CN116061509A - Method for preparing carbon fiber/stainless steel thin layer laminated board based on anodic oxidation process - Google Patents
Method for preparing carbon fiber/stainless steel thin layer laminated board based on anodic oxidation process Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
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- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- 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
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- 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
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- 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
- 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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- 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
- 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
- B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
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- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
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- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
Abstract
The invention relates to a method for preparing a carbon fiber/stainless steel thin layer laminated board based on an anodic oxidation process, which belongs to the technical field of fiber metal laminated board preparation, solves the technical problem of weak connection between stainless steel Bao Daiji FMLs layers, and adopts the following solution: firstly, carrying out direct current anodic oxidation on a stainless steel thin belt in an ethylene glycol-based electrolyte, and carrying out primary surface modification to obtain a porous oxide layer structure; and then, the laid stainless steel thin belt and the carbon fiber prepreg belt are subjected to hot pressing, solidification and molding at a certain temperature and pressure. On the basis, the stainless steel thin strip subjected to direct-current anodic oxidation surface modification is subjected to secondary surface modification in a silane coupling agent hydrolysate, and chemical bonding is introduced between the epoxy resin-based carbon fiber prepreg strip and the stainless steel thin strip. The preparation method is simple and economical to operate, meets the requirement of the interlayer bonding strength of the stainless steel thin belt/carbon fiber prepreg, and is a feasible preparation method for enhancing the interlayer performance of the stainless steel thin belt/carbon fiber laminate.
Description
Technical Field
The invention belongs to the technical field of preparation of fiber metal laminated plates, and particularly relates to a method for preparing a carbon fiber/stainless steel thin-layer laminated plate based on an anodic oxidation process.
Background
Compared with aluminum alloy, the stainless steel with the same thickness has higher specific tensile strength, fatigue strength, rigidity and corrosion resistance as the most extensive engineering structural material, so that the aluminum alloy is applied in the thinning field of the structural engineering material, namely, the mechanical property of the aluminum-based carbon fiber metal laminated plate is far lower than that of the stainless steel-based carbon fiber metal laminated plate when the low-thickness characteristic of the laminated plate is pursued. In addition, as the "hand-torn steel" is gradually mass produced, it is extremely reasonable and effective that the stainless steel ultra-thin strip is used as a metal raw material of the high-strength ultra-thin carbon fiber laminate to reduce the plate thickness. On this basis, many studies have shown that the surface treatment of the metal matrix is extremely effective for improving the interlayer performance of the laminated sheet, which is extremely advantageous for improving the effectiveness of the carbon fiber metal laminated sheet compounding mechanism. However, in the past few decades, there have been many studies on surface modification by anodic oxidation of valve metals (e.g., aluminum, titanium, zirconium, niobium, tantalum, and tungsten), but few studies on surface modification of non-valve metals (e.g., stainless steel and iron) other than magnesium. Therefore, development of related preparation technology of stainless steel-based high-performance FMLs to replace the traditional high-dead-weight metal alloy is not enough.
For FMLs composite structures, when impacted to cause cracks in a metal substrate, the cracks do not propagate rapidly in the initial direction due to the presence of the interlayer resin-based carbon fiber layers, resulting in direct structural failure. In practical cases, cracks can expand to the layers, so that the cracks can remain in the composite material structure for a long time, thereby avoiding the early explosion or failure of FMLs caused by initial cracks, and the bridging effect of the cracks is the biggest advantage of the FMLs and is also a source of excellent mechanical properties of the FMLs.
Therefore, the interlayer connection performance of the epoxy resin/stainless steel is effectively improved, and the problem of weak connection between the metal matrix material and the resin-based carbon fiber reinforcement in the stainless steel-based carbon fiber metal laminated plate can be effectively solved.
Disclosure of Invention
The invention mainly aims to overcome the defects in the prior art, and aims to solve the technical problem of weak connection between stainless steel Bao Daiji FMLs layers, and provides a method for preparing a carbon fiber/stainless steel thin layer laminated plate based on an anodic oxidation process.
The design concept of the invention is as follows: firstly, carrying out direct current anodic oxidation on a stainless steel thin belt in an ethylene glycol-based electrolyte, and carrying out surface modification to obtain a porous oxide layer structure; then, the laid stainless steel thin belt and the carbon fiber prepreg belt are subjected to hot pressing, solidification and molding at a certain temperature and pressure; on the basis, the stainless steel thin strip subjected to direct current anodic oxidation surface modification is subjected to secondary surface modification in a silane coupling agent hydrolysis solution, and chemical bonding is introduced between the epoxy resin-based carbon fiber prepreg strip and the stainless steel thin strip. The anodic oxidation porous oxide layer structure can improve the infiltration degree of epoxy resin and introduce a mechanical locking effect, and the introduction of the silane coupling agent can improve the fluidity of the epoxy resin and simultaneously introduce rich chemical bonding on the surface of the prepreg tape and the surface of the stainless steel thin tape, so that the interlayer connection performance of the stainless steel thin tape and the carbon fiber prepreg tape is greatly enhanced due to the existence of the three reinforcing mechanisms.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method for preparing a carbon fiber/stainless steel sheet laminate based on an anodic oxidation process, comprising the steps of:
s1, removing greasy dirt on the surface of a stainless steel thin belt, sequentially adopting an acetone solution and an ethanol solution to carry out ultrasonic cleaning for 20 minutes, then airing, and preparing an ethylene glycol-based electrolyte for later use;
s2, carrying out direct-current anodic oxidation surface modification treatment on the stainless steel thin strip subjected to ultrasonic cleaning in ethylene glycol-based electrolyte, wherein the construction modification of the anodic oxidation surface porous oxide layer has the following effects: the porous oxide layer is constructed by modifying and preprocessing the anodic oxidation surface, so that the surface roughness of the stainless steel can be increased, the surface energy can be increased, meanwhile, rich hydroxyl groups are introduced to the surface of the oxide layer, the synergistic effect of morphology and chemical bond effect can be achieved, and the infiltration degree of epoxy resin in the prepreg tape on the surface of the stainless steel thin tape can be greatly improved;
s3, sequentially stacking a plurality of layers of carbon fiber prepreg tapes along the 0-degree direction to form a carbon fiber prepreg tape reinforcement, sequentially staggering and stacking the stainless steel thin tape subjected to the direct-current anodic oxidation surface modification treatment in the step S2 and the carbon fiber prepreg tape reinforcement, and enabling the 0-degree fiber direction of the carbon fiber prepreg tape reinforcement to be consistent with the rolling direction of the stainless steel thin tape to prepare a laminated plate blank, wherein the upper surface and the lower surface of the laminated plate blank are the stainless steel thin tape;
s4, placing the laminated plate blank obtained in the step S3 into a hot-press die for hot-press forming, wherein the whole hot-press forming process is carried out under the pressure condition of 0.6 MPa:
the first stage: heating from room temperature to 80 ℃, and preserving heat for 30 minutes, wherein the heating rate is 3.0 ℃/min;
and a second stage: heating from 80 ℃ to 100 ℃, and preserving heat for 30 minutes, wherein the heating rate is 3.0 ℃/min;
and a third stage: heating from 100 ℃ to 120 ℃, and preserving heat for 30 minutes, wherein the heating rate is 3.0 ℃/min;
fourth stage: cooling from 120 ℃ to room temperature at a cooling rate of 0.5 ℃/min;
the carbon fiber/stainless steel sheet laminate was produced.
Further, the thickness of the stainless steel thin belt is 0.015 mm-0.02 mm, the stainless steel thin belt is made of 304L stainless steel, and the 304L stainless steel comprises the following specific chemical components in parts by weight: cr:17wt.% to 18wt.%, ni: 8-11 wt.%, mn < 2wt.%, si < 1wt wt.%, the balance being Fe and unavoidable impurities;
the thickness of the single-layer carbon fiber prepreg tape is 0.06-0.125 mm, and the single-layer carbon fiber prepreg tape is prepared by hot press molding of epoxy resin and unidirectional continuous carbon fiber reinforced materials.
Further, in the step S1, the preparation method of the ethylene glycol-based electrolyte includes: 0.37g of ammonium fluoride was mixed with 0.18mL of deionized water, and 100mL of ethylene glycol was added to the mixture, followed by stirring for 10 minutes, to obtain an ethylene glycol-based electrolyte. The preparation of the glycol-based electrolyte is adjusted according to the usage amount, and the usage amount is required to submerge the thin plate with the depth direction dimension of (design dimension-5) mm, so that the electrolyte is prevented from corroding the working electrode conductive clamp.
Further, in the step S2, the direct current anodic oxidation surface modification treatment includes the steps of:
firstly, fixing a stainless steel thin belt subjected to S1 ultrasonic cleaning on a working electrode, adopting a graphite electrode as a counter electrode, wherein the shape and the size of the graphite electrode are not smaller than those of the stainless steel thin belt, and fixing the distance between the two electrodes to be 30-60 mm;
secondly, setting a direct current power supply in a constant voltage mode, adjusting output voltage to 50-60V, adjusting anodic oxidation time to 30 minutes-5 hours so as to change the aperture and the hole depth of a formed porous oxide layer, bring different infiltration effects, further change interlayer connection performance, and continuously stirring electrolyte (adopting a magnetic stirrer) during anodic oxidation reaction so as to ensure uniform ion distribution in the electrolyte and promote the formation of a porous structure;
thirdly, taking out the stainless steel thin strip after anodic oxidation is completed, flushing with absolute ethyl alcohol, and drying with cold air;
finally, annealing the stainless steel thin strip in a muffle furnace at a heating temperature of 300 ℃ at a heating speed of 1 ℃/min for 2 hours; and cooling to room temperature along with the annealing treatment to obtain the stainless steel thin strip with the porous oxide layer active surface.
Further, in the step S2, a silane coupling agent (Y-R-SiX 3) hydrolysate is prepared, and then the stainless steel ribbon after the direct current anodic oxidation surface modification treatment is put into the silane coupling agent hydrolysate for secondary surface modification treatment. The silane coupling agent is introduced to connect the enhancement layer, and has the following effects: 1. the fluidity of the epoxy resin is improved, and the embedding effect of the epoxy resin and the surface of the stainless steel thin strip is further improved; 2. meanwhile, the silane coupling agent containing inorganic and organic functional groups can simultaneously form strong chemical bonding with inorganic stainless steel surfaces and organic epoxy resin respectively, and finally bridging is formed between the stainless steel thin belt and the epoxy resin, so that the interlayer bonding strength of the stainless steel thin belt and the carbon fiber prepreg belt is improved.
Further, the preparation method of the silane coupling agent hydrolysate comprises the following steps: weighing 90wt.% of ethanol, 1wt.% to 5wt.% of silane coupling agent and 5wt.% to 9wt.% of deionized water according to the weight ratio, stirring for 15 minutes to 25 minutes after mixing, wherein the mixture cannot be uniformly mixed when the stirring time is too short, and the hydrolysis liquid of the silane coupling agent can be hydrolyzed before use when the stirring time is too long; acetic acid is added into the mixed solution dropwise after uniform mixing until the pH value of the solution is 4 so as to meet the conditions of hydrolysis reaction, and then continuously stirring and uniformly mixing to completely carry out the hydrolysis reaction, thus obtaining the silane coupling agent hydrolysate.
Further, the secondary surface modification treatment includes the steps of: soaking the stainless steel thin strip with the porous oxide layer active surface in silane coupling agent hydrolysis liquid, and carrying out ultrasonic treatment for 10-20 minutes to ensure that the coupling agent hydrolysis liquid can fully infiltrate into the porous oxide layer structure on the surface of the stainless steel thin strip; taking out after ultrasonic treatment, standing for 24-48 hours at room temperature, so that the coupling agent hydrolysate immersed in the porous oxide layer structure on the surface of the stainless steel thin strip can fully complete hydrolysis reaction, form richer Si-O-metal covalent bonds with the porous oxide layer on the surface of the stainless steel, and fully expose the organic end at the other end of the coupling agent on the surface of the stainless steel thin strip (to be connected with epoxy resin in the carbon fiber prepreg strip), thereby preparing the stainless steel thin strip to be connected, which is subjected to surface treatment of the silane coupling agent.
Further, in the step S4, the carbon fiber prepreg tapes are fully thawed and then unpacked for use, and the carbon fiber prepreg tape reinforcement between adjacent stainless steel thin tapes at least comprises 8 layers of carbon fiber prepreg tapes.
Further, in the step S5, the heating temperature range of the hot-pressing mold is room temperature to 300 ℃, the temperature precision is ±1 ℃, the maximum pressure is 150KN, and the pressure, the temperature and the dwell time can be adjusted; the hot pressing plate of the hot pressing die is made of stainless steel, and the effective use size of the hot pressing plate is 400mm x 400mm; the leveling precision of the working table surface in the hot-pressing die is +/-0.01 mm.
Compared with the prior art, the invention has the beneficial effects that:
the invention improves the interlayer bonding performance of the stainless steel-based carbon fiber reinforced laminated plate by utilizing the anodic oxidation surface modification process, can further adopt a silane coupling agent to carry out secondary surface modification on the basis, and the porous oxide layer can provide a mechanical locking effect and improve the interlayer bonding capability in physical aspect. Among them, the silane coupling agent provides silanol groups derived from the hydrolysis of alkoxysilane, which can be used to form covalent bonds with-OH groups on the metal surface, and thus bond well with the metal surface. Meanwhile, the reactive organic functional group at the other end of the silane coupling agent may react with the resin, thereby bonding the metal to the polymer matrix through a chemical bond.
(1) Compared with other high-energy surface modification processes such as laser pulse, plasma lattice and the like, the process for constructing the anodic oxide film by electrochemical etching modification has the advantages of simple operation, low cost, less damage to the substrate and no specific requirement on the size of the metal substrate.
(2) Through the construction of the porous oxide layer structure, the infiltration degree of the stainless steel surface to the epoxy resin is improved, the mechanical locking effect of the porous oxide layer structure and the epoxy resin is also introduced, and the introduction of the coupling agent introduces rich chemical bonding on the epoxy resin surface and the stainless steel ribbon surface, so that the bonding strength of the stainless steel ribbon/carbon fiber prepreg is greatly improved due to the existence of the three reinforcing mechanisms.
(3) The metallic material surface coupling agent is modified to form the resin embedded oxide film/coupling agent flexible interface layer, so that the problems of interlayer mismatch and residual stress caused by inconsistent corrosion and thermal expansion coefficients are overcome to a certain extent.
(4) Under the condition of simple curing temperature, the interlayer shearing performance of the stainless steel thin strip/carbon fiber laminated plate can reach 26.5MPa.
(5) Compared with an aluminum alloy-based carbon fiber metal laminated plate, the carbon fiber/stainless steel Bao Daiceng laminated plate prepared based on the anodic oxidation process can effectively reduce the thickness of the metal-based carbon fiber metal laminated plate on the premise of ensuring the mechanical property.
Drawings
FIG. 1 is a schematic illustration of the preparation process of the present invention;
FIG. 2 is a schematic diagram of a direct current anodic oxidation surface modification treatment;
FIG. 3 is a surface topography of a stainless steel thin strip anodized porous oxide film; in fig. 3, the continuous channels are walls of porous oxide layers, and the discontinuous holes are vertical porous oxide layers;
FIG. 4 is a schematic view of a cross-sectional front view of a laminate;
FIG. 5 is a graph showing the interlayer performance change of a stainless steel ribbon/carbon fiber laminate in an anodized surface modification process; wherein 0 represents a blank group, namely a laminate sample obtained by subjecting a stainless steel strip to only a cleaning treatment;
FIG. 6 is a schematic diagram of secondary surface modification to improve interlayer bonding strength;
FIG. 7 is a graph of the surface morphology of a porous oxide film of a stainless steel ribbon after secondary surface modification;
FIG. 8 is an infrared spectrum of a stainless steel ribbon after secondary surface modification;
FIG. 9 is a graph showing interlayer performance change of a stainless steel ribbon/carbon fiber laminate in a secondary surface modification process; wherein 0 represents a blank group, i.e., a laminate sample of example 1 which was not secondarily surface-modified with a silane coupling agent.
In the figure: 1 is a stainless steel thin belt, 2 is a carbon fiber prepreg belt reinforcement.
Description of the embodiments
The invention is described in further detail below with reference to the drawings and examples.
Examples
Stainless steel thin tape 1 and carbon fiber prepreg tape reinforcement 2 are selected as raw materials of the laminate. In example 1, the thickness of the stainless steel strip 1 was 0.02mm, and the stainless steel strip 1 was made ofThe stainless steel is 304L stainless steel, and the 304L stainless steel comprises the following specific chemical components in parts by weight: cr:17wt.% to 18wt.%, ni: 8-11 wt.%, mn < 2wt.%, si < 1wt wt.%, the balance being Fe and unavoidable impurities; the thickness of the single-layer carbon fiber prepreg tape is 0.125mm, and the single-layer carbon fiber prepreg tape is prepared by hot-press molding of epoxy resin and T700 unidirectional continuous carbon fiber reinforced material, wherein the volume fraction of carbon fibers is 40%, and the fiber mass per unit area is 100g/m 2 The mass of the carbon fiber prepreg tape per unit area is 185g/m 2 Volatile content < 1 wt%. The selected silane coupling agent has the brand KH550 and the molecular formula NH 2 CH 2 CH 2 CH 2 Si(OC 2 H 5 ) 3 。
The method for preparing the carbon fiber/stainless steel laminate based on the anodic oxidation process as shown in fig. 1 comprises the following steps:
s1, cutting a stainless steel thin belt 1, wherein the size of the stainless steel thin belt is 100mm or 0.02mm, removing greasy dirt on the surface of the stainless steel thin belt 1, sequentially adopting an acetone solution and an ethanol solution to ultrasonically clean for 20 minutes, then airing, and meanwhile preparing an ethylene glycol-based electrolyte for later use;
the preparation method of the ethylene glycol-based electrolyte comprises the following steps: mixing 0.37g of ammonium fluoride with 0.18mL of deionized water, adding 100mL of ethylene glycol into the mixture, stirring for 10 minutes to obtain ethylene glycol-based electrolyte, adjusting the preparation amount of the electrolyte according to the use amount, immersing the thin plate with the depth direction size of 95mm, and fixing a working electrode conductive clamp by using a stainless steel thin strip 1 with the height of 5mm for fixing the working electrode conductive clamp to prevent the electrolyte from corroding the working electrode conductive clamp, wherein the electrolyte is 679mL after adjustment.
S2, carrying out direct current anodic oxidation surface modification treatment on the stainless steel thin strip 1 subjected to ultrasonic cleaning in ethylene glycol-based electrolyte, wherein the principle of improving interlayer bonding strength through direct current anodic oxidation surface modification is shown in a figure 2, and the method comprises the following steps of:
firstly, fixing a stainless steel thin strip 1 subjected to ultrasonic cleaning in S1 on a working electrode, adopting a graphite electrode (120 mm is equal to 3 mm) as a counter electrode, wherein the shape and the size of the graphite electrode are not smaller than those of the stainless steel thin strip 1, fixing the distance between the two electrodes to be 35mm, and adjusting the use amount of electrolyte to enable the depth dimension of a thin plate immersed in the electrolyte to be 95mm;
secondly, setting a direct current power supply in a constant voltage mode, adjusting the output voltage to 60V, adjusting the anodic oxidation time to 3 hours, and continuously stirring electrolyte during the anodic oxidation reaction to form a porous oxide layer with the aperture of about 25 mu m;
taking out the stainless steel thin strip 1 after anodic oxidation is finished, flushing with absolute ethyl alcohol, and drying with cold air;
finally, annealing the stainless steel thin strip 1 in a muffle furnace at a heating temperature of 300 ℃ at a heating speed of 1 ℃/min for 2 hours; and cooling to room temperature along with the annealing treatment, so as to obtain the stainless steel thin strip 1 with the active surface of the porous oxide layer, wherein the surface morphology of the anodic oxidation porous oxide film of the stainless steel thin strip is shown in figure 3.
S3, unsealing the carbon fiber prepreg tapes after full thawing, sequentially stacking a plurality of layers of carbon fiber prepreg tapes along the direction of 0 degree to form a carbon fiber prepreg tape reinforcement 2, sequentially staggering and stacking the stainless steel thin tape 1 subjected to the direct-current anodic oxidation surface modification treatment in the step S2 and the carbon fiber prepreg tape reinforcement 2, and enabling the direction of 0 degree fiber of the carbon fiber prepreg tape reinforcement 2 to be consistent with the rolling direction of the stainless steel thin tape 1 to prepare a laminated plate blank, wherein the upper surface and the lower surface of the laminated plate blank are both the stainless steel thin tape 1.
S4, placing the laminated plate blank obtained in the step S3 into a hot-pressing die for hot-pressing forming, wherein the heating temperature of the hot-pressing die ranges from room temperature to 300 ℃, the temperature precision is +/-1 ℃, the maximum pressure is 150KN, and the pressure, the temperature and the pressure maintaining time can be adjusted; the hot pressing plate of the hot pressing die is made of stainless steel, and the effective use size of the hot pressing plate is 400mm x 400mm; the leveling precision of the working table surface in the hot-pressing die is +/-0.01 mm, and the whole hot-pressing forming process is carried out under the pressure condition of 0.6 MPa:
the first stage: heating from room temperature to 80 ℃, and preserving heat for 30 minutes, wherein the heating rate is 3.0 ℃/min;
and a second stage: heating from 80 ℃ to 100 ℃, and preserving heat for 30 minutes, wherein the heating rate is 3.0 ℃/min;
and a third stage: heating from 100 ℃ to 120 ℃, and preserving heat for 30 minutes, wherein the heating rate is 3.0 ℃/min;
fourth stage: cooling from 120 ℃ to room temperature at a cooling rate of 0.5 ℃/min;
the stainless steel ribbon/carbon fiber laminate was produced with a front cross-sectional structure as shown in fig. 4.
Short beam shearing experiments of the stainless steel thin belt/carbon fiber laminated plate were carried out on an electronic universal tester according to the standard of ASTM D2344 Standard Test Method for Short-Beam Strength of Polymer Matrix Composite Materials and Their Laminates, and interlayer shearing strength was calculated according to the following formula (1), so as to measure interlayer shearing performance of the stainless steel thin belt/carbon fiber laminated plate. Three-point loading is carried out by adopting a simply supported beam, the loading speed is 1 mm/min, the diameter D of a pressure head is=6 mm, the straight D of a support is=6 mm, the ratio of the span to the thickness is 4:1, and the length of a sample is ensured not to fall in the loading force process.
In the method, in the process of the invention,Pmaximum load (unit: N) for sample failure;bsample width (in mm);hsample thickness (in mm);τ s the shear strength between layers of the sample (unit: MPa).
The bonding strength of the laminate was 21.4MPa (corresponding ordinate value when the abscissa anodic oxidation time was 3h in FIG. 5) as measured by the above-mentioned short beam shearing test, and the bonding strength (15.3 MPa) of the laminate sample (blank control) without any surface treatment was improved by 46.4% (as shown in FIG. 5).
Examples
The method for preparing a carbon fiber/stainless steel laminate based on the anodic oxidation process as shown in fig. 1 is different from example 1 in that: the stainless steel thin strip subjected to the direct current anodic oxidation surface modification treatment is placed into a silane coupling agent hydrolysate for secondary surface modification treatment.
The preparation method of the silane coupling agent hydrolysate comprises the following steps: weighing 90wt.% of ethanol, 1wt.% to 5wt.% of silane coupling agent and 5wt.% to 9wt.% of deionized water according to the weight ratio, mixing, stirring for 15 minutes to 25 minutes, and dripping acetic acid into the mixed solution after uniform mixing until the pH value of the solution is 4, so as to obtain the silane coupling agent hydrolysate.
The principle of improving the interlayer bonding strength by secondary surface modification is shown in fig. 6, and the secondary surface modification treatment comprises the following steps: soaking the stainless steel thin strip with the porous oxide layer active surface in silane coupling agent hydrolysis liquid, carrying out ultrasonic treatment for 10-20 minutes, taking out after ultrasonic treatment is finished, and standing for 24-48 hours at room temperature to obtain the stainless steel thin strip to be connected, which is subjected to surface treatment by the silane coupling agent, wherein the surface morphology graph of the porous oxide film after secondary surface modification is shown in fig. 7, the infrared graph after secondary surface modification is shown in fig. 8, and the formation of Si-O-Fe covalent bonds indicates that the silane coupling agent forms effective modification on the stainless steel surface.
The bonding strength of the laminated plate measured by a short beam shearing experiment is 26.5MPa (corresponding ordinate value when the mass percentage of the silane coupling agent is 3% in the abscissa of fig. 9), which is improved by 23.8% compared with the bonding strength (21.4 MPa) of the laminated plate pattern prepared in example 1 (as shown in fig. 9); the bonding strength (15.3 MPa) of the laminate sample (blank control) without any surface treatment was improved by 73.2%.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A method for preparing a carbon fiber/stainless steel sheet laminate based on an anodic oxidation process, comprising the steps of:
s1, removing greasy dirt on the surface of a stainless steel thin belt, sequentially adopting an acetone solution and an ethanol solution to carry out ultrasonic cleaning for 20 minutes, then airing, and preparing an ethylene glycol-based electrolyte for later use;
s2, carrying out direct-current anodic oxidation surface modification treatment on the stainless steel thin strip subjected to ultrasonic cleaning in ethylene glycol-based electrolyte;
s3, sequentially stacking a plurality of layers of carbon fiber prepreg tapes along the 0-degree direction to form a carbon fiber prepreg tape reinforcement, sequentially staggering and stacking the stainless steel thin tape subjected to the direct-current anodic oxidation surface modification treatment in the step S2 and the carbon fiber prepreg tape reinforcement, and enabling the 0-degree fiber direction of the carbon fiber prepreg tape reinforcement to be consistent with the rolling direction of the stainless steel thin tape to prepare a laminated plate blank, wherein the upper surface and the lower surface of the laminated plate blank are the stainless steel thin tape;
s4, placing the laminated plate blank obtained in the step S3 into a hot-press die for hot-press forming, wherein the whole hot-press forming process is carried out under the pressure condition of 0.6 MPa:
the first stage: heating from room temperature to 80 ℃, and preserving heat for 30 minutes, wherein the heating rate is 3.0 ℃/min;
and a second stage: heating from 80 ℃ to 100 ℃, and preserving heat for 30 minutes, wherein the heating rate is 3.0 ℃/min;
and a third stage: heating from 100 ℃ to 120 ℃, and preserving heat for 30 minutes, wherein the heating rate is 3.0 ℃/min;
fourth stage: cooling from 120 ℃ to room temperature at a cooling rate of 0.5 ℃/min;
the carbon fiber/stainless steel sheet laminate was produced.
2. The method for preparing a carbon fiber/stainless steel sheet laminate based on an anodic oxidation process according to claim 1, wherein: the thickness of the stainless steel thin belt is 0.015 mm-0.02 mm, the stainless steel thin belt is made of 304L stainless steel, and the 304L stainless steel comprises the following specific chemical components in parts by weight: cr:17wt.% to 18wt.%, ni: 8-11 wt.%, mn < 2wt.%, si < 1wt wt.%, the balance being Fe and unavoidable impurities;
the thickness of the single-layer carbon fiber prepreg tape is 0.06-0.125 mm, and the single-layer carbon fiber prepreg tape is prepared by hot press molding of epoxy resin and unidirectional continuous carbon fiber reinforced materials.
3. The method for preparing a carbon fiber/stainless steel sheet laminate based on an anodic oxidation process according to claim 1, wherein: in the step S1, the preparation method of the ethylene glycol-based electrolyte comprises the following steps: 0.37g of ammonium fluoride was mixed with 0.18mL of deionized water, and 100mL of ethylene glycol was added to the mixture, followed by stirring for 10 minutes, to obtain an ethylene glycol-based electrolyte.
4. The method for preparing a carbon fiber/stainless steel sheet laminate based on an anodic oxidation process according to claim 1, wherein: in the step S2, the direct current anodic oxidation surface modification treatment includes the steps of:
firstly, fixing a stainless steel thin belt subjected to S1 ultrasonic cleaning on a working electrode, adopting a graphite electrode as a counter electrode, wherein the shape and the size of the graphite electrode are not smaller than those of the stainless steel thin belt, and fixing the distance between the two electrodes to be 30-60 mm;
secondly, setting a direct current power supply in a constant voltage mode, adjusting the output voltage to 50-60V, adjusting the anodic oxidation time to 30 minutes-5 hours, and continuously stirring electrolyte during the anodic oxidation reaction;
thirdly, taking out the stainless steel thin strip after anodic oxidation is completed, flushing with absolute ethyl alcohol, and drying with cold air;
finally, annealing the stainless steel thin strip in a muffle furnace at a heating temperature of 300 ℃ at a heating speed of 1 ℃/min for 2 hours; and cooling to room temperature along with the annealing treatment to obtain the stainless steel thin strip with the porous oxide layer active surface.
5. The method for preparing a carbon fiber/stainless steel sheet laminate based on an anodic oxidation process according to claim 1, wherein: in the step S2, a silane coupling agent hydrolysate is prepared, and then the stainless steel thin strip subjected to direct current anodic oxidation surface modification treatment is placed into the silane coupling agent hydrolysate for secondary surface modification treatment.
6. The method for preparing a carbon fiber/stainless steel sheet laminate based on an anodic oxidation process according to claim 5, wherein: the preparation method of the silane coupling agent hydrolysate comprises the following steps: weighing 90wt.% of ethanol, 1wt.% to 5wt.% of silane coupling agent and 5wt.% to 9wt.% of deionized water according to the weight ratio, mixing, stirring for 15 minutes to 25 minutes, and dripping acetic acid into the mixed solution after uniform mixing until the pH value of the solution is 4, so as to obtain the silane coupling agent hydrolysate.
7. The method for preparing a carbon fiber/stainless steel sheet laminate based on an anodic oxidation process according to claim 5, wherein: the secondary surface modification treatment comprises the following steps: soaking the stainless steel thin strip with the porous oxide layer active surface in a silane coupling agent hydrolysis solution, and carrying out ultrasonic treatment for 10-20 minutes; and taking out after the ultrasonic treatment is finished, and standing for 24-48 hours at room temperature to obtain the stainless steel thin strip to be connected, wherein the stainless steel thin strip is subjected to surface treatment by the silane coupling agent.
8. A method of making a laminate using stainless steel ribbon and carbon fiber brazing as recited in claim 1, wherein: in the step S4, the carbon fiber prepreg tapes are unpacked after being fully thawed, and the carbon fiber prepreg tape reinforcement between the adjacent stainless steel thin tapes at least comprises 8 layers of carbon fiber prepreg tapes.
9. The method for preparing a carbon fiber/stainless steel sheet laminate based on an anodic oxidation process according to claim 1, wherein: in the step S5, the heating temperature range of the hot-pressing die is room temperature-300 ℃, the temperature precision is +/-1 ℃, the maximum pressure is 150KN, and the pressure, the temperature and the dwell time can be adjusted; the hot pressing plate of the hot pressing die is made of stainless steel, and the effective use size of the hot pressing plate is 400mm x 400mm; the leveling precision of the working table surface in the hot-pressing die is +/-0.01 mm.
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