CN110281603B

CN110281603B - Composite laminate with honeycomb core and method of making same

Info

Publication number: CN110281603B
Application number: CN201810216712.5A
Authority: CN
Inventors: 贾志刚; 金磊; 宋涛
Original assignee: DuPont Safety and Construction Inc
Current assignee: DuPont Safety and Construction Inc
Priority date: 2018-03-15
Filing date: 2018-03-15
Publication date: 2021-10-08
Anticipated expiration: 2038-03-15
Also published as: CN110281603A

Abstract

The present invention relates to a composite laminate panel having a honeycomb core material. The composite laminate comprises a preform and two skin layers covering the outer surface of the preform, wherein the preform comprises a honeycomb core, an adhesive film and a barrier film which are sequentially arranged on the outer surface of the honeycomb core, and a plurality of tubular rivets which are inserted through the preform. The invention also relates to a method of making the composite laminate by a Vacuum Assisted Resin Infusion (VARI) process.

Description

Composite laminate with honeycomb core and method of making same

Technical Field

The present invention relates to composite laminates having a honeycomb core and methods of making the same, particularly by a liquid forming process.

Background

Honeycomb core composite panels have been widely used in various applications due to their light weight, high strength, high stiffness characteristics, but are most mainly used in the aerospace industry and in mass transportation vehicles, such as parts of floors, secondary structural members, roofs, wall panels, luggage racks, etc. of airplanes and parts of floors, skirtings, compartment roofs, luggage racks, partition walls, etc. of trains. Such honeycomb core composite panels must typically be prepared by using prepregs containing adhesives, such as epoxy prepregs and phenolic prepregs, as the upper and lower skins, and then by conventional autoclave molding methods. Therefore, the prepreg uniformity of the prepreg and the flowability of the prepreg resin are correspondingly highly required, and the processing cost and the energy consumption are increased, and are also increased due to the limitation of the size of the die.

On the other hand, the liquid forming process adopts a closed die or a semi-closed die, takes non-prepreg as upper and lower skins, only needs a small amount of auxiliary materials, has low cost, and can ensure that liquid resin before forming can flow fully, at least one surface of the prepared product is smooth and uniform, and is not limited by the size of the die. Thus, the preparation of honeycomb core composite panels by a liquid forming process is clearly advantageous over the aforementioned autoclave forming methods. The most significant advantage of the liquid forming process in the aerospace industry is its ability to produce complex shapes, i.e., combining multiple detailed parts into one structure.

The key point of the problem is that the core material structure of the honeycomb core composite board is provided with open holes, and in order to avoid unnecessary weight increase caused by liquid resin flowing into the holes, isolation adhesive films are usually adopted to seal two surfaces of the core material. For example, EP0722825a1 discloses a Resin Transfer Molding (Resin Transfer Molding) process for preparing a corresponding honeycomb core composite board from a combination of a glue film, a prepreg and a dry fabric. However, the challenge of using dry fabrics as the upper and lower skins without using prepregs is that the liquid resin injected from one side does not quickly and uniformly wet the skins on the opposite side, so that the part has uneven resin and starved. One solution is to lay a resin flow-guiding net at least on the side opposite to the glue inlet side, but by this means it is not possible to obtain a product having at least one smooth and uniform surface. However, typical components in the aerospace industry are characterized by having aerodynamic (aerodynamic), decorative, and controlled fit surfaces (controlled fit-up surfaces). The surface properties of honeycomb core composite panels used for such components also have high quality requirements.

Disclosure of Invention

The invention provides a composite laminate with a honeycomb core, which sequentially comprises:

(a) a first skin layer;

(b) a first barrier film;

(c) a first adhesive film;

(d) a honeycomb core;

(e) a second adhesive film;

(f) a second barrier film;

(g) a second skin layer;

(h) a plurality of tubular rivets;

(i) the self-expanding sealant is coated around the tubular rivet; and

(j) a matrix derived from a liquid binder;

wherein the content of the first and second substances,

the liquid binder is selected from the group consisting of phenolic resins, epoxy resins, unsaturated polyester resins, vinyl ester resins, and combinations thereof; and has a viscosity of from 100cp to 500cp at 25 ℃;

said layers (b), (c), (d), (e) and (f) being stacked in sequence to form a preform; and

the tubular rivets are inserted through the preform and are spaced apart from each other by a distance of 30mm to 200 mm.

The present invention also provides a method of manufacturing the composite laminate, comprising:

i) sequentially stacking (b) a first separator film, (c) a first adhesive film, (d) a honeycomb core, (e) a second adhesive film, and (f) a second separator film to form a preform;

ii) inserting a plurality of tubular rivets through the preform and spaced from each other by a distance of 30mm to 200 mm;

iii) coating the periphery of each tubular rivet with a self-expanding sealant;

iv) covering the outer surface of the preform obtained in step (iii) with a first and a second skin layer, respectively; and

v) curing the preform covered with the first and second skin layers obtained in step (iv) by a Vacuum Assisted Resin Infusion (VARI) method.

The invention further provides an article or component in a vehicle or a movable temporary dwelling comprising the composite laminate of the invention, wherein the vehicle comprises an automobile, a ship, a train, a maglev, a drone or an airplane, and the movable temporary dwelling comprises a shelter or a movable dwelling.

The invention further provides the use of the composite laminate of the invention in the manufacture of an article or part in a transportation vehicle or a movable temporary dwelling, wherein the transportation vehicle comprises an automobile, a ship, a train, a maglev, a drone or an aircraft, and the movable temporary dwelling comprises a shelter or a movable dwelling.

Various other features, aspects, and advantages of the present invention will become more apparent with reference to the following description, examples, and appended claims.

Drawings

FIG. 1 shows a schematic vertical cross-section of a composite laminate of the present invention comprising upper and lower layers of a honeycomb core and showing a tubular rivet and a self-expanding sealant wrapped therearound.

Figure 2 shows a schematic view of a tubular rivet used in the composite laminate of the present invention.

FIG. 3 shows a schematic representation of a tubular rivet insertion position used in some embodiments of the invention.

Detailed Description

Unless otherwise indicated, all publications, patent applications, patents, and other references mentioned herein are expressly incorporated by reference in their entirety for all purposes as if fully set forth.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the case of conflict, the present specification, including definitions, will control.

Trademarks are shown in capital letters, except where explicitly indicated.

All percentages, parts, ratios, etc., are by weight unless otherwise indicated.

The term "made from …" is used herein synonymously with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The phrase "consisting of …" does not include any unspecified elements, steps or components. If in the claims, such phrase is intended to mean that the claims do not include materials other than those listed, but include impurities normally associated therewith. When the phrase "consisting of …" appears in the clause of the main body of the claims, rather than following the preamble, it limits only the elements listed in the clause; other elements as a whole are not excluded from the claims.

The phrase "consisting essentially of …" is used to define a composition, method, or apparatus that includes other materials, steps, features, components, or elements in addition to those literally set forth, provided that such other materials, steps, features, components, or elements do not materially affect the basic and novel characteristics of the claimed invention. The term "consisting essentially of …" covers a range between "comprising" and "consisting of …".

The term "comprising" is intended to include embodiments encompassed by the terms "consisting essentially of … …" and "consisting of … …". Similarly, the term "consisting essentially of … …" is intended to include embodiments encompassed by the term "consisting of … …".

When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of values, including any upper range limit or higher preferable value and any lower range limit or lower preferable value, regardless of whether ranges are separately disclosed. For example, when reciting a range of values of "1 to 5," the range of values should be understood to include the ranges of values of "1 to 4," "1 to 3," "1-2 &4-5," "1-3 &5," and the like. Where a range of values is stated herein, unless otherwise stated, the range of values is intended to include the endpoints thereof, and all integers and fractions within the range of values.

When the term "about" is used to describe a value or range of values, this disclosure should be understood to include the specific value or value recited.

Furthermore, unless expressly stated to the contrary, "or" means "or" including "and" not "excluding. For example, any one of the following satisfies condition a "or" B: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), and both a and B are true (or present).

Furthermore, "a" and "an" preceding an element or component of the invention are intended to be non-limiting with respect to the number of instances (i.e., occurrences) of the element or component. Thus, "a" or "an" should be understood to include one or at least one and the singular forms of stated elements or components also include the plural unless the number is obviously singular.

"mol%" or "mol%" refers to mole percent.

In the present description and/or claims, the term "homopolymer" means a polymer obtained by polymerization of a monomer; "copolymer" refers to a polymer resulting from the polymerization of two or more monomers. Such copolymers include copolymers, terpolymers or multipolymers.

As used herein, the terms of various polymers such as "polyamide", "polyester", "polyurethane" and the like include not only polymers containing repeat units derived from monomers known to polymerize to form polymers of the type in question, but also other copolymerizable comonomers which may be up to 25 mole%, derivatives thereof and the like. In addition, the aforementioned polymers also include mixtures, blends, etc. of these polymers with different types of other polymers.

In describing certain polymers, it is understood that applicants sometimes refer to a polymer by the number of monomers used to prepare the polymer or monomers used to prepare the polymer. While such description may not include the specific nomenclature used to describe the final polymer, or may not include the definition of "the product made by the … process," any such recitation of monomers and amounts should be interpreted to mean that the polymer includes those monomers (e.g., the copolymerized units of those monomers) or that amount of such monomers, as well as their corresponding polymers and compositions.

In this context, the term "fiber" refers to a relatively flexible, elongate body having a ratio of its length to its width in cross-section perpendicular to the length of at least greater than 10. The fiber cross-section may be any shape such as circular, flat or oval, but is typically circular. The fiber cross-section may be solid or hollow, preferably solid. A single fiber may be formed from only one filament (filament) or from multiple filaments. Fibers formed from only one filament are referred to herein as "single filament" fibers or "monofilament" fibers, and fibers formed from multiple filaments are referred to herein as "multifilament" fibers. As used herein, the term "yarn" (yarn) refers to a single strand of yarn composed of a plurality of fibers, which may be untwisted (i.e., flat yarn) or twisted. The term "yarn" is used interchangeably with the term "fiber".

The thickness of the fiber is generally characterized by a linear density called "denier" or "dtex"; "denier" is the weight in grams of 9000 meters of fiber and "dtex" is the weight in grams of 10000 meters of fiber.

As used herein, "layer" describes a generally planar arrangement of skins, insulation films, cling films, or reinforcing fabrics. As used herein, "first certain layer/film", "second certain layer/film" generally merely indicates the order in which the layers or films are laid in forming the laminate structure and does not represent the relationship of the layers or films in or out of the final application of the composite laminate.

As used herein, the terms "lamination" and "laminate" refer to the process and article made by bonding two or more films or other sheets together. The layers may be bonded by using an adhesive, heat, pressure, or other means.

The embodiments of the invention described in this summary section include any other embodiments described herein, all of which can be combined in any manner, and the descriptions of variables in the embodiments apply not only to the various sheets and films used with the composite laminates of the invention, but also to the composite laminates of the invention, and to the articles of the invention.

The materials, methods, and examples herein are illustrative only and, unless otherwise specified, should not be construed as limiting. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

The present invention is described in detail below.

Skin layer

In the present invention, the first skin layer (a) and the second skin layer (g) each independently comprise at least one layer of a reinforcing fabric comprising glass fibers, carbon fibers, aramid fibers, or a combination thereof.

The glass fiber is an inorganic non-metallic fiber with excellent performance, and has the advantages of good insulativity, strong heat resistance, good corrosion resistance and high mechanical strength, but has the defects of brittleness and poor wear resistance. In the present invention, the reinforcing fabric is preferably a glass fiber comprising C-glass (medium alkali glass) or E-glass (alkali-free glass).

The carbon fiber refers to inorganic polymer fiber with carbon content higher than 90%, and is called graphite fiber when the carbon content is higher than 99%. Carbon fibers have the advantages of high warp strength and modulus, no creep, good fatigue resistance, small coefficient of thermal expansion, and good corrosion resistance, but have the disadvantage of poor impact resistance.

Aramid fibers (abbreviated as "aramid") have heat resistance, chemical resistance and flame retardancy. In the present invention, the aramid fibers comprise fibers produced from poly (p-phenylene terephthalamide) homopolymers, poly (p-phenylene terephthalamide) copolymers, poly (m-phenylene isophthalamide) homopolymers, poly (m-phenylene isophthalamide) copolymers, polysulfone amide homopolymers, polysulfone amide copolymers, and mixtures thereof.

Herein, the term "para-aramid" refers to poly (p-phenylene terephthalamide) homopolymer and poly (p-phenylene terephthalamide) copolymer; the term "meta-aramid" refers to poly (m-phenylene isophthalamide) homopolymers and poly (m-phenylene isophthalamide) copolymers.

Commercially available glass fibers such as, but not limited to, 468 alkali-free glass fibers produced by CPIC; commercially available carbon fibers such as, but not limited to, T700 produced by Toray; commercially available aramid fibers are available, for example, but not limited to, under the trade name DuPont

Para-aramid of the series, and having the trade name

A series of meta-aramid fibers.

It is known that the characteristics of the reinforcing fabric are not only determined by the fiber properties, yarn structure, but also the fabric structure and the thread count are important factors. In the present invention, the structure suitable for the reinforcing fabric may be a woven fabric, a unidirectional fabric or a non-woven fabric; preferably a woven or nonwoven fabric.

Woven fabrics generally refer to fabrics in which continuous filaments are woven in any pattern known to those skilled in the art, with a substantial number of continuous filaments in both the warp and weft directions, and the weave of such fibers is generally more stable than unidirectional fabrics. The woven fabric may take any woven configuration or pattern, such as, but not limited to, plain weave, twill weave, satin weave, rib weave (leno), or basket weave (square), among others.

By unidirectional fabric is meant that more than 80% of the continuous filaments are aligned parallel along the length (or warp direction) and no or less than 20% in the other direction (or weft direction) and are typically warp knitted with spun yarns. There are various methods of weaving unidirectional fabrics, and common methods include woven unidirectional fabrics, laid unidirectional fabrics, and stitch-bonded unidirectional fabrics.

The non-woven fabric is a fabric without warp and weft, does not need to be woven by spinning, and has the advantages of light weight and easy shaping. The manufacturing process usually comprises the steps of forming a web structure by directionally or randomly arranging short fibers or filaments, and then reinforcing the web structure by mechanical, thermal bonding or chemical methods. Nonwoven products according to the production process can be classified into spunlaced nonwoven fabrics, heat-sealed nonwoven fabrics, air-laid nonwoven fabrics, wet-laid nonwoven fabrics, spunbonded nonwoven fabrics, meltblown nonwoven fabrics, needle-punched nonwoven fabrics, stitch-bonded nonwoven fabrics, and the like.

As used herein, the term "prepreg" refers to a fabric impregnated with a thermosetting or thermoplastic resin, an intermediate material commonly used in the preparation of composite materials. In the case of the composite materials required by the current aviation and aviation, the prepreg has high precision requirements on resin content, impregnation uniformity, viscosity and paving performance, so that the cost for manufacturing the composite materials is increased.

In the present invention, the first skin layer (a) and the second skin layer (g) are not prepregs; i.e. a dry fabric without resin. Because the composite laminate having the honeycomb core is manufactured through a liquid molding process, and the method has solved the problem of uneven impregnation, the material cost of the prepreg as the upper and lower skin layers is saved.

The reinforcing fabrics used as the first and second skin layers (a) and (g) each independently have about 20g/m²To about 660g/m²And the reinforcing fabric is a woven, unidirectional or non-woven fabric.

Isolation film

As described in the background of the invention, one of the problems to be solved in manufacturing a composite panel including a honeycomb core using a liquid molding process is to prevent a liquid adhesive from penetrating into cells of the honeycomb core. In the present invention, the addition of a barrier film between the skin layer and the honeycomb core is used to address this problem. One skilled in the art can select a suitable polymeric material for the release film depending on the liquid adhesive used.

In the present invention, the first and second separation films (b, f) each independently comprise ethylene- (meth) acrylate (EA or EMA), anhydride-modified ethylene- (meth) acrylate (anhydride-modified EA or EMA), ethylene-vinyl acetate (EVA), anhydride-modified ethylene-vinyl acetate (anhydride-modified EVA), ethylene-acid ionomer (ethylene-acid oligomer), polyamide, polyurethane, polyester, polyimide, or a combination thereof.

In some embodiments, the first release film (b) and the second release film (f) are the same and comprise ethylene- (meth) acrylate, anhydride-modified ethylene- (meth) acrylate, ethylene-vinyl acetate, anhydride-modified ethylene-vinyl acetate, ethylene-acid ionomer, or a combination thereof.

In other embodiments, the first release film (b) and the second release film (f) each independently comprise an anhydride-modified ethylene- (meth) acrylate, an anhydride-modified ethylene vinyl acetate, an ethylene acid ionomer, or a combination thereof.

As used herein, the term "(meth) acrylate" is intended to mean an alkyl acrylate or methacrylate.

The ethylene- (meth) acrylate is a copolymer comprising polymerized units of ethylene and from about 6 to about 40 weight percent of polymerized units of at least one alkyl (meth) acrylate. The alkyl portion of the alkyl (meth) acrylate may contain 1 to 6 or 1 to 4 carbon atoms, for example, methyl, ethyl, and branched or unbranched propyl, butyl, pentyl, and hexyl groups. Preferred alkyl groups include methyl, ethyl and butyl groups, and combinations of two or more of these groups are also preferred. Preferred ethylene- (meth) acrylate copolymers include ethylene ethyl (meth) acrylate and ethylene methyl (meth) acrylate.

Ethylene Vinyl Acetate (EVA) is a copolymer of ethylene and vinyl acetate, with the vinyl acetate content typically being between 5 and 45 wt%, the remainder being ethylene. The properties of EVA are related to its vinyl acetate content, molecular weight, and melt index. When the content of vinyl acetate is increased at a constant melt index, the elasticity, flexibility, compatibility, transparency, etc. are also increased. When the vinyl acetate content is reduced, the performance of the material is close to that of polyethylene, the rigidity is increased, and the wear resistance and the electrical insulation are improved. When the content of the vinyl acetate is constant, the molecular weight of the EVA is increased along with the reduction of the melt index, and the impact property and the environmental stress cracking resistance of the EVA are correspondingly improved.

Herein, the term "anhydride-modified polymer" and more specific terms such as "anhydride-modified ethylene-vinyl acetate", "and" anhydride-modified ethylene- (meth) acrylate "are intended to mean that an anhydride of Maleic Anhydride (MAH), fumaric acid, or the like is added to the polymer by copolymerization, grafting, or blending. Preferably, such modified polymers have anhydride functionality grafted onto or polymerized with them, not merely blended with them. Typically, the anhydride will be present in an amount of from about 1 to about 20 weight percent, based on the total weight of the copolymer.

The anhydride-modified ethylene- (meth) acrylates are commercially available, such as, but not limited to, those produced by DuPont

2100 series; an example of the acid anhydride-modified ethylene-vinyl acetate is manufactured by DuPont

3800 series.

As used herein, the term "ionomer" refers to the product of ionic polymerization, i.e., a polymer containing interchain ionic bonds. The ionomer comprises at least one thermoplastic resin selected from metal salts based on olefin/acid copolymers; metal salts based on ethylene-acid copolymers and ethylene- (meth) acrylic acid copolymers are preferred. As used herein, the term "ionomer" also includes ethylene- (meth) acrylic acid copolymers and ethylene-acid-acrylate terpolymers. The metal salt is derived from a neutralizing agent (e.g., an inorganic base) that serves to at least partially neutralize the carboxylic acid groups of the copolymer. After neutralization, the ionomer may generally contain any feasible monovalent or divalent cation, including lithium, sodium, potassium, magnesium, calcium, barium, copper, zinc, or ammonium ions.

The ethylene-acid ionomers are commercially available, such as, but not limited to, those produced by DuPont corporation

A series of ionomers.

With respect to the aramid, see the foregoing, the film prepared therefrom has excellent pressure tightness, thermal stability, and chemical stability. Commercially available aramid films such as, but not limited to, Mictron manufactured by Toray corporation^TMThe para-aramid film is high in rigidity, heat resistance and barrier property.

Polyurethane (PU) refers to a polymer that contains urethane features in the backbone. Polyurethanes are classified into polyester polyurethanes and polyether polyurethanes. The polyester polyurethane is prepared by taking diisocyanate and polyester as raw materials. The polyether polyurethane is prepared from diisocyanate and polyether. The most commonly used diisocyanates are aromatic diisocyanates, Toluene Diisocyanate (TDI) and methylene diphenyl diisocyanate (MDI). Commercially available polyurethane films, such as but not limited to those produced by BASF

S85 series, which is a polyether polyurethane (polyether polyurethane).

Polyesters are a class of thermoplastic polymers containing ester functional groups in their main chain, which have a number of excellent properties, such as: high dimensional stability, high insulation, chemical resistance, heat resistance, thermal aging resistance, abrasion resistance, and the like, and the production cost thereof is also lower than that of polyamide, polycarbonate, and the like. Commercially available polyester films, such as but not limited to Teflex from Imperial corporation^TMWhich is a polyethylene terephthalate (PET) film.

Polyimide (Polyimide) is a polymer with imide repeating units and has the advantages of wide application temperature, chemical corrosion resistance, high strength and the like. The polyimide is prepared by taking dianhydride and diamine as raw materials, carrying out condensation polymerization in an aprotic polar solvent such as dimethyl formamide dimethyl sulfoxide to generate polyamic acid, and then heating, curing and dehydrating to obtain the polyimide. Commonly used dianhydrides and diamines are pyromellitic dianhydride (PMDA) and 4,4' -diaminodiphenyl ether. Commercially available polyimide films, such as but not limited to those produced by DuPont

In the present invention, the first separator (b) and the second separator (f) each independently have about 20g/m²To about 100g/m²And a thickness of about 20 μm to about 100 μm.

Adhesive film

In the present invention, the adhesive film functions to ensure that the separator film can closely conform to and seal the open cells of the honeycomb core. The adhesive is preferably in the form of a film, and is characterized by excellent adhesion and durability, easy handling, and uniform application amount. Suitable adhesive films include those that have been widely used in the fields of aerospace, high-speed trains, ships, and the like for honeycomb sandwich structures, including epoxy-based adhesive films; an adhesive film based on an acrylate resin or an adhesive film based on a urethane resin.

In some embodiments, the first adhesive film (c) and the second adhesive film (e) each independently comprise an epoxy resin, an acrylate resin, or a polyurethane resin.

In other embodiments, the first adhesive film (c) and the second adhesive film (e) are the same and are composed of a resin selected from the group consisting of epoxy resins, acrylate resins, and urethane resins.

In still other embodiments, the first adhesive film (c) and the second adhesive film (e) are composed of an epoxy resin.

The first adhesive film (c) and the second adhesive film (e) each independently comprise an epoxy resin, an acrylate resin, or a polyurethane resin; and its glass transition temperature (T)_g) From about 60 ℃ to about 160 ℃.

The first adhesive film (c) and the second adhesive film (e) each independently have about 100g/m²To about 300g/m²And a thickness of 100 to 300 μm.

Examples of commercially available adhesive films include, but are not limited to, epoxy adhesive film J69B, T available from Heilongjiang petrochemical institute_gIs about 100 ℃; acrylate adhesive film MS768, T produced by 3M_gAbout 80 ℃; and produced by BASF

Polyurethane adhesive film S85, T_gIs about 80 deg.c.

Honeycomb core

In the present invention, the honeycomb core is a plate having a honeycomb structure, which is composed of a sheet including aramid, polycarbonate, polypropylene, steel, aluminum alloy, or glass fiber. These boards with a honeycomb structure are referred to herein simply as honeycomb boards, such as aramid honeycomb boards, glass fiber honeycomb boards, aluminum honeycomb boards, and the like.

The cell walls of the honeycomb plate can be made of non-metal sheets or metal foils; wherein the non-metal honeycomb plate is made of sheets of aramid, polycarbonate, polypropylene, glass fiber or the like; the metal honeycomb plate is made of metal foils of steel, aluminum alloy and the like. The flakes of non-metallic material described herein, sometimes also referred to as "paper" for their manner of manufacture and appearance, can be made using conventional processes and equipment, such as, but not limited to, meta-aramid paper, para-aramid paper. In addition, the process of making honeycomb panels is also well known to those skilled in the art.

The honeycomb board as the honeycomb core is preferably composed of sheets of meta-aramid paper, para-aramid paper, aluminum foil, aluminum alloy foil, and glass fiber; more preferably, the honeycomb panel is composed of meta-aramid paper and para-aramid paper.

The cross-sectional shape of each cell of the honeycomb panel may be hexagonal, over-stretched (hexagonal), circular, or corrugated. The thickness of the honeycomb used in the honeycomb core (d) of the present invention depends on the end use or desired properties of the composite laminate. When the density of the honeycomb panel is constant, the weight of the honeycomb panel increases with the thickness. The honeycomb panel has a thickness of about 2mm to about 300mm, a cell size of about 1.6mm to about 20.0mm, a cell wall thickness of about 0.1mm to about 0.3mm, and a density of about 24Kg/m³To about 200Kg/m³。

Examples of commercially available honeycomb panels include, but are not limited to, aramid honeycomb panels such as those produced by Hexcel

HRH-78

And HRH-49

A series of cellular boards. Commercially available honeycomb panels of other materials such as, but not limited to, PC honeycomb panels and polypropylene honeycomb panels (e.g., PP8-80) manufactured by Qingdao Bobo panels, Inc.; manufactured by Hertz under the trade name

An aluminum alloy honeycomb panel of, and

HRP series glass fiber honeycomb plate.

Tubular rivet

In the invention, the two skin layers (a) and (g) of the composite laminated plate are composed of dry fabric instead of prepreg, and in order to solve the problem that the skin layers on the opposite sides of the composite laminated plate can be quickly and uniformly soaked by liquid resin injected from one side, the invention provides a solution that a plurality of tubular rivets are inserted between the two skin layers to be used as a flow guide pipe. In other words, in the composite laminate of the present invention, the layers other than the two skin layers, i.e., the layers (b), (c), (d), (e), and (f), are sequentially stacked to form a preform. A plurality of tubular rivets having a suitable inner diameter and length for the hollow tube are then inserted through the preform. The distance of the tubular rivets from each other can be adjusted according to the viscosity of the liquid adhesive used, typically the distance is between about 30mm and about 200mm, preferably the tubular rivets are equidistantly spaced from each other. The number of tubular rivets is not excessive in order not to excessively increase the overall weight of the composite laminate. At the same time, the length of the tubular rivet is a length substantially equal to the thickness of the preform, in order not to affect the appearance of the composite laminate. In other words, when the two skin layers are impregnated as opaque materials, the tubular rivets are hidden from the appearance of the composite laminate, not unlike the appearance of a laminate article using prepreg as the skin layer.

In this context, the term "substantially equal" is intended to mean that the difference between the value and the reference value is no more than 10% of the value, or no more than 5% of the value, or no more than 3% of the value, or no more than 1% of the value, based on the reference value. For example, when the preform has a thickness of 10mm, the length of the tubular rivet may be between 9mm and 11 mm. It will be appreciated by those skilled in the art that as the length of the tubular rivet is increased, it will differ from the thickness of the preform by a lesser proportion. Generally, the tubular rivet will have a length greater than 20mm which differs from the thickness of the preform by at most 2mm, preferably by no more than 1mm, more preferably by no more than 0.5 mm.

A tubular rivet (see fig. 2) suitable for use in the present invention is a flat head having a diameter (D1) of about 1.6mm to about 20.0mm, a head thickness (L1) of about 0.1mm to about 1.0mm (L1), a hollow tube having an inner diameter (D2) of about 1.2mm to about 19.6mm, a tube wall thickness (D3) of about 0.2mm to about 0.9mm, and a length (L2) substantially equal to the preform thickness. The tubular rivet is constructed of a metallic material comprising copper, nickel, aluminum, titanium, alloys thereof, or stainless steel, and a non-metallic material comprising polyamide or polyester. One skilled in the art can select a tubular rivet having a suitable outer diameter depending on the cell size of the honeycomb core. Commercially available tubular rivets such as, but not limited to, blind rivets manufactured by the manufacturers of the Tankwy hardware tools company.

Self-expanding sealant

In the invention, in order to fix the tubular rivet and fill the gap between the tubular rivet and the prefabricated member, especially the gap between the tubular rivet and the cell of the honeycomb core, self-expanding sealant is adopted for filling and sealing. For ease of application, a sealant having good adhesion, room temperature curing, and no solvent is preferably used. The self-expanding sealant comprises expandable polystyrene or expandable polyurethane.

Examples of commercially available sealants include, but are not limited to, for example, polystyrene foam (CA-197) manufactured by Cemedine, Japan, and polyurethane foam sealants manufactured by Sanyo (SANO), USA.

Liquid adhesive

Vacuum Assisted Resin Infusion (VARI) is a molding process in which the fibers of a fabric are vacuumed to remove air bubbles, a liquid binder is introduced to permeate the fibers and fabric, and the curing takes place. Liquid adhesives suitable for VARI must first have a relatively low viscosity, preferably a viscosity of 100cp to 500cp at 25 ℃, optionally with a hardener. The liquid adhesive most preferably has a suitable gel time, typically from about 5 minutes to about 150 minutes at a temperature of 25 ℃. As used herein, the term "gel time" refers to the time required for a liquid adhesive to transition from a flowable liquid state to a solid gel. Depending on the time required for suction and injection, one skilled in the art may choose a liquid adhesive with a suitable gel time.

In addition, the liquid adhesive, when cured, becomes the matrix in the skin layer and therefore also has good heat resistance, flame retardancy, chemical resistance, and also meets the mechanical performance requirements of the article or part depending on the particular application.

In the present invention, the liquid binder is selected from the group consisting of phenolic resins, epoxy resins, unsaturated polyester resins, vinyl ester resins, and combinations thereof.

In some embodiments of the invention, the liquid binder is selected from the group consisting of phenolic resins, epoxy resins, unsaturated polyester resins, vinyl ester resins, and combinations thereof.

In other embodiments of the present invention, the liquid binder is selected from the group consisting of phenolic resins, epoxy resins, and combinations thereof.

The liquid binder is used in an amount of about 40 to about 150 wt%, preferably about 60 to about 100 wt%, based on the total weight of the dry fabric as the first and second skin layers (a) and (g).

Examples of such commercially available liquid binders include, but are not limited to, phenolic resins (viscosity of 150cp to 250cp) manufactured by the jen seoul group, model PF 7203-1; amiable Kesons corporation (Axson), model EPOLAM2040 epoxy resin (viscosity 150cp to 300cp after mixing hardener); type HS-2102 unsaturated polyester resins (viscosity of 170 to 200cp) and type HS-4430RT epoxy modified vinyl ester resins (viscosity of 100 to 150cp) manufactured by Hezhou Huake polymers.

Preparation of composite laminates

As shown in fig. 1, the layered structure of the composite laminate 100 of the present invention comprises, in order: (a) a first skin layer 11a, (b) a first separator film 12a, (c) a first adhesive film 13a, (d) a honeycomb core 14, (e) a second adhesive film 13b, (f) a second separator film 12b, (g) a second skin layer 11b, and (h) a plurality of tubular rivets 15 inserted through the preform including the (b) layer(s) and (f) layer(s), and (i) a self-expanding sealant 16 wrapped around the tubular rivets.

In this context, it is the "/" separating each different layer from its adjacent layers to describe the structure of the composite laminate. The composite laminate of the present invention can have a laminate structure represented by [ (a)/(b)/(c)/(d)/(e)/(f)/(g) ]. When the fabric as the first skin layer (a) is not a single piece of fabric, for example, two pieces of fabric (a1), it is represented by [ (a1) x2/(b)/(c)/(d)/(e)/(f)/(g) ]; when the fabric as the first skin layer (a) is a combination of different fabrics (a1) and (a2), it is represented by [ (a1) (a2)/(b)/(c)/(d)/(e)/(f)/(g) ].

iii) coating the periphery of each tubular rivet with a self-expanding sealant;

iv) covering the outer surface of the preform obtained in step (iii) with a first skin layer (a) and a second skin layer (g), respectively; and

iv) curing the preform covered with the first and second skin layers obtained in step (iv) by a Vacuum Assisted Resin Infusion (VARI) process.

The detailed steps of curing according to the VARI method may include:

A. vacuumizing: applying vacuum (i.e., negative pressure) to the mold containing the [ first skin layer/preform/second skin layer ] to remove air from the reinforcement fabric as a skin layer; and

B. adhesive injection (adhesive infusion): introducing the liquid binder under vacuum;

C. and (5) curing.

The VARI process parameters suitable for use in preparing the composite laminates of the present invention, such as pressure, curing temperature and time, generally depend on the materials and thicknesses of the liquid adhesive and release film, bonding film, honeycomb core and skin layers. Meanwhile, the inner diameter, the number and the spacing of the hollow pipes of the tubular rivets also influence the time for glue absorption and injection. For example, when the thickness of the preform is constant, the pitch of the same size tubular rivet is increased, and the time for sucking and injecting the glue is naturally correspondingly prolonged. Those skilled in the art may determine appropriate process parameters accordingly.

In the method of the present invention, the curing is carried out at a pressure of from about-0.08 MPa to about-0.10 MPa and a temperature of from about 25 ℃ to about 120 ℃ for from about 1 hour to about 24 hours; for example, the curing time is typically about 24 hours at 25 ℃.

In some embodiments, curing is performed at a temperature of from about 25 ℃ to about 120 ℃, or from about 40 ℃ to about 110 ℃, or from about 60 ℃ to about 90 ℃; and for about 1 hour to about 24 hours, or about 2 hours to about 8 hours.

As described in the background of the invention, the first step in the manufacture of composite laminates comprising honeycomb cores using a liquid forming process is to address the problem of excluding liquid adhesive from the cells of the honeycomb material, which has been addressed by the use of release and bonding films. In addition, the problem of ensuring that two non-prepreg skin layers can be uniformly soaked under the condition of not laying a resin flow guide net is solved, and the manufactured part has at least one smooth and uniform surface. The gloss of the article can be measured according to the method of ASTM D2457. The honeycomb core is formed by inserting a plurality of tubular rivets into the honeycomb core, so that the problems are solved, and the liquid adhesive is further prevented from penetrating into the spaces of the honeycomb core by coating the tubular rivets with the self-expanding sealant. In addition, because the inserted plurality of tubular rivets are covered by two skin layers, when the first and second skin layers are impregnated with an opaque reinforcing fabric, the resulting composite laminate is not visually different from a comparative laminate using a prepreg as the skin layer.

In view of cost and ease of manufacture, in the present invention, the reinforcing fabrics of the first and second skin layers are preferably the same, the first and second release films are also the same, and the first and second adhesive films are also the same.

In one embodiment of the present invention, the composite laminate has a laminated structure of [ (a)/(b)/(c)/(d)/(c)/(b)/(a) ], that is, a honeycomb core and a sandwich panel having a symmetrical structure.

In the present invention, the above-mentionedThe composite laminate produced by the process generally has a total thickness of about 5mm to about 300mm and an areal density of 0.35Kg/m²To 20Kg/m². The total thickness and face density of the composite laminate of the present invention can be easily adjusted by using honeycomb cores of different thicknesses and densities and reinforcing fabrics for the first and second skin layers.

An article or part comprising, consisting essentially of, consisting of, or consisting of a composite laminate of the present invention, an article or part consisting of a composite laminate of the present invention, or an article or part made by a method of making a composite laminate of the present invention, not only greatly reduces material, equipment and manufacturing costs due to its manufacture by a liquid forming process with tubular rivets as the flow conduit and the non-prepreg skin layer, but the article also maintains structural and appearance integrity and has at least one surface that is smooth and uniform, so long as the mold used in the manufacturing process is flat and smooth on one side.

The composite laminates of the present invention may be used to prepare articles or parts in transportation vehicles or mobile temporary housing (mobile temporary housing), such as, but not limited to: articles or parts for use in the preparation of vehicles including automobiles, ships, trains, maglevs, drones, or airplanes; and movable temporary dwellings, including shelter or components in mobile homes. The article or component includes, but is not limited to, a floor, a skirt, a roof, a wall panel, a roof rack, a deck panel, a partition wall, or other secondary structural member.

Examples

The abbreviation "E" stands for "examples" and "CE" stands for "comparative examples", the numbers following which indicate in which example the composite board sample was prepared. The examples and comparative examples were both prepared and tested in a similar manner. Percentages are by weight unless otherwise indicated.

Material

Dry fabric (a 1): the glass fiber fabric produced by New Material Ltd of Betulhec, Changzhou is biaxial fabric with 0-degree and 90-degree directionsKnitted fabric, i.e. a stitch-bonded unidirectional fabric, with an areal density of 658g/m²Water content<0.2% and the surface is silane sized.

Dry fabric (a 2): the para-aramid fabric produced by Jiangsu Tianqi high tech Co Ltd is a plain weave fabric with an areal density of 220g/m²Water content<3.5% and the surface is silane sized.

Prepreg (a'): purchased from Gurit, Inc., is a fiberglass fabric prepreg having an areal density of 520g/m²And contains 42% phenolic resin based on the total weight of the prepreg.

Prepreg (a "): purchased from Yixing Hua constant high-performance fiber weaving Co Ltd, is a para-aramid fabric prepreg with the surface density of 523g/m²And contains 42% of epoxy resin based on the total weight of the prepreg.

Separator (b 1): supplied by DuPont

3861A film which is the acid anhydride-modified EVA film, has a thickness of 50 μm and an area density of 49g/m²The melting point was 80 ℃ and the Vicat softening point was 56 ℃.

Adhesive film (c 1): purchased from Heilongjiang petrochemical industry, model J69B, is bisphenol A type epoxy adhesive film with a thickness of 250 μm and an areal density of 292g/m²And T_gIs 100 ℃.

Honeycomb panel (d 1): obtained from Jiangsu Jun source (Junyuan) with model JY1-4.8, and is prepared from

The meta-aramid honeycomb plate made of T722 paper has hexagonal cells, the size of the cells is 4.8mm, and the density of the honeycomb is 48Kg/m³The thickness is 10 mm.

Tubular rivet: the hollow copper rivet produced by Guwanji manufacturers has a flat head with a diameter of 5.9mm and a thickness of 0.5 mm; the inner diameter of the hollow pipe is 3.2mm, the outer diameter is 3.9mm, and the thickness of the pipe wall is 0.35 mm; the rivet length is 10 mm.

Self-expanding sealant: expandable polyurethane adhesives from SANO corporation, foam at 5 to 35 ℃, at a foam expansion of 80.

Liquid adhesive 1: phenol resin produced by the Jinan Shengquan group, with a resin model of PF7203-1 and a curing agent of PF7203-1A, at a mixing ratio of 100:7 (by weight), has a viscosity of about 150 to 250cp at 25 ℃.

Liquid adhesive 2: an epoxy resin manufactured by amiable croissant corporation, having a resin model of EPOLAM2040 and a curing agent of EPOLAM 2047, mixed in a ratio of 100:32 (by weight), and having a viscosity of about 290cp at 25 ℃.

Method for manufacturing composite laminates of examples 1-2 and comparative examples 1-2

Example 1

Two sheets of the separator (b1), two sheets of the adhesive film (c1), and one honeycomb panel (d1), which were cut into a square having a side length of 40cm, were sequentially stacked to form a preform having a structure of [ (b1)/(c1)/(d1)/(c1)/(b1) ]. Penetrating four hollow copper rivets (the inner diameter of a hollow tube is 4mm, and the length of the hollow tube is 10mm) through the prefabricated member; the location of each rivet was 100mm from the edge of the preform and 200mm apart from each other (see fig. 3A), and the peripheral gap of each rivet was sealed with an expandable polyurethane adhesive. A clean plate glass mold (size of 60cm square with thickness of 5mm) was coated with a release agent, and then a first dry glass fiber fabric (a1) (40cm x40cm) as a first skin layer, a preform into which a tubular rivet had been inserted, and a second dry glass fiber fabric (a1) as a second skin layer were sequentially placed. And continuously laying nylon 6 stripping cloth (the size is 50cm square and the thickness is 0.1mm) and a polypropylene stripping film (the size is 50cm square and the thickness is 0.1mm) and a polyester diversion net (the size is 50cm square and the thickness is 2.5mm) as a consumption layer on the second skin layer in sequence. Finally, the positions of the vacuum tube, the rubber inlet tube and the overflow tube are fixed, and two layers of nylon 6 vacuum bags (the size is 70cm square, the thickness is 0.05mm) are paved and sealed in a layered mode through adhesive tapes.

Applying a vacuum to the mold containing the preform to remove air from the fibers of the fabric in the dry state, the vacuum pressure being between-0.08 MPa and-0.1 MPa. About 300g of the liquid adhesive 1 (a phenol resin adhesive) was sucked and injected through the inlet hose, and the degree of impregnation of the skin layers on both sides was observed until excess liquid adhesive was discharged through the overflow pipe, and about 30 minutes passed. And putting the mould into a drying oven, and curing for 5 hours at a vacuum pressure of-0.08 MPa to-0.10 MPa and a temperature of 70 ℃. Then, the heating was stopped, the vacuum was turned off, and after the sample was cooled to room temperature, taken out of the oven, and the vacuum bag and the sacrificial layer were removed, a laminate, which is an embodiment of the composite laminate of the present invention, was obtained, and the side surface thereof, which was adhered to the flat glass mold, was smooth, and had a laminate structure of [ (a1)/(b1)/(c1)/(d1)/(c1)/(b1)/(a1) ]. The amount of matrix derived from the liquid adhesive 1, estimated by subtracting the weight of the raw materials of each layer from the weight of the laminate produced, was 67% of the total weight of the first and second skin layers (i.e., the total weight of the dry fabric), converted to equal about 40% of the matrix in the cured skin layers.

Example 2

The material and method were the same as in example 1 except that the dry fabrics used for the upper and lower skin layers were each three pieces of para-aramid fabric (a2) and that liquid adhesive 2 (epoxy adhesive) was used for the suction-injection. The laminate obtained had a laminate structure of [ (a2) x3/(b1)/(c1)/(d1)/(c1)/(b1)/(a2) x3], and the surface of one side was smooth. The amount of matrix derived from the liquid adhesive 2 is 67% of the total weight of the first and second skin layers, converted to equal about 40% of the matrix contained in the cured skin layers.

Comparative example 1

Six sheets of prepreg (a ') cut into a square of 40cm in side length, two sheets of adhesive film (c1), and one honeycomb panel (d1) of the same size were stacked in this order to form a preform having a structure of [ (a ') x3/(c1)/(d1)/(c1)/(a ') x3 ].

On a flat stainless steel mold (consisting of two 60cm x 3cm stainless steel plates), a first release paper was laid down, the preform was placed in the center of the mold, a second release paper (50cm x 50cm) was placed on the preform, and the mold was closed. The mold was then placed in a hot press (manufactured by Shanghai Metashui Co.) preheated to 120 deg.C, the press was closed, and hot pressed at 120 deg.C for 60 minutes with a pressure of 0.2 MPa. After hot pressing, removing the mold from the hot press; after the sample was cooled to room temperature, it was taken out to obtain a laminate of comparative example 1 having a structure of [ (a ') x3/(c1)/(d1)/(c 1)/(a') x3 ].

Comparative example 2

The honeycomb core was made of the same material and made in the same manner as in comparative example 1 except that the prepregs used as the upper and lower skin layers were three prepregs (a ") containing 42% epoxy resin, respectively, and the laminate thus obtained had a structure of [ (a") x3/(c1)/(d1)/(c1)/(a ") x3 ].

Test method

Tensile strength: the laminate sheet products (40 cm. times.40 cm) obtained in examples 1-2 and comparative examples 1-2 were cut into a plurality of test specimens (5 cm. times.5 cm) and tested for tensile strength in the thickness direction according to ASTM C297 standard, the results of which are shown in Table 1. Failure modes were observed in the honeycomb core for all tested samples, confirming good adhesion between layers of the laminate of the example, without delamination problems.

Thickness: the thickness of the laminate samples was measured with a micrometer caliper. Each sample was measured 3 to 5 times at different points, the results averaged and reported in table 1.

Surface density: the laminate samples were measured for length and width with a straight ruler, weighed with a balance, calculated for weight per unit area, averaged, and reported in table 1.

Gloss: the surface gloss of each laminate sample was measured at an angle of incidence of 60 degrees according to ASTM D2457 in GU (gloss unit), with higher values indicating a smoother surface being tested.

TABLE 1

From the results of table 1, the following discussion is evident.

The laminate E1 produced by the composite laminate manufacturing method of the present invention had the same values of areal density, thickness and comparative example CE1, and the tensile strength of E1 was also slightly higher than that of CE 1. Since the surface gloss of the composite panel is mainly determined by the mold used and the smoothness of the fabric used for the skin layer, comparing the gloss of the smooth side of E1 with that of the surface of CE1, it can be deduced that the surface of the flat glass mold used to make E1 is smoother than the surface of the stainless steel mold used to make CE 1. Similarly, the same reasoning can be derived by comparing the gloss data for the smooth surface of E2 and the surface of CE 2.

General vacuum infusion process in order to obtain a composite panel that is completely impregnated with binder, an auxiliary wicking material, similar to the sacrificial layer of example 1, laid on the second skin layer, was necessary, and thus the gloss of the surface of the article was expected to be similar to the gloss values of the matte side of examples 1 and 2. In contrast, the composite laminated plate of the invention can make the fabric of the skin layer directly attached to the surface of the mould by the method provided by the invention, and can obtain the composite plate with at least one smooth surface. Comparing the gloss values of the smooth and rough sides of E1, it was confirmed that the method of the present invention is advantageous over the conventional vacuum infusion process in that the composite laminate of the present invention is produced with at least one surface that is smooth and uniform.

In some embodiments of the invention, the matte side of the composite laminate of the invention has a gloss of at least greater than 10, or greater than 25, or greater than 50, wherein the gloss is measured at an angle of incidence of 60 degrees according to the method of ASTM D2457.

While the invention has been illustrated and described in typical embodiments, it is not intended to be limited to the details shown, since various modifications and substitutions can be made without departing in any way from the spirit of the present invention. Accordingly, various modifications and equivalents of the invention herein disclosed may occur to persons skilled in the art using no more than routine experimentation, and all such modifications and equivalents are believed to be within the spirit and scope of the invention as defined by the following claims.

Claims

1. Composite laminate panel with a honeycomb core comprising in sequence:

(a) a first skin layer;

(b) a first barrier film;

(c) a first adhesive film;

(d) a honeycomb core;

(e) a second adhesive film;

(f) a second barrier film;

(g) a second skin layer;

(h) a plurality of tubular rivets;

(i) the self-expanding sealant is coated around the tubular rivet; and

(j) a matrix derived from a liquid binder;

wherein the content of the first and second substances,

the tubular rivets are inserted through the preform and are spaced apart from each other by a distance of 30mm to 200 mm;

the first skin layer (a) and the second skin layer (g) are dry state fabrics containing no resin.

2. The composite laminate of claim 1 wherein

The first skin layer (a) and the second skin layer (g) are not prepregs; and each independently comprises at least one layer of reinforcing fabric comprising glass fibers, carbon fibers, aramid fibers, or combinations thereof;

the first release film (b) and the second release film (f) each independently comprise ethylene- (meth) acrylate, anhydride-modified ethylene- (meth) acrylate, ethylene vinyl acetate, anhydride-modified ethylene vinyl acetate, ethylene acid ionomer, polyamide, polyurethane, polyester, polyimide, or a combination thereof;

the first adhesive film (c) and the second adhesive film (e) each independently comprise an epoxy resin, an acrylate resin, or a polyurethane resin; and their glass transition temperature is from 60 ℃ to 160 ℃;

the honeycomb core (d) is a plate having a honeycomb structure, which is composed of a sheet comprising aramid, polycarbonate, polypropylene, steel, aluminum alloy, or glass fiber; the cross section of each cell of the honeycomb plate is hexagonal, overstretched hexagonal, circular or corrugated; and

the self-expandable sealant is composed of expandable polystyrene or expandable polyurethane.

3. The composite laminate as claimed in claim 1, which has a total thickness of 5mm to 300mm and an areal density of 0.35Kg/m²To 20Kg/m²。

4. The composite laminate as claimed in claim 2, wherein the reinforcing fabrics used as the first skin layer (a) and the second skin layer (g) each independently have 20g/m²To 660g/m²And the reinforcing fabric is a woven, unidirectional or non-woven fabric.

5. The composite laminate of claim 1 wherein the first and second release films (b, f) each independently have 20g/m²To 100g/m²And a thickness of 20 μm to 100 μm.

6. The composite laminate of claim 1 wherein the first cling film (c) and the second cling film (e) each independently have 100g/m²To 300g/m²And a thickness of 100 to 300 μm.

7. The composite laminate of claim 1 wherein the honeycomb core (d) is made of meta-aramid paper or para-aramidA honeycomb panel of an amine paper having a thickness of 2mm to 300mm, a cell size of 1.6mm to 20.0mm, a cell wall thickness of 0.1mm to 0.3mm, and a density of 24Kg/m³To 200Kg/m³。

8. The composite laminate of claim 1 wherein each tubular rivet has a flat head with a diameter of 1.6mm to 20.0mm, a head thickness of 0.1mm to 1.0mm, a hollow tube having an inner diameter of 1.2mm to 19.6mm, a tube wall thickness of 0.2mm to 0.9mm, and the tubular rivet has a length substantially equal to the preform thickness; and the tubular rivet is composed of a metallic material and a non-metallic material, the metallic material comprises copper, nickel, aluminum, titanium, alloys thereof, or stainless steel, and the non-metallic material comprises polyamide or polyester; wherein "the tubular rivet has a length substantially equal to the preform thickness" means that the tubular rivet length differs from the preform thickness by no more than 10% of the preform thickness.

9. The composite laminate of claim 1 wherein the liquid adhesive-derived matrix content is from 40 to 150 wt% of the total weight of the first and second skin layers (a, g).

10. A method of manufacturing the composite laminate of claim 1, comprising:

iii) coating the periphery of each tubular rivet with a self-expanding sealant;

v) curing the preform covered with the first and second skin layers obtained in step (iv) by a vacuum assisted resin infusion process.

11. The method of claim 10, wherein the curing step is performed at 25 ℃ to 120 ℃ and a pressure of-0.08 MPa to-0.10 MPa for 1 hour to 24 hours.

12. An article or component in a vehicle or a movable temporary dwelling comprising the composite laminate of claim 1, wherein the vehicle comprises an automobile, a ship, a train, a maglev, a drone, or an airplane, and the movable temporary dwelling comprises a shelter or a movable house.

13. Use of the composite laminate according to claim 1 in the manufacture of an article or part in a transportation vehicle or a movable temporary dwelling, wherein the transportation vehicle comprises an automobile, a ship, a train, a maglev, a drone or an airplane, and the movable temporary dwelling comprises a shelter or a movable dwelling.