CN107868448B - Continuous fiber reinforced long carbon chain nylon composite board - Google Patents
Continuous fiber reinforced long carbon chain nylon composite board Download PDFInfo
- Publication number
- CN107868448B CN107868448B CN201711014561.7A CN201711014561A CN107868448B CN 107868448 B CN107868448 B CN 107868448B CN 201711014561 A CN201711014561 A CN 201711014561A CN 107868448 B CN107868448 B CN 107868448B
- Authority
- CN
- China
- Prior art keywords
- fiber
- nylon
- fiber cloth
- temperature
- pressure
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping 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
- B29C70/34—Shaping 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 and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Moulding By Coating Moulds (AREA)
- Laminated Bodies (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to a continuous fiber reinforced long carbon chain nylon composite board, which is formed by heating and molding a plurality of layers of nylon/fiber cloth composite sheets, wherein the nylon/fiber cloth composite sheets are composed of nylon resin and fiber cloth, under the heating condition, the nylon resin is melted, the solid is changed into melt to be immersed into the fiber cloth, the fiber is coated and bonded, and the continuous fiber reinforced long carbon chain nylon composite board is formed by calendaring, cooling and solidifying. The composite board provided by the invention has the advantages of high strength, high modulus, impact resistance, corrosion resistance, secondary processing molding, recyclability, large design freedom degree, large-scale continuous production and the like, is an ideal substitute material for metal and thermosetting composite materials, and is widely applied to structural materials in industries such as machinery, automobiles, rail transit, ships, aerospace vehicles and the like.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a continuous fiber reinforced long carbon chain nylon composite board.
Background
With the development of industries such as automobiles, rail transit equipment, ships, aviation and the like, particularly the development of lightweight technology, the development of polymer composite materials is promoted. Particularly, thermosetting composite materials are developed rapidly, and the thermosetting composite materials comprise thermosetting carbon fiber composite materials and thermosetting glass fiber composite materials which are widely applied. The thermosetting composite material has the characteristics of high strength and modulus, light specific gravity, corrosion resistance and the like, but has the defects of poor impact resistance, poor low-temperature resistance, difficult secondary processing, low production efficiency, non-recyclability and the like.
The continuous fiber reinforced nylon has the advantages of high strength, high modulus, high temperature resistance and the like. The plastic can be used for structural parts of automobiles, rail transit vehicles and engineering machinery, and steel is replaced by plastic, so that light weight of vehicle equipment is realized. Continuous glass fiber reinforced polypropylene composite materials have been industrialized; carbon fiber thermoset composites are also commercially available. However, the glass fiber reinforced polypropylene composite material has low strength, and the carbon fiber thermosetting composite material is difficult to perform secondary molding and cannot be recycled. Continuous glass fiber reinforced general nylon compositeThe material has high strength, but the general nylon is easy to absorb water, so that the composite board is easy to deform under high humidity, the low-temperature impact resistance is not high, the specific gravity of the material is larger, and about 1.6kg/cm3. Therefore, the high-strength and high-low temperature resistant composite material is developed and used for aircraft body, empennage, wing plate making and unmanned aerial vehicle body materials; the rail transit vehicle, the automobile body and the material for the parts and the structural parts of the automobile body have extremely important significance.
In each of the published patents, the glass fiber reinforced nylon and the carbon fiber reinforced general nylon are prepared into the composite material by adopting a double-screw co-extrusion process, for example, the glass fiber reinforced nylon patent comprises: CN106479167/CN106366656A/CN106167619A/CN105602244A/CN105504798A/C N105295370A/CN 10541931315A; carbon fiber reinforced nylon patent: CN103289368B/CN103786277B/CN102558847B/CN201710150374.5, and the like, in the aramid fiber reinforced nylon patent, CN103627164A provides a method for preparing a high-temperature resistant nylon composite material by blending and extruding aramid short fibers and high-temperature nylon resin through double screws; CN103788624A proposes a method for preparing a high-temperature-resistant nylon composite material by adding aramid short fibers into high-temperature-resistant nylon salt for melt polymerization; however, the above patents do not relate to the continuous impregnation of long carbon chain nylon powder into fiber and its blended fabric to prepare high strength and high and low temperature resistant nylon composite material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a continuous fiber reinforced long carbon chain nylon composite board which has the advantages of high strength, high modulus, impact resistance, corrosion resistance, secondary processing molding, recyclability, large design freedom, large-scale continuous production and the like, is an ideal substitute material for metal and thermosetting composite materials, and can be widely used as a structural material in industries such as machinery, automobiles, rail transit, ships, aerospace vehicles and the like.
The invention provides a continuous fiber reinforced long carbon chain nylon composite board, which is formed by heating and compression molding a plurality of layers of nylon/fiber cloth composite sheets. The nylon/fiber cloth composite sheet is formed by melting nylon resin and fiber cloth under the heating condition, immersing the nylon resin into the fiber cloth, coating and bonding fibers, and rolling, cooling and solidifying the fiber cloth. The nylon resin is used as a fiber coating binder, so that each fiber of the fiber cloth is coated and bonded together through the nylon resin to form a whole, namely the sheet; meanwhile, when a plurality of composite sheets are superposed, heated and pressed, the nylon resin is melted, and the sheets are bonded together to form a whole, namely the composite board.
The weight ratio of nylon resin to fiber cloth in the nylon/fiber cloth composite sheet is (30-40): (60-70). The thickness of the nylon/fiber cloth composite sheet is generally 0.34 +/-0.01 m, the width is 0.5-1.6m, the number of the laid layers of the composite sheet is 5-40, when the overall thickness is (1.7-13.6) +/-0.1 mm, the width is 0.5-1.6m, the length is 1.0-1.8m, preferably 10-30 layers, and when the overall thickness is (3.4-10.0) +/-0.1 mm, the width is 0.5-1.2m, and the length is 1.0-1.8 m.
The nylon resin has excellent mechanical properties, particularly excellent low-temperature resistance, polar groups such as macromolecular chain amide groups, amino-hexancarboxyl groups and the like, and strong cohesiveness to fibers; the nylon resin comprises one or two or more of aliphatic nylon and semi-aromatic nylon, and the mixture is not limited by weight parts, and the aliphatic nylon specifically comprises PA6, PA56, PA66, PA610, PA611, PA612, PA1010, PA613, PA11, PA12, PA46 and PA 1313; semi-aromatic nylon PA4T, PA6T, PA9T, PA10T, PA11T, PA12T and PA 13T.
The fiber cloth in each layer of the nylon/fiber cloth composite sheet is carbon fiber cloth A, glass fiber cloth B, basalt fiber cloth C, aramid fiber cloth D, carbon fiber/glass fiber mixed fabric E, carbon fiber/basalt fiber mixed fabric F, carbon fiber/aramid fiber mixed fabric J, aramid fiber/glass fiber mixed fabric H or aramid fiber/basalt fiber mixed fabric I, and the fiber cloth in each layer can be the same or different. Wherein the weight ratio of the carbon fiber to the glass fiber in the carbon fiber/glass fiber mixed fabric E is 2: 8, wherein the weight ratio of carbon fibers to basalt fibers in the carbon fiber/basalt fiber mixed fabric F is 2: 8, wherein the weight ratio of carbon fiber to aramid fiber in the carbon fiber/aramid fiber mixed fabric J is 2: 8, wherein the aramid fiber/glass fiber mixed fabric H is characterized in that the weight ratio of the aramid fiber to the glass fiber is 2: 8, wherein the weight ratio of aramid fibers to basalt fibers in the aramid/basalt fiber mixed fabric I is 2: 8; weaving of fiber clothThe mode is plain weave 1 or twill weave 2, according to different application, can be single structure or two kinds of weaving mode composite designs. The carbon fiber, the glass fiber, the aramid fiber and the basalt fiber are high-strength and high-modulus materials, and especially when the carbon fiber and the aramid fiber have extremely high strength and modulus and are compounded with nylon, the carbon fiber, the glass fiber, the aramid fiber and the basalt fiber play a good role in reinforcing nylon resin. The two composites can be used for preparing high-strength high-modulus composite materials. The invention adopts nylon resin as the coating bonding material and fiber cloth as the framework material, solves the problems that the fiber in the board is unevenly distributed and the mechanical property of the board is uneven because the fiber slides along with the melt flow of nylon in the heating and molding process of the unidirectional fiber as the enlarging material, and ensures that the composite board has uniform performance in all directions. The gram weight of the fiber cloth is 100-600g/m2Preferably 200-400g/m2。
Compared with the use of tows, the fiber cloth is adopted as the reinforced framework material of the composite material, and the fibers form a plurality of interlacing points through weaving, so that slippage of the fibers in the resin melting impregnation and mould pressing processes is effectively avoided, the fibers are uniformly dispersed, the uniformity of the performance of the composite material is ensured, and the composite material has high strength and high modulus.
The fiber cloth used as the framework in each composite sheet in the composite board can be combined randomly according to different application field requirements, and the fiber cloth in each layer of nylon/fiber cloth composite sheet is mainly selected from carbon fiber cloth A, glass fiber cloth B, basalt fiber cloth C, aramid fiber cloth D, carbon fiber/glass fiber mixed fabric E, carbon fiber/basalt fiber mixed fabric F, carbon fiber/aramid fiber mixed fabric J, aramid fiber/glass fiber mixed fabric H or aramid fiber/basalt fiber mixed fabric I.
The fiber cloth of each layer can be formed by selecting the same cloth or mixing a plurality of cloths, and the specific laying forms can be (1) A type, (2) B type, (3) C type, (4) D type, (5) E type, (6) F type, (7) J type, (8) H type and (9) I type; or two different fiber cloths such as (10) ABAB type, (11) ACAC type, (12) ADAD type, (13) BCBC type, (14) BDBD type and the like are alternately paved; or (15) nAMBnA type, (16) nAMCNA type; (17) nBmAnB type, (18) nBmDnB type (19) nDmBnD type, (20) nDmCnD type, (21) nBmBmAnB type, (22) nBmDnDnB type or (23) nBnBxDnB type, wherein n, m and x represent specific layer numbers and are generally 1-20, and specific values of n, m and x can be selected according to use requirements and cost, wherein n, m and x represent specific fiber cloth forms (A type, B type, C type and D type) in front of the fiber cloth forms, and represent that the fiber cloth forms are n, m and x layers, and the values of n, m and x can be the same or different. The single fiber cloth and the mixed fiber cloth can be laid in a mode of (24) AnEA type, (25) AnFA type, (26) AnJA type, (27) AnHA type, or (28) AnIA type; or (29) BnEB type, (30) BnFB type, (31) BnJB type, (32) BnHB type, (33) BnIB type; (34) CnEC type, (36) CnFC type, (36) CnJC type, (37) CnHC type, (39) CnIC type; (40) DnED type, (41) DnFD type, (43) DnJD type, (44) DnHD type, (45) DnID type, where n is in front of the specific fiber cloth form, typically a value of 1-28.
The composite board has two weaving structures of plain weave 1 and twill weave 2, the two structures endow the composite board with different mechanical properties, and for common board application, the weaving structures can be (first) all plain weave 1 type structures or (second) all twill weave 2 type structures; the complex structural parts need to be designed into a layering structure, and can be in a cross structure of 12121 and 21212, or a cross structure of 1m21 type, a cross structure of 2m12 type, a cross structure of 1m21m21 type and a cross structure of (b 2m12m 12) type. m is 2-15. 1 indicates a plain structure, and 2 indicates a twill structure.
The nylon/fiber cloth composite sheet can also contain an antioxidant, an ultraviolet-resistant absorbent and a lubricant, and the antioxidant, the ultraviolet-resistant absorbent and the lubricant are mixed in nylon resin when the nylon resin is crushed, and are fused together with the nylon resin and then are immersed in the fiber cloth. The weight ratio of the nylon resin to the antioxidant is (30-60): (0.3-0.8); the weight ratio of the nylon resin to the anti-ultraviolet absorbent is (30-60): (0.2-0.8); the weight ratio of the nylon resin to the lubricant is (30-60): (0.1-1.0).
The antioxidant is a hindered phenol compound, and specifically comprises one of N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propyl ] hexanediamine (A), tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propyl ] pentaerythritol ester (B), beta- (3, 5-dibutyl-4-hydroxyphenyl) propylene N-octadecyl ester (C), and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6(1H,2H,5H) -trione (D).
The anti-ultraviolet light absorber is triazine imidazole, specifically comprises one of UV321, UV323, UV325, UV327, UV328 and UV329, and the dosage of the anti-ultraviolet light absorber is 0.2-0.8 parts, preferably 0.3-0.6 parts
The lubricant is one or more of erucamide, zinc stearate, calcium stearate, silicone and pentaerythritol ester.
The hindered phenol antioxidant and the ultraviolet-resistant absorbent are compounded for use, so that the aging resistance of the composite material can be greatly improved, and the composite material is suitable for outdoor occasions. Ensuring that the composite material keeps excellent mechanical property under long-term outdoor exposure condition.
The preparation process of the continuous fiber reinforced long carbon chain nylon composite board provided by the invention comprises gap molding and continuous molding, wherein one of the gap molding and the continuous molding is selected for molding preparation. The method comprises the following specific steps:
gap die pressing: the technological process sequentially comprises the working procedures of preheating, heating and pressing, constant temperature and pressure, constant pressure cooling, shaping, trimming, packaging and the like. The process conditions are as follows: preheating temperature: 250 ℃ and 280 ℃, pressure: 1-3 MPa; heating temperature: 260 ℃ and 320 ℃, the pressure is 2-5MPa, and the time is 0.5-1.0 hour; constant temperature and pressure: temperature: 260 ℃ and 320 ℃, time: 1-2 hours, and the pressure is 3-8 MPa; constant-pressure cooling: pressure 3-8MPa, temperature 80-120 ℃, time: 0.5-1.0 hour; cooling time: 0.5-1.0 hour, temperature: 60-80 ℃.
And (3) continuous die pressing process: the die pressing process of the nylon/fiber cloth composite sheet formed by the aliphatic nylon comprises the following steps: traction speed: preheating temperature of 3-20 m/min: 180 ℃ and 220 ℃, and the temperature rise of the mould pressing is as follows: 210 ℃ and 250 ℃, and the constant temperature is: 210 ℃ and 240 ℃, temperature rise and pressurization: 2-8MPa, constant-temperature mould pressing of 5-10MPa, constant-pressure cooling pressure: 5-10MPa, temperature: 120-140 ℃; cooling temperature: 60-70 ℃; the molding process of the nylon/fiber cloth composite sheet formed by the semi-aromatic nylon comprises the following steps: traction speed: 3-20m/min, preheating temperature: 280-300 ℃, mold pressing temperature rising: 320 ℃ and 350 ℃, and the constant temperature is as follows: 300-340 ℃, heating and pressurizing: 2-8MPa, constant-temperature mould pressing of 5-10MPa, constant-pressure cooling pressure: 5-10MPa, temperature: 120 ℃ and 140 ℃, cooling temperature: 60-80 ℃.
The continuous fiber reinforced long carbon chain nylon composite board provided by the invention mainly has the following applications: the automobile spare tire bracket is used for an automobile passenger car engine cover, an engine chassis, a rear box cover, a top plate and a spare tire bracket; commercial vehicle leaf springs, box bodies, cab ceilings and mini-bus leaf springs; rail transit vehicles; a motor car ceiling and a truck box body; unmanned aerial vehicles and other aircraft fuselage and blades; a container body.
The continuous fiber reinforced long carbon chain nylon composite board has the performance characteristics of high strength and high modulus, the highest bending strength reaches 650MPa, and the modulus is more than 3.5 GPa; the low temperature resistance is excellent, and the notch impact strength at the low temperature of-50 ℃ can reach 90KJ/m 2; has light specific gravity and density of 1.6g/cm3(ii) a Corrosion resistance and can be recycled; secondary processing such as molding, machining, welding can be performed. The performance test of the continuous fiber reinforced long carbon chain nylon composite board provided by the invention is carried out according to the following standards:
tensile strength (MPa): ASTM D638-2014;
bending strength (MPa): ASTM D790-2007;
flexural modulus (MPa): ASTM D790-2007;
notched impact strength (kJ/m 2): ASTM D756-1993;
heat distortion temperature (. degree. C.): astm d 648.
PA6 used in the invention is purchased from the tomb petrochemical company, PA66 is purchased from the Henan Flat-topped mountain Shenma group company, PA11 and PA12 are purchased from the Suwei chemical company, PA10T is purchased from the Guangzhou Jinfa science and technology shares company, and other nylon resins are commercially available; carbon fiber cloth and aramid fiber cloth are purchased from Jiangsu, and glass fiber cloth, basalt fiber cloth and mixed fiber cloth are purchased from Jiangsu Hongfa composite material company Limited.
The preparation method of each layer of nylon/fiber cloth composite sheet material comprises the following steps:
the method comprises the following steps: preparation of nylon resin powder:
the freeze crushing powder making process includes freezing nylon resin with liquid nitrogen at-30 deg.c to-50 deg.c, and grinding into 50-100 micron size powder in a mill. Preferably, the temperature of the liquid nitrogen is-35 to-45 ℃, and the particle size of the powder is 50 to 80 mu m.
Step two: preparing a composite material by impregnating fiber cloth with nylon powder:
1. and (3) adding the antioxidant, the ultraviolet light absorber, the lubricant and the nylon resin powder obtained in the step one into a mixer in proportion, stirring for 3-10min (preferably 5-8min) at a stirring speed of 100-300prm (preferably 150-200prm), and then discharging, and adding the mixed material into a storage tank of a powder metering feeder for later use.
2. The fiber cloth roll is drafted and preheated by a guide roller, and then enters a powder metering feeder, the powder metering feeder continuously and uniformly spreads the mixed powder in a storage tank on the fiber cloth according to a proportion, the fiber cloth roll is compacted by the guide roller and enters a heating box, the nylon resin powder is melted in the heating process, the nylon resin powder is changed into a flowable melt from a solid, the flowable melt is immersed into fiber spaces of the fiber cloth, the fibers are infiltrated and coated, and then the composite material is obtained through cooling, calendaring, solidification, air cooling and rolling.
The process comprises the following steps: the preheating temperature of the heating box is 120-280 ℃, the heating melting temperature of the nylon resin powder in the heating box is 220-350 ℃, the heating time of the nylon resin powder in the heating box is 3-50min, the traction speed of the guide roller during drafting is 3-40m/min, the temperature of the cooling compression roller is 50-80 ℃, and the air cooling time is 2-10 min.
The preheating temperature of the fiber cloth is preferably 160-260 ℃, the preheating temperature of the aliphatic nylon resin is preferably 160-180 ℃, and the preheating temperature of the semi-aromatic nylon resin is preferably 200-260 ℃, so that the surface temperature of the fiber cloth is close to the melting point of nylon, and the nylon resin powder is immediately melted and adhered to the fiber cloth when being spread on the fiber cloth.
The melting temperature of the nylon resin powder is preferably 230-330 ℃, the aliphatic nylon resin is preferably 230-260 ℃, and the semi-aromatic nylon is preferably 280-330 ℃; the melt temperature of the nylon resin powder directly influences the melt flowability of the nylon resin powder, the melt flowability influences the infiltration and coating effect, the melt viscosity of the nylon resin melt is small when the melt temperature is high, the infiltration speed of the nylon resin melt on the fiber cloth is high, the coating effect is good, but the degradation of nylon molecules is caused when the melt temperature is too high, and finally the performance of the composite material is reduced; if the melting temperature is low, the nylon resin powder is melted slowly, the melt viscosity is high, the infiltration speed is low, the final coating effect is poor, and the performance of the composite material is affected as a result. Therefore, it is very important to reasonably design the melting temperature of the nylon resin powder. The invention adopts a high-temperature rapid melting dipping scheme from the consideration of melting speed, melt viscosity, infiltration speed and effect and product performance. Not only ensures the performance of the product, but also improves the productivity.
The heating time is preferably 4-20 min. The heating time is related to the melting speed of the nylon resin powder, the nylon resin powder can not be heated too long, the nylon resin can be degraded if the heating time is too long, and the nylon resin can be incompletely melted if the heating time is too short, so that the fiber cloth can not be well infiltrated and coated;
the preferred drawing speed is 5-10m/min, and the drawing speed influences the retention time of the material in the heating box, the resin melting and infiltrating effect, the performance and the productivity of the composite material. In a word, the melting temperature, the heating time and the traction speed are reasonably adjusted to ensure the performance of the composite material.
Detailed Description
Example 1:
the first step is as follows: PA612 is selected to be respectively compounded with fiber cloth A, B, C, D, E, J, H to prepare a composite sheet, and the weight ratio of PA612 to A, B, C, D, E, J, H is 30: 70, the fiber cloth is plain weave 1 and twill weave 2. The preparation process comprises the following steps: 21kg of PA612 was frozen and pulverized into 60um powder, and 7kg of each fiber cloth A, B, C, D, E, J, H was taken. And (3) spreading the PA612 powder on the fiber cloth A, B, C, D, E, J, H respectively according to a proportion, sending the mixture into a heating box, heating the mixture to 260 ℃ for 6min, and obtaining 14 PA 612/fiber cloth composite sheets after calendering and cooling.
The second step is that: and selecting several typical sheet laying schemes, and carrying out die pressing to prepare the composite board. 11 laying modes (1), (2), (3), (5), (8), (15), (21), (22), (24) (29) and (36) are selected according to the composition of the fiber cloth, and then the first, the second, the third and the fifth are selected according to the weaving structure of the fiber cloth.
The composite board is laid in 4 modes, and the total number of the composite board layers is 15. Wherein n in the (15) layer structure is 3, m is 9, n and m in (21) and (22) are both 3, n in (24), (29) and (36) are both 13, and the die pressing process is carried out. The technological process includes the steps of preheating, heating and pressing, constant temperature and pressure, constant pressure cooling, setting, trimming, packing and other steps. The process conditions are as follows: preheating temperature: 250 ℃, pressure: 1 MPa; heating temperature: the temperature is 260 ℃, the pressure is 3Pa, and the time is 0.5 hour; constant temperature and pressure: temperature: 260 ℃, time: 2 hours, pressure 5 Pa; constant-pressure cooling: pressure 5Pa, temperature 120 ℃, time: 1.0 hour; cooling time: 0.5 hour, temperature: at 60 ℃. The 22 composite boards with different structures are prepared by the process, the thickness is 5 +/-0.1 mm, the width is 1.0m, and the length is 1.5 m.
And sampling from the prepared plate body, and testing the mechanical property and the thermal property of the plate body. Are shown in Table 1.
Example 2:
taking 16kg of PA6 powder, and compounding the powder with 24kgA and 24kgB in a weight ratio of 40: 60. A. The gram weight of B is 400g/m2The sheet preparation process was the same as in example 1.
The sheet material layering mode is 3 according to (1), (2) and (22), the weaving structure is (1), (2), (22) and (c), m is 6, and the mould pressing process is the same as the example. 4 composite boards with different structures are prepared according to the process, the thickness is 5 +/-0.1 mm, the width is 1.0m, and the length is 1.5 m.
And sampling from the prepared plate body, and testing the mechanical property and the thermal property of the plate body. Are shown in Table 1.
Example 3:
PA10T and A, B. Taking 16kg of PA10T powder, and compounding the powder with 24kgA and 24kgB according to the weight ratio of 40: 60. A. The gram weight of B is 400g/m2. The sheet preparation process comprises the following steps: uniformly spreading the PA10T powder on A, B cloth, feeding into a heating box, heating to 320 ℃, heating for 10min, and rolling and cooling to obtain 4 composite sheets.
The sheet material layering mode is that n is 3 according to (1), (2) and (22), the weaving structure is that (1) and (2), (22) are that (c) and (c), and m is 6 in (c). The mould pressing process comprises the working procedures of preheating, heating mould pressing, constant temperature and pressure, constant pressure cooling, shaping, edge cutting, packaging and the like. The process conditions are as follows: preheating temperature: 280 ℃, pressure: 1 MPa; heating temperature: 320 ℃, the pressure is 3Pa, and the time is 0.5 hour; constant temperature and pressure: temperature: 320 ℃, time: 2 hours, pressure 5 Pa; constant-pressure cooling: pressure 5Pa, temperature 160 ℃, time: 1.0 hour; cooling time: 0.5 hour, temperature: at 60 ℃.4 composite boards with different structures are prepared according to the process, the thickness is 5 +/-0.1 mm, the width is 1.0m, and the length is 1.5 m.
And sampling from the prepared plate body, and testing the mechanical property and the thermal property of the plate body. Are shown in Table 1.
TABLE 1 composite sheet Properties
As seen from Table 1, the continuous fiber reinforced nylon composite board prepared by the present invention has high strength, high modulus, high impact resistance and excellent heat resistance. The carbon fiber reinforced nylon has the tensile strength of 889MPa at most, the bending strength of 1250PMa at most, and the notch impact strength at the low temperature of-50 ℃ is mostly 100kJ/m2The heat distortion temperature is generally about 200 ℃ and can reach as high as 280 ℃.
Claims (4)
1. A continuous fiber reinforced long carbon chain nylon composite board is characterized in that,
the continuous fiber reinforced long carbon chain nylon composite board is formed by heating, molding and forming a plurality of layers of nylon/fiber cloth composite sheets,
the nylon/fiber cloth composite sheet is composed of nylon resin and fiber cloth, wherein the nylon resin is molten under the heating condition and is immersed into the fiber cloth, the fiber is coated and bonded, and the nylon/fiber cloth composite sheet is formed by rolling, cooling and solidifying;
the number of layers of the nylon/fiber cloth composite sheet is 5-40, the thickness of each layer is the same, when the overall thickness is (1.7-13.6) + -0.1 mm, the width is 0.5-1.6m, the length is 1.0-1.8m, when the overall thickness is (3.4-10.0) + -0.1 mm, the width is 0.5-1.2m, and the length is 1.0-1.8 m;
the nylon/fiber cloth composite sheet also contains an antioxidant, an anti-ultraviolet absorbent and a lubricant, wherein the weight ratio of the nylon resin to the antioxidant is (30-60): (0.3-0.8); the weight ratio of the nylon resin to the anti-ultraviolet absorbent is (30-60): (0.2-0.8); the weight ratio of the nylon resin to the lubricant is (30-60): (0.1-1.0);
the fiber cloth in each layer of the nylon/fiber cloth composite sheet is carbon fiber cloth A, glass fiber cloth B, basalt fiber cloth C, aramid fiber cloth D, carbon fiber/glass fiber mixed fabric E, carbon fiber/basalt fiber mixed fabric F, carbon fiber/aramid fiber mixed fabric J, aramid fiber/glass fiber mixed fabric H or aramid fiber/basalt fiber mixed fabric I, and the fiber cloth in each layer can be the same or different;
wherein the weight ratio of the carbon fiber to the glass fiber in the carbon fiber/glass fiber mixed fabric E is 2: 8, wherein the weight ratio of carbon fibers to basalt fibers in the carbon fiber/basalt fiber mixed fabric F is 2: 8, wherein the weight ratio of carbon fiber to aramid fiber in the carbon fiber/aramid fiber mixed fabric J is 2: 8, wherein the aramid fiber/glass fiber mixed fabric H is characterized in that the weight ratio of the aramid fiber to the glass fiber is 2: 8, wherein the weight ratio of aramid fibers to basalt fibers in the aramid/basalt fiber mixed fabric I is 2: 8; the weaving mode of the fiber cloth is plain weave or twill weave, and the weaving modes of the fiber cloth in each layer of the nylon/fiber cloth composite sheet can be the same or different;
the heating and compression molding comprises gap molding and continuous molding, and the technical process sequence of the gap molding comprises the working procedures of preheating, heating and compression, constant temperature and pressure, constant pressure cooling, shaping, trimming and packaging; the process conditions are as follows: preheating temperature: 250 ℃ and 280 ℃, pressure: 1-3 MPa; heating temperature: 260 ℃ and 320 ℃, the pressure is 2-5MPa, and the time is 0.5-1.0 hour; constant temperature and pressure: temperature: 260 ℃ and 320 ℃, time: 1-2 hours, and the pressure is 3-8 MPa; constant-pressure cooling: pressure 3-8MPa, temperature 80-120 ℃, time: 0.5-1.0 hour; cooling time: 0.5-1.0 hour, temperature: 60-80 ℃;
the continuous die pressing process specifically comprises the following steps: the die pressing process of the nylon/fiber cloth composite sheet formed by the aliphatic nylon comprises the following steps: traction speed: preheating temperature of 3-20 m/min: 180 ℃ and 220 ℃, and the temperature rise of the mould pressing is as follows: 210 ℃ and 250 ℃, and the constant temperature is: 210 ℃ and 240 ℃, temperature rise and pressurization: 2-8MPa, constant-temperature mould pressing of 5-10MPa, constant-pressure cooling pressure: 5-10MPa, temperature: 120-140 ℃; cooling temperature: 60-70 ℃; the molding process of the nylon/fiber cloth composite sheet formed by the semi-aromatic nylon comprises the following steps: traction speed: 3-20m/min, preheating temperature: 280-300 ℃, mold pressing temperature rising: 320 ℃ and 350 ℃, and the constant temperature is as follows: 300-340 ℃, heating and pressurizing: 2-8MPa, constant-temperature mould pressing of 5-10MPa, constant-pressure cooling pressure: 5-10MPa, temperature: 120 ℃ and 140 ℃, cooling temperature: 60-80 ℃;
the preparation process of the nylon/fiber cloth composite sheet comprises the following steps:
the method comprises the following steps: preparing nylon resin powder by adopting a freezing and crushing powder preparation process;
step two: preparing a composite material:
(1) mixing an antioxidant, an ultraviolet absorber and a lubricant with nylon resin powder in proportion, and adding the mixture into a storage tank of a powder metering feeder after mixing;
(2) and after being drawn and preheated by a guide roller, the fiber cloth roll enters a powder metering feeder, the powder mixed in the storage tank is continuously and uniformly spread on the fiber cloth by the powder metering feeder in proportion, is compacted by the guide roller and enters a heating box, the nylon resin powder is melted and immersed in fiber spaces of the fiber cloth in the heating process, and then is cooled, calendered, solidified, air-cooled and rolled to obtain the composite material.
2. The continuous fiber reinforced long carbon chain nylon composite board according to claim 1, wherein the weight ratio of the nylon resin to the fiber cloth in the nylon/fiber cloth composite sheet is (30-40): (60-70).
3. The continuous fiber reinforced long carbon chain nylon composite board according to claim 1, wherein the nylon resin is one or two or more of aliphatic nylon and semi-aromatic nylon, and the aliphatic nylon includes PA6, PA56, PA66, PA610, PA611, PA612, PA1010, PA613, PA11, PA12, PA46, and PA 1313; the semi-aromatic nylon comprises PA4T, PA6T, PA9T, PA10T, PA11T, PA12T and PA 13T.
4. The continuous fiber reinforced long carbon chain nylon composite board according to any one of claims 1-3, wherein the composite board is used for automobile passenger car engine covers, engine chassis, trunk covers, roofs, spare tire carriers, commercial car leaf springs, boxes, cab roofs, mini-bus leaf springs, rail transit vehicles, motor car roofs, truck boxes, unmanned aerial vehicle fuselages, paddles, or container boxes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711014561.7A CN107868448B (en) | 2017-10-26 | 2017-10-26 | Continuous fiber reinforced long carbon chain nylon composite board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711014561.7A CN107868448B (en) | 2017-10-26 | 2017-10-26 | Continuous fiber reinforced long carbon chain nylon composite board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107868448A CN107868448A (en) | 2018-04-03 |
| CN107868448B true CN107868448B (en) | 2020-12-01 |
Family
ID=61753341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711014561.7A Active CN107868448B (en) | 2017-10-26 | 2017-10-26 | Continuous fiber reinforced long carbon chain nylon composite board |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107868448B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705572A (en) * | 2018-12-29 | 2019-05-03 | 山东新升实业发展有限责任公司 | A kind of long carbon chain nylon wrist strap and preparation method thereof and purposes |
| CN110792460B (en) * | 2019-10-31 | 2021-11-30 | 神华神东煤炭集团有限责任公司 | Hydraulic support side protection plate and preparation method thereof |
| CN111572059B (en) * | 2020-05-13 | 2021-07-06 | 株洲时代工程塑料科技有限责任公司 | Continuous glass fiber reinforced thermoplastic composite material and preparation method thereof |
| CN115260752A (en) * | 2021-04-30 | 2022-11-01 | 上海凯赛生物技术股份有限公司 | Polyamide 56 resin composition and continuous fiber-reinforced polyamide 56 composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001294674A (en) * | 2000-04-17 | 2001-10-23 | Unitica Fibers Ltd | Soft reinforced fiber sheet |
| CN103786277A (en) * | 2014-01-27 | 2014-05-14 | 上海日之升新技术发展有限公司 | Preparation method of continuous long carbon fiber reinforced nylon and equipment for preparing nylon |
| CN105086436A (en) * | 2015-09-14 | 2015-11-25 | 长沙五犇新材料科技有限公司 | Continuous glass fiber reinforced flame-retardant nylon composite board and production process thereof |
-
2017
- 2017-10-26 CN CN201711014561.7A patent/CN107868448B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001294674A (en) * | 2000-04-17 | 2001-10-23 | Unitica Fibers Ltd | Soft reinforced fiber sheet |
| CN103786277A (en) * | 2014-01-27 | 2014-05-14 | 上海日之升新技术发展有限公司 | Preparation method of continuous long carbon fiber reinforced nylon and equipment for preparing nylon |
| CN105086436A (en) * | 2015-09-14 | 2015-11-25 | 长沙五犇新材料科技有限公司 | Continuous glass fiber reinforced flame-retardant nylon composite board and production process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107868448A (en) | 2018-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107868448B (en) | Continuous fiber reinforced long carbon chain nylon composite board | |
| CN107840975B (en) | Preparation method of continuous fiber reinforced nylon composite material | |
| CN110239175B (en) | Light fiber reinforced polymer sandwich structure | |
| CN111572059B (en) | Continuous glass fiber reinforced thermoplastic composite material and preparation method thereof | |
| WO2016127521A1 (en) | Method for manufacturing composite product made of short-fibre reinforced thermosetting resin by means of 3d printing | |
| EP2430080B1 (en) | Overmolded polyamide composite structures and processes for their preparation | |
| WO2012058351A1 (en) | Overmolded polyamide composite structures and processes for their preparation | |
| AU2010259207A1 (en) | Method of delivering a thermoplastic and/or crosslinking resin to a composite laminate structure | |
| CN102615839A (en) | Continuous fiber reinforced thermoplastic prepreg tape braided fabric and continuous fiber reinforced thermoplastic prepreg tape plate preparation method | |
| CN111171557A (en) | Continuous fiber reinforced polyamide composite material and preparation method and application thereof | |
| JP6816382B2 (en) | Press molding material | |
| DE112016004611T5 (en) | Overmolded carbon fiber structures with adjusted void content and uses thereof | |
| KR20170110915A (en) | Long fiber reinforced polyamide pellet, polyamide resin composition including the same and molded article thereof | |
| Köhler et al. | An overview of impregnation methods for carbon fibre reinforced thermoplastics | |
| CN102990999A (en) | Large tow carbon fiber composite with improved flexural property and surface property | |
| US20110244250A1 (en) | Composite materials and method of making | |
| CN113232384A (en) | Continuous long fiber reinforced thermoplastic composite board and preparation method and application thereof | |
| CN102924907B (en) | Continuous glass fiber/nylon composite,preparation method and application thereof | |
| CN115674797A (en) | Bio-based polyamide composite board and preparation method and application thereof | |
| DE112015005737T5 (en) | Shaping materials with improved surface quality | |
| CN108440955A (en) | Continuous lod fire-retardant nylon composite material and preparation method and application | |
| CN109808201A (en) | Forming method is prepared with the fibre-reinforced wearing composite material of nanometer gradient | |
| CN115304800A (en) | High-flame-retardancy continuous fiber reinforced nylon 6 composite material and preparation method thereof | |
| CN110272587A (en) | A kind of cold-resistant High-temperature-resflamet flamet retardant composite material and preparation method thereof | |
| CN110804297B (en) | Basalt fiber mesh cloth reinforced composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A kind of continuous fiber reinforced long carbon chain nylon composite board Effective date of registration: 20210526 Granted publication date: 20201201 Pledgee: Bank of Changsha Limited by Share Ltd. Liuyang branch Pledgor: CHANGSHA WUBEN NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2021430000014 |