80 DEG C hereinafter, demoulding, pull the nonporous film or polyimide seal bag of polytetrafluoroethylene (PTFE), along band pull out composite wood Expect the core of product internal residual, or slightly cools down 10~20 DEG C when core constituent material is drawn when being easy pull-out for viscous liquid Go out film.Obtain the continuous polyimide fiber reinforced epoxy based composites system with zigzag cavity of forming Part or continuous aramid fiber reinforced epoxy based composites product.
It is from embodiment as can be seen that the present invention relates to a kind of method preparing complicated inner cavity composite product, i.e., sharp With rigidity at a temperature of a kind of composite molding, and it is warming up to no more than the fusible material as liquid under product heat distortion temperature Material is used as core material, therefore the structure and inner-cavity structure of composite product are well kept when curing molding, and improves temperature After can easily remove intracavitary core, finally obtain the composite product with complicated cavity structure.The present invention can not only make The composite product of the standby continuous lod with various cavity structures, and decoring speed is fast, and core material can be repeatedly It uses.
Although above having used general explanation and specific embodiment, the present invention is described in detail, at this On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore, These modifications or improvements without departing from theon the basis of the spirit of the present invention belong to the scope of protection of present invention.

Claims (6)

1. a kind of method preparing complicated inner cavity product, which is characterized in that this method includes:
A, the continuous fiber of pre-soaked resin is wrapped in the whose surfaces for being enclosed with isolation film at room temperature, or by continuous fiber resin Prepreg is coated with the core for obtaining being enclosed with precast body in the whose surfaces for being enclosed with isolation film;
B, the core for being enclosed with precast body is put into mold, so that core and precast body is sealed against each other using fluid sealant and isolation film Isolation;
C, precast body curing molding is obtained into curing molding product at curing temperatures;
D, it is warming up to after core constituent material is fused into liquid, apply compressed air discharge curing molding product intracavitary becomes liquid The core of state, cooling and demolding, the remaining core of removal intracavitary and isolation film, obtain complicated inner cavity product,
Continuous fiber described in the continuous fiber and/or continuous fiber resin of the pre-soaked resin is selected from carbon fiber, glass fibers At least one of dimension, aramid fiber and polyimide fiber, the resin are selected from epoxy resin, unsaturated polyester (UP), benzo At least one of oxazines resin and bimaleimide resin, the isolation film is polytetrafluoroethylene (PTFE) nonporous film, described close Sealing is silicon rubber, and briquetting pressure is 0.4-1 megapascal, and the condition of cure is:Temperature is 100-200 DEG C, and the core is constituted Material is hard solid under the solidification temperature, higher than it is more than 30~100 DEG C of the solidification temperature as flowable liquid, And the viscosity of the liquid is less than 1000Pa.s.
2. according to the method described in claim 1, it is characterized in that, step d is replaced with:
D ', cooling and demolding are warming up to after core constituent material is fused into liquid, pour out core or apply compressed air discharge solidification The core as liquid of molded article intracavitary, the remaining core of removal intracavitary and isolation film, obtain complicated inner cavity product.
3. according to the method described in claim 1, it is characterized in that, the continuous fiber and/or continuous fiber of the pre-soaked resin Resin in resin is bimaleimide resin, and core constituent material is hard solid at 180 DEG C or 200 DEG C or less, is higher than 30~100 DEG C or more of this 180 DEG C or 200 DEG C and no more than precast body heat distortion temperature when, become flowable liquid, viscosity Less than 1000Pa.s.
4. according to the method described in claim 1, it is characterized in that, the continuous fiber and/or continuous fiber of the pre-soaked resin Resin in resin is epoxy resin, and core constituent material is hard solid at 120 DEG C or less, a certain in 150~200 DEG C More than temperature become flowable liquid, and the viscosity of the liquid is less than 1000Pa.s.
5. according to the method described in claim 1, it is characterized in that, the continuous fiber and/or continuous fiber of the pre-soaked resin Resin in resin is epoxy resin, and core constituent material is hard solid at 180 DEG C or less, a certain in 210~250 DEG C More than temperature become flowable liquid, and the viscosity of the liquid is less than 1000Pa.s.
6. according to the method described in claim 1, it is characterized in that, the core constituent material be polyether-ether-ketone, the core structure Crystalline melt temperature at material is that viscosity is less than 1000Pa.s at 140~145 DEG C, 160 DEG C or 180 DEG C;
Alternatively, the core constituent material is modified polyarylether ketone copolymers, being when crystalline melt temperature is 200 DEG C, 250 DEG C can Flow liquid;
Alternatively, the core constituent material is the low-melting-point metal blend that fusing point is less than 220 DEG C.
CN201610313430.8A 2016-05-12 2016-05-12 A method of preparing complicated inner cavity product Expired - Fee Related CN106003753B (en)

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CN109318511A (en) * 2017-08-01 2019-02-12 北京鸿鹄雄狮技术开发有限公司 A kind of low cost preparation method of complicated inner cavity composite product
IT201800005302A1 (en) 2018-05-11 2019-11-11 TRANSMISSION SIDE BICYCLE CRANK, EQUIPPED WITH STRESS / DEFORMATION DETECTOR FOR A TORQUE OR POWER METER, AS WELL AS RELATED METHODS
IT201800005294A1 (en) 2018-05-11 2019-11-11 COMPONENT OF BICYCLE IN COMPOSITE MATERIAL AND RELATED MANUFACTURING PROCESS
IT201800005299A1 (en) 2018-05-11 2019-11-11 BICYCLE COMPONENT EQUIPPED WITH STRESS / DEFORMATION SENSOR COMPENSATED FOR TEMPERATURE
IT201800005297A1 (en) 2018-05-11 2019-11-11 BICYCLE CRANK AND RELATIVE CRANKSET
CA3042547A1 (en) 2018-05-11 2019-11-11 Campagnolo S.R.L. Bicycle crankarm provided with electric/electronic system
CN113352645A (en) * 2021-06-03 2021-09-07 哈尔滨工程大学 Integrated preparation method of foam filled composite material hemispherical auxetic structure

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