TWI622634B - 複合材料之黏結 - Google Patents

複合材料之黏結 Download PDF

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Publication number
TWI622634B
TWI622634B TW103123701A TW103123701A TWI622634B TW I622634 B TWI622634 B TW I622634B TW 103123701 A TW103123701 A TW 103123701A TW 103123701 A TW103123701 A TW 103123701A TW I622634 B TWI622634 B TW I622634B
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TW
Taiwan
Prior art keywords
resin
composite substrate
release layer
matrix resin
curing
Prior art date
Application number
TW103123701A
Other languages
English (en)
Other versions
TW201512361A (zh
Inventor
李奧納 麥亞當斯
達利夫Ｋ 柯里
Original Assignee
塞特工業公司
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Publication of TW201512361A publication Critical patent/TW201512361A/zh
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Publication of TWI622634B publication Critical patent/TWI622634B/zh

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Classifications

    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/483—Reactive adhesives, e.g. chemically curing adhesives
    • B29C65/4835—Heat curing adhesives
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/50—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like
    • B29C65/5057—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like positioned between the surfaces to be joined
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/022—Mechanical pre-treatments, e.g. reshaping
    • B29C66/0224—Mechanical pre-treatments, e.g. reshaping with removal of material
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/303—Particular design of joint configurations the joint involving an anchoring effect
    • B29C66/3032—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined
    • B29C66/30321—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined making use of protrusions belonging to at least one of the parts to be joined
    • B29C66/30322—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined making use of protrusions belonging to at least one of the parts to be joined in the form of rugosity
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/721—Fibre-reinforced materials
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7316—Surface properties
    • B29C66/73161—Roughness or rugosity
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/737—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
    • B29C66/7375—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured
    • B29C66/73751—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured the to-be-joined area of at least one of the parts to be joined being uncured, i.e. non cross-linked, non vulcanized
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7394—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoset
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B37/0038—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving application of liquid to the layers prior to lamination, e.g. wet laminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B32B37/025—Transfer laminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/12—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by the relative arrangement of fibres or filaments of different layers, e.g. the fibres or filaments being parallel or perpendicular to each other
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
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    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/721—Fibre-reinforced materials
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

本發明係關於用於表面預處理之剝離層及一種在膠合黏結之前之表面預處理之方法。將富含樹脂之剝離層塗覆至可固化、基於樹脂之複合基板上，隨後共固化。在共固化之後，該複合基板係完全固化而該剝離層中的該基質樹脂保持部分固化。當移除該剝離層時，暴露出具有化學活性官能基之粗糙、可黏結表面。可將具有該化學活性、可黏結表面之該複合基板黏結至另一複合基板以形成共價黏結結構。

Description

複合材料之黏結
習知地將膠合黏結用作接合複合結構(諸如航太工業中使用之複合結構)之方法。當前，複合結構之膠合黏結主要藉由以下三種方式中之一種來進行：(1)共固化、(2)共黏結及(3)二次黏結。
「共固化」涉及藉由同時固化及黏結來接合未固化複合部件，其中將該等複合部件與黏著劑一起固化，產生化學鍵結。然而，難以將此技術應用於未固化預浸體之黏結中以製造具有複雜形狀之大型結構部件。未固化複合材料，例如預浸體，為黏性(亦即觸感為黏性)的且缺乏自行支撐所必需的剛性。因此，未固化複合材料為難以處理的。舉例而言，在具有複雜三維形狀之工具上難以組裝及黏結未固化複合材料。
「共黏結」涉及藉由膠合黏結將預固化複合部件接合至未固化複合部件，其中黏著劑及未固化複合部件係在黏結期間固化。預固化複合物通常在膠合黏結之前需要額外的表面預處理步驟。
「二次黏結」為藉由膠合黏結將預固化複合部件接合在一起，其中僅將黏著劑固化。此黏結方法典型地需要在黏結表面處對每個經預先固化的複合部件進行表面預處理。
用於共黏結及二次黏結之適當表面處理為獲得膠合黏結結構中之最高程度黏結線完整性的先決條件。黏結線完整性一般係指黏結界面之整體品質及穩固性。習知共黏結及二次黏結方法典型地包括在膠 合黏結之前遵循製造商說明書對複合結構進行表面處理。表面處理包括(但不限於)噴粒處理、砂磨、剝離層、上底漆等。此等表面處理方法主要藉由表面之機械粗糙化來改良黏著作用。粗糙表面由於黏結界面處之機械聯鎖而可實現更好的黏著。預固化複合結構之該共黏結或二次黏結具有以下侷限性：黏結機制係僅經由機械聯鎖產生，而無如共固化黏結中的化學鍵之形成。該等表面處理，若不適當地進行，則在使用最終黏結結構期間可變為黏結失效之來源。此外，在複合物黏結總成之界面處未形成化學鍵之情況下，黏結線品質之評估為至關重要的，以確保存在適當黏結。不幸的是，黏結線品質之評估通常為困難的且此項技術中已知的用於量測黏結線品質之當前技術並非良好適於量測及評估弱黏結之所有潛在來源。
在航太工業中，黏著劑係典型地與機械緊固件(例如鉚釘、螺釘及螺栓)組合使用以安全且可靠地固定結構材料。在飛機中很少將結構黏著劑用作用於接合結構部件之唯一機制。膠合黏結部件與藉由機械緊固件接合的部件相比呈現顯著優點，包括：重量較輕、減少應力集中、耐久性、較少部件數等。儘管具有此等益處，但部分由於評估黏結線完整性之難度，膠合黏結之使用受到限制。當前，不存在用於量測接合部件之黏結強度的非破壞性方法。用於量測膠合黏結接合之強度的唯一方式為找到極限強度，其係藉由破壞黏結而獲得。由於顯而易見的原因，此類型之破壞性測試在諸如飛機組裝之工業製造環境下為不實用的。此外，驗證測試大量試樣以確定黏著劑之平均負載能力並不能保證各個及每一個黏結結構將具有預期的黏結強度。
為了滿足諸如美國之國家的某些航空認證要求，當前需要主要結構之結構複聯。當前先進技術黏結方法不能夠滿足此等要求。當前，僅共固化結構被美國聯邦航空管理局(FAA)認可用於主要結構且廣泛地用於航太工業中。因此，仍需要可在製造環境下使用的膠合黏 結方法或技術，如在產生可靠且高強度的化學黏結的同時提供黏結線品質之極佳再現性之方法。此外，仍需要可滿足結構複聯要求(例如由美國FAA提出之要求)而不增加額外製造步驟的黏結方法。
本發明提供一種富含樹脂之剝離層，其由經樹脂基質浸漬之編織品組成，該樹脂基質與複合預浸體之樹脂基質不同。剝離層經設計使得其可與複合基板(例如預浸體或預浸體疊層)共固化，且在移除該剝離層時，在完全固化複合基板之固化表面上保留剝離層樹脂之薄、連續性薄膜，但剝離層樹脂部分固化。部分固化剝離層樹脂薄膜提供具有化學反應性官能基之表面，該等化學反應性官能基能夠在隨後的黏結步驟中與黏著性樹脂發生化學反應。此剝離層經設計使得其可應用於各種複合基板，諸如預浸體，以改質其表面，從而獲得改良的黏著及黏結特性。因此，本文所揭示之剝離層提供優於當前先進技術方法之黏結技術中之步驟變化。
本文亦揭示一種在膠合黏結之前的新穎的表面預處理方法。此表面預處理方法涉及將上文所述的富含樹脂之剝離層塗覆至可固化、基於樹脂之複合基板上，隨後共固化。在共固化之後，複合基板完全固化而剝離層中的基質樹脂保持部分固化。當移除剝離層時，暴露出具有化學活性官能基之粗糙、可黏結表面。亦揭示用於將具有化學活性、可黏結表面之複合基板黏結至另一複合基板以形成共價黏結結構之方法。
10‧‧‧剝離層
11‧‧‧複合基板
12‧‧‧表面
13‧‧‧複合基板
14‧‧‧黏著膜
15‧‧‧共價黏結結構
20‧‧‧未固化預浸體層
圖1A至圖1C說明根據本發明之一個實施例之製備用於膠合黏結之複合基板之表面的方法。
圖1D至圖1E說明在表面預處理之後的複合基板之膠合黏結。
圖2A示意性說明層合至纖維加強型複合基板上之富含樹脂之剝 離層。
圖2B示意性說明在共固化及移除剝離層之後的圖2A中所示之複合基板。
圖3展示根據本發明之實施例之與富含樹脂之剝離層堆疊在一起，隨後共固化的複數個未固化預浸體層。
圖4展示含有1：1之環氧樹脂：固化劑比率之剝離層之FT-IR(傅里葉變換紅外(Fourier Transform Infrared))光譜。
圖5展示含有不足量的固化劑之剝離層之FT-IR光譜。
圖6為根據一個實例之展示不同剝離層系統之熱機械分析(TMA)之圖。
本文所揭示之新穎的表面預處理方法能夠產生一種化學活性複合表面，其可經由使用基於樹脂之黏著劑而以化學方式黏結至另一基板。此黏結方法之一個優點為在複合表面與黏著劑之間產生化學黏結，從而在複合基板之間產生更強的黏結。此方法之另一優點為其最小化對複合基板之黏結表面之污染作用。此外，此黏結方法可以工業規模實踐且無需實質性改變工業中當前使用之基礎結構。
本文所揭示之黏結方法允許藉由在待黏結表面產生化學反應性官能基，從而產生共固化結構來實現可認證的黏結方法之方式。因此，本文所揭示之新穎的黏結方法提供一種在不增加額外製造步驟之情況下滿足諸如由美國FAA提出之結構複聯要求之方式。
前述化學活性複合表面係藉由使用富含樹脂之剝離層產生。圖1A至圖1C說明如何使用富含樹脂之剝離層來產生具有化學活性官能基之可黏結表面。參考圖1A，首先將可固化剝離層10層合至未固化或可固化複合基板11之最外側表面上。未固化/可固化複合基板係由用未固化或可固化基質樹脂灌注或浸漬之加強纖維組成，該基質樹脂 含有一或多種熱固性樹脂。可固化剝離層10係由用不同於複合基板之未固化/可固化基質樹脂之可固化基質樹脂灌注或浸漬之編織品組成。剝離層10之基質樹脂亦含有一或多種熱固性樹脂；然而，其經配製使得當複合基板11在相同固化條件下完全固化時，剝離層樹脂僅部分固化。接著，藉由在高溫下加熱預定時間直至複合基板11完全固化而剝離層10僅部分固化來進行剝離層10與複合基板11之共固化。作為共固化之結果，剝離層基質樹脂與複合基質樹脂混合且發生反應。控制剝離層樹脂之流變及固化動力以獲得所需的剝離層樹脂基質與複合基板之樹脂基質之間的混合量，從而最大化樹脂基質之共固化，藉此確保在共固化之後，表面上保留足量的剝離層樹脂。在共固化之後，將剝離層(包括其中的織品)剝離(圖1B)以產生具有化學活性官能基之粗糙、可黏結表面12(圖1C)。粗糙、可黏結表面12係藉由在移除剝離層之後保留在複合基板11上的部分固化剝離層樹脂之薄膜提供。
可在0psi至80psi(0MPa至0.55MPa)範圍內之壓力下在室溫至375℉(191℃)範圍內之溫度下進行剝離層10與複合基板11之共固化保持1小時至12小時。此外，可在高壓釜中或藉由一種其中不施加外壓力之高壓釜外方法來實現共固化。
如圖1D中所示，可藉由包夾在基板之間且與可黏結表面12接觸之可固化、樹脂基黏著膜14將具有可黏結表面12之固化複合基板11接合至另一複合基板13。基於樹脂之黏著膜14處於未固化或部分固化狀態中且具有能夠與可黏結表面12上的化學活性官能基發生反應之化學官能基。在影響黏結之後續熱處理期間，此等官能基相互反應以形成化學鍵或共價鍵。
複合基板13可為已經受與關於複合基板11所描述相同之剝離層表面預處理之固化複合基板，以便形成具有化學活性官能基之對應物可黏結表面。經接合之複合基板11及13接著在高溫下經受熱處理以固化 黏著劑，產生共價黏結結構15(圖1E)，此係稱作二次黏結。可將黏著膜14塗覆至複合基板11之可黏結表面12及複合基板13之可黏結表面中之任一者或其兩者上。
或者，複合基板13之可黏結表面可藉由其他已知的諸如噴砂處理、噴粒處理、乾式剝離層表面預處理等表面處理來製備。「乾式剝離層」為無水編織品(不含樹脂)，通常是由耐綸、玻璃或聚酯製造，將其塗覆至複合基板之黏結表面上，隨後固化。在固化之後，移除該乾式剝離層以暴露出紋理化黏結表面。
在另一實施例中，當將複合基板13接合至固化複合基板11時，複合基板13處於未固化狀態。在此情況下，在隨後的加熱步驟中同時固化未固化複合基板13及可固化黏著膜14，此係稱作共黏結。
在根據本文所揭示之方法之複合基板的共黏結或二次黏結期間，在存在於基於樹脂之黏著劑中之反應性部分與來源於富含樹脂之剝離層之複合基板的可黏結表面上之化學反應性官能基之間形成化學鍵或共價鍵。因此，共價黏結結構本質上不具有黏著劑-複合物界面。本文所述之可黏結表面上的化學活性官能基之存在藉由增加黏結基板之間的黏結強度及提高黏結可靠度來使隨後的黏結方法最佳化。此外，共價黏結結構比藉由習知的共黏結或二次黏結方法製備之黏結結構更耐污染。
如本文所用之術語「固化(cure)」及「固化(curing)」涵蓋藉由混合基礎組分、在高溫下加熱、曝露於紫外光及輻射而產生的聚合材料之聚合及/或交聯。如本文所用之「完全固化」係指100%程度之固化。如本文所用之「部分固化」係指低於100%程度之固化。
剝離層樹脂可含有一或多種固化劑(curing agents)(或固化劑(curatives))或可不含任何固化劑。在剝離層樹脂含有固化劑之實施例中，在與複合基板共固化之後，部分固化剝離層之固化程度可在完全 固化之10%-75%的範圍內，例如25%-75%或25%-50%。在剝離層樹脂不含任何固化劑之實施例中，除在複合物-剝離層界面處之外，在與複合基板共固化之後剝離層大部分係未固化。
熱固性樹脂系統之固化程度可藉由差示掃描熱量測定法(DSC)確定。熱固性樹脂系統在固化期間進行不可逆化學反應。隨著樹脂系統中的組分固化，由樹脂放出熱量，其係藉由DSC儀器監測。固化之熱量可用於確定樹脂材料之固化百分比。作為實例，以下簡單計算可提供此資訊：%固化=[△H未固化-△H固化]/[△H未固化]×100%
剝離層
本發明之富含樹脂之剝離層係由用可固化基質樹脂浸漬之織品組成，且視所浸漬之織品之特定類型而定，具有以剝離層之總重量計至少20重量%的樹脂含量。在某些實施例中，樹脂含量在20重量%-80重量%的範圍內，較佳為20重量%-50重量%。在一個實施例中，本發明之富含樹脂之剝離層含有以剝離層之總重量計：20重量%-80重量%的熱固性基質樹脂、2重量%-20重量%的固化劑及5重量%-40重量%的額外改質劑或填料添加劑。
圖2A示意性說明層合至纖維加強型複合基板上之富含樹脂之剝離層。圖2B示意性說明在共固化及移除剝離層之後的具有剩餘剝離層樹脂之殘餘層之複合基板。在剝離期間的破裂線係在纖維-樹脂界面處，但不在織品內。選擇剝離層樹脂組合物及織品構造，使得在移除剝離層之後無斷裂纖維留在複合基板之表面上。較佳地，由於不完全固化，在固化之後保留在複合基板之表面上的剝離層樹脂具有低於複合樹脂基質之玻璃轉移溫度(Tg)之玻璃轉移溫度。較低樹脂Tg亦允許表面剝離層樹脂在隨後黏結步驟期間經歷黏性流，藉此產生剝離層樹脂可與黏著性樹脂混合之條件。
在一個實施例中，剝離層之基質樹脂係由可固化樹脂組合物形成，該組合物包括：一或多種熱固性樹脂；至少一種固化劑；及視情況選用之添加劑、改質劑及填充劑。根據另一實施例，剝離層之樹脂組合物含有一或多種熱固性樹脂，但不包括任何固化劑。
適合的熱固性樹脂包括(但不限於)環氧樹脂、酚醛樹脂、苯酚、氰酸酯、雙順丁烯二醯亞胺、苯并噁嗪、聚苯并噁嗪、聚苯并噁唑酮、其組合及其前驅物。
特別適合的為每分子具有複數個環氧官能基之多功能環氧樹脂(或聚環氧化物)。聚環氧化物可為飽和、不飽和、環狀或非環狀、脂族、芳族或雜環聚環氧化物化合物。適合的聚環氧化物之實例包括聚縮水甘油醚，其係在鹼存在下藉由表氯醇或表溴醇與多酚之反應來製備。因此，適合的多酚為例如間苯二酚、鄰苯二酚、對苯二酚、雙酚A(雙(4-羥基苯基)-2,2-丙烷)、雙酚F(雙(4-羥基苯基)甲烷)、氟4,4'-二羥基二苯甲酮、雙酚Z(4,4'-亞環己基雙酚)及1,5-羥基萘。作為用於聚縮水甘油醚之基底之其他適合的多酚為已知的酚醛清漆樹脂型酚及甲醛或乙醛之縮合產物。
適合的環氧樹脂之實例包括雙酚A或雙酚F之二縮水甘油醚，例如可購自Dow Chemical Co.之EPONTM 828(液體環氧樹脂)，D.E.R.331、D.E.R.661(固體環氧樹脂)；胺基酚之三縮水甘油基醚，例如來自Huntsman Corp.之ARALDITE® MY 0510、MY 0500、MY 0600、MY 0610。其他實例包括酚基酚醛清漆環氧樹脂，可自Dow Chemical Co以DEN 428、DEN 431、DEN 438、DEN 439及DEN 485商購；甲酚基酚醛清漆環氧樹脂，可自Ciba-Geigy Corp.以ECN 1235、ECN 1273及ECN 1299商購；烴酚醛清漆環氧樹脂，可自Huntsman Corp.以TACTIX® 71756、TACTIX® 556及TACTIX® 756商購。
剝離層樹脂組合物較佳為將在高溫下固化之單組分系統，且因 此其含有一或多種固化劑。當加熱至高於室溫之溫度時，該等固化劑能夠實現剝離層樹脂組合物之選擇性組分之交聯或固化。為達成本文所述之目的，選擇固化劑的量使得每1當量環氧樹脂分子較佳存在約0.1至約1當量固化劑，更佳在0.1-0.5之間。選擇固化劑與環氧樹脂之精確比率，使得在與複合基板共固化之後保留最佳數目之化學活性表面官能基。用於剝離層樹脂之適合的固化劑可包括(但不限於)脂族及芳族胺、三氟化硼複合物、胍、雙氰胺、雙脲(例如2,4-甲苯雙-(二甲基脲)、4,4'-亞甲基雙-(苯基二甲基脲))及二胺基二苯碸(例如4,4'-二胺基二苯碸或4,4'-DDS)。可使用一或多種固化劑且固化劑之總量以樹脂組合物之總重量計可在2重量%-20重量%的範圍內。
亦可將呈顆粒形式(例如粉末)之無機填充劑添加至剝離層樹脂組合物中作為流變改質組分以控制樹脂組合物之流動及防止在其中黏聚。適合的無機填充劑包括(但不限於)煙霧狀二氧化矽、滑石、雲母、碳酸鈣、氧化鋁、研磨或沈澱的白堊、石英粉末、氧化鋅、氧化鈣及二氧化鈦。若存在，則剝離層樹脂組合物中之填充劑的量可為以樹脂組合物之總重量計0.5重量%至40重量%，較佳為1-10重量%，更佳為1-5重量%。
可藉由將上述樹脂組合物塗佈至編織品上來形成富含樹脂之剝離層，以便使用習知溶劑或熱熔融塗佈方法來完全浸漬織品中之紗線。接著使濕潤的剝離層乾燥(若需要)以降低揮發性物質含量，較佳降低至低於2重量%。可藉由在室溫下的風乾隔夜，隨後在140℉-170℉下烘乾，或視需要藉由在高溫下烘乾以減少乾燥時間來進行乾燥。隨後，可藉由將可移除剝離型紙或合成薄膜(例如聚酯薄膜)塗覆至相對側上來保護經乾燥之富含樹脂之剝離層。該等剝離型紙或合成薄膜將在使用用於表面黏結之剝離層之前移除。
在一個實施例中，調節剝離層樹脂之組合物中之熱固性樹脂與 固化劑之比率，使得該組合物含有不足以用於與100%熱固性樹脂反應必要之量的固化劑，且因此，由於此不足，在預先確定之固化循環結束時將存在來自熱固性樹脂材料的未反應或非交聯官能基。例如，在預先確定之固化循環中若需要X量之固化劑以獲得100%程度之固化，則在剝離層樹脂組合物中可使用低於X的量，例如至多80%的X，較佳25%-50%的X以實現部分固化。熱固性樹脂材料含有未反應/非交聯官能基，其為用於上文所論述之可黏結表面的化學活性官能基之來源。
複合基板
在此上下文中，複合基板係指纖維加強型樹脂複合物，包括預浸體或預浸體疊層(諸如用於製造航空複合結構者)。如本文所用之術語「預浸體」係指已用可固化基質樹脂浸漬之纖維材料層(例如單向纖維束或帶、非織氈或織品層)。複合基板中的基質樹脂可處於未固化或部分固化狀態。纖維加強型材料可呈編織或非編織織品層或單向帶形式。「單向帶」係指加強纖維層，其係在相同方向上對準。如本文所用之術語「預浸體疊層」係指複數個堆疊在堆疊配置中之預浸體層。
可手動或藉由諸如自動鋪帶(ATL)之自動方法完成預浸體層之疊層。可將疊層內的預浸體層安置在相對於彼此之所選擇的定向上。例如，預浸體疊層可包含具有單向纖維架構之預浸體層，其中該等纖維相對於疊層之最大維度(諸如長度)以所選角度θ，例如0°、45°或90°定向。另外應理解，在某些實施例中，預浸體可具有纖維架構之任何組合，諸如單向對準纖維、多向纖維及編織品。
根據一個實施例(圖3中所說明)，可將複數個未固化預浸體層20與上文描述為最外層之可固化、富含樹脂之剝離層11堆疊在一起，隨後共固化且移除剝離層以提供如上文參考圖1A至圖1C所述之具有化 學活性官能基的可黏結表面。作為實例，預浸體層之數目可為2-100層或10-50層。
可藉由使用基質樹脂系統輸注或浸漬連續性纖維或編織品、形成材料之可彎性及黏性薄片來製造預浸體。通常此係稱作預浸方法。可指定該等纖維之精確規格、其定向及樹脂基質之調配物以實現用於預浸體之吾人所需用途之最佳效能。亦可根據需求指定每平方公尺之纖維量。
在預浸中，以可控方式用基質樹脂浸漬加強纖維且接著冷凍以抑制樹脂之聚合。接著在冷凍狀態下運送及儲存冷凍預浸體直至需要時。當自預浸體製造複合材料部件時，將預浸體解凍至室溫，切割成一定尺寸且組裝至模具上。一旦定位，在壓力下固結及固化預浸體以獲得所需的具有最小空隙之纖維體積部分。
術語「浸漬」係指將可固化基質樹脂材料引入加強纖維中以便藉由樹脂部分或完全囊封纖維。用於製造預浸體之基質樹脂可呈樹脂薄膜或液體之形式。此外，在黏結之前，基質樹脂係處於可固化/未固化狀態。可藉由施加熱量及/或壓力來促進浸漬。
作為實例，浸漬方法可包括：(1)連續移動纖維通過熔融浸漬基質樹脂組合物之(經加熱之)槽以完全或實質上完全浸濕該等纖維；或(2)擠壓頂部及底部樹脂薄膜與並聯配置之連續性、單向纖維或織品層相抵。
複合基板(例如預浸體)中之加強纖維可呈短切纖維、連續性纖維、長絲、纖維束、集束、薄片、層及其組合之形式。連續性纖維可進一步採用單向(在一個方向上對準)、多向(在不同方向上對準)、非編織、編織、針織、縫合、捲繞及編織構型以及旋流墊、毛氈墊及短切墊結構中之任一者。編織纖維結構可包含複數個編織纖維束，各纖 維束係由複數個長絲組成，例如數千個長絲。在其他實施例中，可藉由交叉纖維束針、投緯針織針或少量諸如熱塑性樹脂之樹脂黏合劑將該等纖維束固持在位置上。
纖維材料包括(但不限於)玻璃(包括電氣玻璃或E玻璃)、碳、石墨、芳族聚醯胺、聚醯胺、較高模數聚乙烯(PE)、聚酯、聚對伸苯基苯并噁唑(PBO)、硼、石英、玄武岩、陶瓷及其組合。
就諸如用於航空及汽車應用之高強度複合材料之製造而言，較佳的是，加強纖維具有大於3500MPa之抗張強度。
一般而言，複合基板之基質樹脂與剝離層樹脂之基質樹脂類似。其含有一或多種熱固性樹脂作為主要組分以及少量添加劑用於在固化之前或在固化之後改良樹脂基質之特性，該等添加劑諸如固化劑、催化劑、共聚單體、流變控制劑、增黏劑、流變改質劑、無機或有機填充劑、熱塑性或彈性韌化劑、穩定劑、抑制劑、顏料/染料、阻燃劑、反應性稀釋劑及熟習此項技術者熟知的其他添加劑。
適用於複合基板之基質樹脂的熱固性樹脂為上文參考剝離層之基質樹脂所述之樹脂。
適用於複合基板之基質樹脂之環氧樹脂包括芳族二元胺、芳族單一級胺、胺基酚、多元酚、多元醇、聚羧酸之聚縮水甘油衍生物。適合的環氧樹脂之實例包括諸如雙酚A、雙酚F、雙酚S及雙酚K之雙酚之聚縮水甘油醚；及甲酚基與酚基酚醛清漆環氧樹脂之聚縮水甘油醚。
添加固化劑及/或催化劑可提高固化率及/或降低基質樹脂之固化溫度。用於熱固性樹脂之固化劑係適當地選自已知的固化劑，例如胍(包括經取代之胍)、脲(包括經取代之脲)、三聚氰胺樹脂、胍胺、胺(包括一級及二級胺、脂族及芳族胺)、醯胺、酸酐(包括聚羧酸酐)及其混合物。
韌化劑可包括熱塑性及彈性聚合物，及諸如核-殼型橡膠粒子、聚醯亞胺粒子、聚醯胺粒子之聚合粒子。
無機填充劑可包括煙霧狀二氧化矽石英粉末、氧化鋁、板狀填充劑，諸如雲母、滑石或黏土(例如高嶺土)。
黏著劑
用於黏結複合基板之黏著劑為適用於與未固化或可固化複合基板一起共固化之可固化組合物。可固化黏著劑組合物可包含一或多種熱固性樹脂、固化劑及/或催化劑、及視情況選用之韌化劑、填充材料、流動控制劑、染料等。熱固性樹脂包括(但不限於)環氧樹脂、不飽和聚酯樹脂、雙順丁烯二醯亞胺、聚醯亞胺、氰酸酯、酚等。
可用於可固化黏著劑組合物之環氧樹脂包括每分子具有複數個環氧樹脂基之多官能環氧樹脂，諸如揭示用於剝離層及複合基板之基質樹脂之樹脂。
固化劑可包括例如胍(包括經取代之胍)、脲(包括經取代之脲)、三聚氰胺樹脂、胍胺、胺(包括一級及二級胺、脂族及芳族胺)、醯胺、酸酐及其混合物。特別適合的為潛在的基於胺之固化劑，其可在高於160℉(71℃)的溫度下活化，較佳在高於200℉的溫度下，例如350℉。適合的潛在的基於胺之固化劑之實例包括雙氰胺(DICY)、胍胺、胍、胺基胍及其衍生物。特別適合的潛在的基於胺之固化劑為雙氰胺(DICY)。
可將固化促進劑與潛在的基於胺之固化劑結合使用以促進環氧樹脂與基於胺之固化劑之間的固化反應。適合的固化促進劑可包括經烷基及芳基取代之脲(包括芳族或脂環族二甲基脲)；基於甲苯二胺或亞甲基二苯胺之雙脲。雙脲之實例為2,4-甲苯雙(二甲基脲)。作為實例，可將雙氰胺與經取代之雙脲組合用作固化促進劑。
韌化劑可包括熱塑性或彈性聚合物，及諸如核-殼型橡膠(CSR)粒 子之聚合粒子。適合的熱塑性聚合物包括具有或不具有反應性官能基之聚芳碸。具有官能基之聚芳碸之實例包括例如具有封端胺官能基之聚醚碸-聚醚醚碸(PES-PEES)共聚物。適合的彈性聚合物包括羧基封端丁二烯腈聚合物(CTBN)及胺封端丁二烯丙烯腈(ATBN)彈性體。CSR粒子之實例包括以商標Kane Ace®市售者，諸如MX 120、MX 125及MX 156(全部含有25重量%的分散在液體雙酚A環氧樹脂中之CSR粒子)。
無機填充劑可呈粒狀物形式，例如粉末、薄片，且可包括煙霧狀二氧化矽石英粉末、氧化鋁、雲母、滑石及黏土(例如高嶺土)。
實例
提供以下實例以說明本發明之某些態樣。在以下實例中，除非另外指明，否則表中所示之量係以重量份(「pbw」)計。
實例1
基於表1中所示之調配物製備四份可固化剝離層樹脂混合物。使用與標記為對照物之樹脂混合物相同的調配物製備標記為樹脂-17、樹脂-11、樹脂-8之樹脂混合物，但4,4'-二胺基二苯碸(4,4'-DDS)固化劑之量由20.9份分別變為17pbw、11.3pbw、8.3pbw。
使用熱熔融方法混合樹脂混合物，隨後將上述樹脂混合物中之每一者塗佈至來自Porcher Industries之聚酯基織品材料(Porcher 8115)上。接著將所得經樹脂浸漬之織品層用作剝離層材料。
藉由10層CYCOM 977-2(含有經基於環氧樹脂之基質樹脂浸漬之碳纖維之預浸體材料，可自Cytec Engineered Materials購得)手動堆疊所製備的剝離層材料中之每一者，其中剝離層形成外表皮。接著藉由在80psi下在350℉下加熱3小時使未固化層合物固化。在固化之後，手動移除該剝離層(包括織品)以產生具有可黏結表面之固化複合物件。對照物剝離層完全固化且在黏結表面上實質上未產生官能基，但其他剝離層提供含有未反應之環氧樹脂官能基之部分固化表面。接著使用基於環氧樹脂之黏著劑FM 309-1(可自Cytec Engineered Materials購得)將具有可黏結表面之固化複合物件黏結(經由二次黏結)至另一相同複合物件。基於環氧樹脂之黏著劑未固化且含有提供胺官能基之胺型固化劑。藉由在40psi下以每分鐘3℉加熱至350℉且保持90分鐘來進行二次黏結。
表1中所揭示之剝離層調配物經設計使得4,4'-DDS固化劑之含量為變化的以選擇性控制在與預浸體層共固化之後剩餘的未反應之環氧樹脂官能基的量。顯而易見的是，藉由降低剝離層調配物中4,4'-DDS的量，在與預浸體層共固化期間消耗較少的環氧基，藉此允許保留可隨後與黏著劑之官能基發生反應之環氧官能基。
黏結結構之機械特性及表徵
藉由根據ASTM D5528完成之G1c破裂韌性測試確定上述產生的黏結結構之機械效能。G1c結果展示於表2中。
表2展示借助於部分固化剝離層材料(樹脂-17、樹脂-11及樹脂-8)形成之黏結結構與由使用完全固化剝離層(對照物)形成之黏結結構相比產生更強的黏結強度。更重要的是，失效模式，其為所需失效類 型，在含有部分固化剝離層之系統中變得更有內聚性。
實例2
在部分固化剝離層表面上之活性官能基之保留係經由使用傅里葉變換紅外(FT-IR)光譜法之剝離層材料之調查證實。FT-IR光譜法為用於表徵官能基之有效光譜工具且允許鑑別材料之結構組分。剝離層係由具有不足量的固化劑(亦即固化劑)之樹脂組合物形成且對照剝離層係由具有1：1之環氧樹脂：固化劑比率之樹脂組合物形成。剝離層組合物展示於表3中。
如實例1中所描述，將各剝離層與預浸體層堆疊在一起且共固化。圖4展示對照剝離層材料之FT-IR光譜，其含有足夠固化劑以完全固化其中的熱固性樹脂，且圖5展示其中存在不足量的固化劑之剝離層材料之FT-IR光譜，使得在共固化期間不消耗所有的熱固性樹脂，從而產生部分固化剝離層。在約914cm-1處的峰為特徵帶，其歸因於環氧乙烷環之伸縮振動。吸光度之高度或峰高度為存在於既定材料中之環氧基之量的指標。如在圖5中可見，部分固化剝離層在共固化之後具有更高的環氧官能基之量。
以此類方式產生的表面活性官能基之存在與傳統的二次黏結結構相比具有在基板-黏著劑界面處提供化學鍵之益處。因此，本發明之方法提供一種二次黏結複合材料以產生共固化結構之方式。此黏結方法之改進在於其為黏結結構提供可靠性及結構複聯。
實例3
經由熱機械分析(TMA)研究實例1中之剝離層調配物以分析玻璃轉移溫度。圖6展示研究結果且表明可藉由修改調配物比率來控制剝離層樹脂表面之Tg。
實例4
標記為樹脂-12及樹脂-6之兩種可固化剝離層樹脂混合物係基於表4中所示之調配物製備。使用熱熔融方法製備樹脂混合物，隨後將上述樹脂混合物中之每一者塗佈至來自Porcher Industries之基於聚酯之織品材料(Porcher 8115)上。接著將所得經樹脂浸漬之織品層用作剝離層材料。
將所製備之剝離層材料中之每一者藉由10層CYCOM 977-2手動堆疊，其中剝離層形成外表皮。接著藉由在80psi下在350℉下加熱3小時使未固化層合物固化。作為比較，以類似方式製備另一個預浸體疊層，不同之處在於用乾式聚酯織品剝離層(Porcher 8115)替換上述製備的富含樹脂之剝離層。在固化之後，手動移除各剝離層以產生具有可黏結表面之固化複合物件。接著使用基於環氧樹脂之黏著劑FM 309-1將具有可黏結表面之固化複合物件黏結(經由二次黏結)至另一個相同複合物件上。基於環氧樹脂之黏著劑未固化且含有提供胺官能基之胺型固化劑。藉由在40psi下以每分鐘3℉加熱至350℉且保持90分鐘來進行二次黏結。
亦藉由CYCOM 977-2預浸體材料之兩個10層堆疊、在預浸體堆疊之間包夾FM 309-1黏著劑及藉由在80psi下在350℉下加熱90分鐘共 固化來製備共固化對照結構。
黏結結構之機械特性及表徵
此實例中產生的黏結結構之機械效能係藉由根據ASTM D5528進行之G1c破裂韌性測試確定。G1c結果展示於表5中。
實例5
藉由上述實例4之基於樹脂-6的剝離層堆疊CYCOM 977-2預浸體材料之4層層合物作為外表皮。接著藉由在80psi下在350℉下加熱3小時來使未固化層合物固化，藉此樹脂-6剝離層在固化循環結束時部分固化。在移除剝離層之後，接著將具有部分固化、殘餘剝離層薄膜之固化複合層合物黏結至以類似方式製備、固化之層合物(亦含有部分固化、殘餘剝離層薄膜)上，其中經剝離層處理之表面面向彼此且基於環氧樹脂之黏著劑FM 309-1夾在中間。基於環氧樹脂之黏著劑未固化且含有提供胺官能基之胺型固化劑。在黏結期間，黏結總成亦黏著於2"×2"鋁固定塊。整個總成經真空裝袋且在高壓釜中藉由在40psi下以每分鐘3℉加熱至350℉且保持90分鐘來固化。接著藉由表面張力之拉伸在Instron測試機上測試固化層合物以評估失效之破裂力學。
藉由遵循上述程序類似地製造對照層合物，藉由使用乾式剝離層置換上述基於樹脂-6之剝離層來製備二次黏結面板且藉由在一個步驟中固化整個總成來產生共固化面板(但不使用剝離層)。
表6展示來自固化層合物之平拉力測試的結果且表明基於樹脂-6之剝離層的有效性。亦藉由分析失效模式來評估樹脂-6剝離層對界面特性之影響以確定剝離層是否不利地影響黏結能力。根據破裂試樣之分析，總成之弱點為預浸體層合物。該等結果清楚地表明使用樹脂-6 剝離層可提供增強結構強度之穩固黏結表面。

Claims (18)

  1. 一種用於在膠合黏結之前之表面預處理的方法，其包含：(a)提供複合基板，其包含用可固化、第一基質樹脂浸漬之加強纖維；(b)將可移除、富含樹脂之剝離層塗覆至該複合基板之表面上，該剝離層包含用可固化、不同於該第一基質樹脂之第二基質樹脂浸漬之編織品；(c)使該複合基板與該剝離層共固化直至該複合基板完全固化而該剝離層中之該第二基質樹脂保持部分固化；及(d)自該複合基板之表面移除該剝離層，在該複合基板之表面上留下部分固化第二基質樹脂之薄膜，該薄膜提供具有化學活性官能基之粗糙、可黏結表面。
  2. 如請求項1之方法，其中該第二基質樹脂包含一或多種多功能環氧樹脂，且在移除該剝離層之後，該粗糙、可黏結表面上之該等化學活性官能基包含環氧官能基。
  3. 如請求項1之方法，其中該第二基質樹脂包含至少一種熱固性樹脂及至少一種用於使該熱固性樹脂交聯的固化劑，且熱固性樹脂與固化劑之莫耳比係使得在步驟(c)中，在共固化之後，在該剝離層中存在未反應之非交聯熱固性樹脂。
  4. 如請求項3之方法，其中固化劑與熱固性樹脂之該比率係使得存在不足以用於與100%該熱固性樹脂反應必要之量的固化劑。
  5. 如請求項1之方法，其中該第二基質樹脂包含一或多種多功能環氧樹脂，但不含任何用於使該等環氧樹脂交聯之固化劑。
  6. 如請求項1之方法，其中保留在該複合基板之表面上的部分固化第二基質樹脂之該薄膜由於不完全固化而具有低於該複合基板之基質樹脂的玻璃轉移溫度(Tg)之玻璃轉移溫度。
  7. 一種固化複合基板，其具有藉由如請求項1之方法產生之具有化學活性官能基之粗糙、可黏結表面。
  8. 一種黏結方法，其包含：(a)提供第一複合基板，其包含用可固化、第一基質樹脂浸漬之加強纖維；(b)將可移除、富含樹脂之剝離層塗覆至該第一複合基板之表面上，該剝離層包含用可固化、不同於該第一基質樹脂之第二樹脂基質浸漬之編織品；(c)使該第一複合基板與該剝離層共固化直至該第一複合基板完全固化而該剝離層中之該第二基質樹脂保持部分固化；(d)自該第一複合基板之表面移除該剝離層，在該第一複合基板之表面上留下部分固化第二基質樹脂之薄膜，該薄膜提供具有化學活性官能基之粗糙、可黏結表面；(e)藉由在該等複合基板中間之可固化黏著膜將該固化、第一複合基板接合至第二複合基板，該黏著膜與該第一複合基板之該可黏結表面接觸，其中該可固化黏著膜包含能夠與該第一複合基板之該可黏結表面上的該等化學活性官能基反應之化學活性官能基；及(f)使該黏著膜固化以形成共價黏結結構，藉此該黏著膜上的該等官能基與該第一複合基板之該可黏結表面上的該等官能基反應以形成共價鍵。
  9. 如請求項8之黏結方法，其中該第二複合基板係在接合至該固化、第一複合基板之前固化。
  10. 如請求項8之黏結方法，其中該固化、第二複合基板包含具有化學活性官能基之粗糙、可黏結表面，該表面係藉由與用於形成該固化、第一複合基板之該粗糙、可黏結表面相同之方法製備。
  11. 如請求項9之黏結方法，其中該第二複合基板在接合至該第一複合基板之前係未固化或部分固化，且在步驟(f)期間，該黏著膜及該第二複合基板係同時固化。
  12. 如請求項9之黏結方法，其中該第二基質樹脂包含一或多種多功能環氧樹脂，且在移除該剝離層之後，該第一複合基板之該粗糙、可黏結表面上的該等化學活性官能基包含環氧官能基。
  13. 如請求項12之黏結方法，其中該可固化黏著膜包含至少一種多功能環氧樹脂及至少一種能夠與多功能環氧樹脂反應之脂族或環狀胺化合物。
  14. 如請求項9之黏結方法，其中該第二基質樹脂包含至少一種熱固性樹脂及至少一種用於使該熱固性樹脂交聯之固化劑，且熱固性樹脂與固化劑之莫耳比係使得存在不足以用於與100%該熱固性樹脂反應必要之量的固化劑，且因此在步驟(c)中，在共固化之後，在該剝離層中存在未反應之非交聯熱固性樹脂。
  15. 一種共價黏結結構，其係藉由如請求項9之方法產生。
  16. 一種可固化複合結構，其包含：在複合基板之表面上之可移除、富含樹脂之剝離層，其中該複合基板包含用可固化、第一基質樹脂浸漬之加強纖維且該剝離層包含用可固化、不同於該第一基質樹脂之第二基質樹脂浸漬之織品，及其中該第二基質樹脂含有不足以用於在將引起該第一基質樹脂完全固化的相同固化條件下完全固化該第二基質樹脂之量的固化劑。
  17. 如請求項16之可固化複合結構，其中該第二基質樹脂包含至少一種熱固性樹脂及至少一種用於使該熱固性樹脂交聯之固化劑，且熱固性樹脂與固化劑之莫耳比係使得存在不足以用於與100%該熱固性樹脂發生反應必要之量的固化劑，當該第一基質樹脂及該第二基質樹脂均經受相同固化條件時，將引起該第一基質樹脂完全固化，且因此當該第一基質樹脂完全固化時，在該剝離層中存在未反應之非交聯熱固性樹脂。
  18. 如請求項17之可固化複合結構，其中該第二基質樹脂中之該至少一種熱固性樹脂為多功能環氧樹脂。
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