CN103507203B - A kind of metal-resin composite and preparation method thereof - Google Patents
A kind of metal-resin composite and preparation method thereof Download PDFInfo
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- CN103507203B CN103507203B CN201210209465.9A CN201210209465A CN103507203B CN 103507203 B CN103507203 B CN 103507203B CN 201210209465 A CN201210209465 A CN 201210209465A CN 103507203 B CN103507203 B CN 103507203B
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- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14336—Coating a portion of the article, e.g. the edge of the article
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- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/1418—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the inserts being deformed or preformed, e.g. by the injection pressure
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- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14336—Coating a portion of the article, e.g. the edge of the article
- B29C45/14344—Moulding in or through a hole in the article, e.g. outsert moulding
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- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- ing And Chemical Polishing (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The invention provides a kind of metal-resin composite and preparation method thereof.Metal-resin composite comprises metal base and resin piece, some indentations are contained on the surface of described metal base, the width of described indentation is 10-200um, and the degree of depth of described indentation is 1um-200um, and the resin combination forming described resin piece is filled in described indentation.The metal-resin composite adhesion of preparation is strong, special can from the multi-direction raising adhesion such as horizontal and vertical after etching liquid process, to the vertical end contact combined, the anti-adhesion such as to fracture is more excellent, and method of the present invention is simple and easy to realize, applied range, for the development of industry is laid a good foundation.
Description
Technical field
The present invention relates to a kind of metal-resin composite and preparation method thereof.
Background technology
In the part manufacture field of automobile, household electrical appliance goods, industrial machine etc., require the integral molding techniques of metal and resin, current industry adopts adhesive under normal temperature or heating by combination integrated with synthetic resin for metal.Although adopt said method can prepare metal and integrally moulded complex, but adhesion is poor between the complex metal obtained according to these methods and plastic cement, and adhesive acid-fast alkali-proof poor performance, complex cannot carry out the surface treatments such as follow-up anodic oxidation.Thus, all the time, people are examining whether more reasonably by the engineering resin of high strength and the integrated method of the alloy of aluminium alloy and so on always.
Those skilled in the art is by having researched and proposed nanoprocessing treatment technology, nanoprocessing treatment technology (NMT) is exactly metal combination technology integrated with plastic cement, it passes through metal-surface nano process, allow plastic cement directly ejection formation on the metal surface, make metal and plastic cement can integrated molding.For effective combination of metal and plastic cement, nanometer forming technique is a kind of best methods, and can replace embedding injection conventional at present or zinc-aluminium, magnalium die casting, one can be provided to have price competition, high performance gold moulds integration product.Compared with bonding technique, NMT technology has obvious advantage, such as: the overall weight of minimizing product, excellent strength, working (machining) efficiency are high.NMT technology range of application contains vehicle, information technoloy equipment and 3C Product, and product can be allowed towards more frivolous, more miniature future development.
The existing integrated molding technology just like disclosing aluminium alloy and resin combination, adopt amine substance, such as: carbamate, one hydrazine hydrate, the aqueous solution of ethylenediamine etc. carries out surface treatment to aluminium alloy and obtains nano level micropore, erode away nano level hole, and amine groups is retained in aluminium alloy nano aperture, last injection moulding is by the reaction of amine groups and injected plastics material, resin and aluminum alloy junction are combined together, thus obtain the plastic-aluminum integration product of certain tensile shear strength, and adopt the technology that this type of amine substance corrodes, etching time is longer and hole that is aluminum alloy surface formation is too little, resin is difficult to direct injection moulding and enters nano level hole, reduce the bond strength of aluminium alloy and resin, i.e. stretch-proof poor-performing, the combination of resin and aluminium alloy simultaneously mainly relies on amine groups, the kind of the resin used is very limited, the resin that this technology can adopt at present only has PPS(polyphenylene sulfide), PA(polyamide), PPA(polyphthalamide resin), PBT(polybutylene terephthalate (PBT)) etc. four resinoids, practical ranges is also narrow, and the amine substance adopted is poisonous, there is volatile material, be unfavorable for safety in production, environmental-protecting performance is poor.
Also have and by anodic oxidation preparation, there is the aluminium oxide rete in the cave of diameter 0.05-0.08 micron in aluminum alloy surface, plastic-aluminum integration product is obtained again with resin-bonded, but the hole that the aluminum alloy surface that the method obtains is formed is too little and resin is difficult to direct injection moulding enters nano level hole, reduce the bond strength of aluminium alloy and resin, i.e. stretch-proof poor-performing.
Also have and directly corroded in aluminum alloy surface by the acidic etching liquid containing inorganic halogen compounds, then injection moulding obtains plastic-aluminum integration product, and adopt this type of etching solution to corrode the technology of aluminum alloy surface, there is the etchant concentration low time long, etchant concentration high exothermic heat of reaction is large, the bad control of temperature, and etch process step is numerous and diverse, is unfavorable for large-scale production, the sunk structure of etch processes is mostly in wedge shape simultaneously, after injection moulding, resin piece easily comes off, and the adhesion between metal and resin is poor.
Summary of the invention
The present invention in order to the weak technical problem of the adhesion of the metal and resin that solve metal-resin composite of the prior art, provide a kind of metal and resin-bonded power strong and easily prepare metal-resin composite of easy large-scale production and preparation method thereof.
First object of the present invention is to provide a kind of metal-resin composite, comprise metal base and resin piece, wherein, the surface of metal base is formed with some indentations, the width of described indentation is 10-200um, the degree of depth of described indentation is 1-200um, and the resin combination forming described resin piece is filled in described indentation.
Second object of the present invention is to provide the preparation method of above-mentioned metal-resin composite, comprises following steps:
S1, indentation: form some indentations on the surface of the metal base through pre-treatment and obtain the impressed metal base of tool;
S2, injection moulding: the impressed metallic substrate surface of tool resin combination being injection-moulded in step S1 gained, obtains metal-resin composite after shaping.
The present invention surprisingly finds can obtain metal and the strong metal-resin composite of resin piece adhesion by technology of the present invention, indentation of the present invention can well be combined with resin piece when injection moulding, metal and resin is made to have stronger adhesion, and score structure of the present invention is unique, during injection moulding, resin is also easier to enter, adhesion is strong, the present invention realizes the present invention by indentation, method is simple and easy to realize, and it is pollution-free, working environment is excellent, on metal appearance substantially without impact, synthetic resin is not also specially required, the scope of application is wider, be more suitable for large-scale production, for the development of metal-resin integration is laid a good foundation.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of metal-resin composite, comprise metal base and resin piece, the surface of described metal base is formed with some indentations, the width of described indentation is 10-200um, the degree of depth of described indentation is 1-200um, and the resin combination forming described resin piece is filled in described indentation, and metal and resin have good adhesion, and technique is simple and easy to large-scale production, pollution-free working environment is excellent.
The present invention is preferably laser scored, and laser scored economy is quick, and efficiency is high and environmental pollution is little.
Shape the present invention of indentation is not particularly limited, can have any shape, only needing can by the clamping of partial tree oil/fat composition within it, the shape that can be rule also can for irregular shape, can be level and smooth line also can be the line of non-flat cunning, in better situation, indentation can be selected from one or more in straight line, broken line, curve, polygon, circle, spirality or ellipse.Indentation can be one, namely only need carve, such as, for less face, only need carve a spirality or uninterrupted between the figure of scoring pattern that of being made up of continuous print line is more complicated or multiple repetition.Be generally multiple, namely under needing engraving how, be interrupted between multiple indentation, discrete described indentation is at the some indentation pattern of the surface composition of metal base, the indentation pattern of the present invention to composition is not particularly limited, can design according to actual conditions, such as straight line can be formed, broken line, curve, polygon, circular, spirality, oval, array, concentric circles group, one or more indentation pattern in sets of parallel or rice font, also the font etc. of other complexity can be formed, straight line wherein, broken line, curve, polygon, circular, the simple pattern such as spirality and ellipse refers to herein and is made up of multiple discrete snick, array can join together by four directions such as triangle, circle, rectangles the figure formed, sets of parallel the present invention longer straight line that can be indentation be longer straight line or be made up of multiple short indentation, then this multiple longer straight line is parallel to each other, and preferably it can be parallel to the limit of metal base simultaneously.Number the present invention of indentation pattern of composition does not limit, and can be a more complicated pattern, also can be multiple pattern, the relation the present invention between multiple pattern also limit, and can be the same or different.The unit indentation of composition indentation pattern also can be the same or different, such as, when indentation is multiple circle, concentric circles group can be formed in metallic substrate surface, also can form circular array, namely the center of circle of multiple indentation in a straight line, separate between circle and circle.
Length the present invention of indentation does not limit, and can design according to the size number of metal surface area and indentation.Preferably, the length of single indentation is greater than 1um, and the length of indentation generally refers to the length of carving herein, such as when multiple long linear indentation composition sets of parallel, namely refer to the length of the long straight line of every bar, when indentation is parallel to metal edges simultaneously, be generally slightly shorter than the metal length of side; When forming concentric circles group by multiple circular score line, namely refer to the girth of each circle; The total length of origin-to-destination is referred to when an indentation itself forms spirality.
Preferably, indentation comprises multiple, is covered with the surface that metal base need contact with resin piece, and between adjacent two indentations, minimum distance is 1-200um, optimizes the adhesion of metal and resin further.Preferably indentation is straight line further, and be parallel to each other between indentation, the distance between parallel indentation is 10-100um.
Indentation is the spill cutting formed in metallic substrate surface, preferably, the bottom surface of spill cutting and wall have micropore or pit, wherein, micropore is generally pore space structure, pit is generally surperficial collapsed configuration, the preferred structure of the present invention does not damage metallicity, by optimizing the wall construction of spill cutting, improve the bonded area of resin and metal body, improve the resin of melting to the compactedness on metal body surface, form resin and the horizontal and vertical solid of metal body to fill and combine, special in meticulous equipment such as handset shells, the end face plastic parts of such as mobile phone combines, contact surface only has 1-10mm wide, the width of part contact surface even only has 1-3mm, contact surface is little, and be the vertical combination of long structure, frangibility, stressed large structure member such as grade, the preferred technical scheme of the present invention is by multidirectional adhesion, particularly the lateral junction of the holes filling of facing the wall and meditating of spill cutting is made a concerted effort, problems can be solved preferably, resin is combined tightr with metallic matrix, greatly improve the adhesion of metal and resin, the not only bending that vertically combines of the stripping of anti-resin piece but also anti-elongated member, there is outstanding beneficial effect.
Preferably, the degree of depth of micropore or pit is 10nm-100um, forms resin and metal body horizontal and vertical solid and fills and combine, the adhesion of further raising metal and resin.
Metal the present invention do not limit, can be known to the skilled person various need with the metal of resin-bonded, select according to product, preferable alloy of the present invention is aluminium alloy or aluminium, better adhesion can be had with resin by technical scheme of the present invention, and be widely used.
Wherein, resin combination be can with the various resin combinations of corrupt split, the present invention is not particularly limited, and can select according to actual needs, such as, can be thermoplastic resin composition.Preferably, resin combination is selected from one or more in polyphenylene sulfide (PPS), poly-o-phenylenediamine (PPA), polybutylene terephthalate (PBT) or nylon (NYLON), better adhesion can be had with resin by technical scheme of the present invention, and be widely used.
As a further improvement on the present invention, fluidity improver can be adopted in thermoplastic resin, the fluid ability of resin can be improved, improve further metal and the adhesive force of resin and the injection moulding performance of resin.Under preferable case, with the thermoplastic resin of 100 weight portions for benchmark, the fluidity improver also containing 1-5 weight portion in described thermoplastic resin.Under preferable case, described fluidity improver is cyclic polyester.
Resin combination of the present invention can also containing other property-modifying additives etc., and the present invention is not particularly limited, and can arrange as required, such as, can also contain filler in resin combination.Described filler is the various fillers that those skilled in the art commonly use, such as, can be various fiberfill or powdery filler.Described fiberfill can be selected from one or more in glass fibre, carbon fiber and aramid fibre; Described powder-type filler can be selected from one or more in calcium carbonate, magnesium carbonate, silica, heavy barium sulfate, talcum powder, glass and clay.More preferably in situation, all there is the linear expansion coefficient close with metal base, in the present invention, with the matrix resin of 100 weight portions for benchmark for making the horizontal, longitudinal of plastics composite, fiberfill content is 50-150 weight portion, and the content of powder-type filler is 50-150 weight portion.
Thickness the present invention of the resin piece of injection moulding is not particularly limited, and can design as required, and the thickness of the resin piece be preferably formed can be 0.5 ~ 10mm.
Invention also provides the preparation method of above-mentioned metal-resin composite, comprise following steps:
S1, indentation: form some indentations on the surface of the metal base through pre-treatment and obtain the impressed metal base of tool.The method the present invention forming some indentations on the surface of the metal base through pre-treatment does not limit, such as can CNC, hand engraving or etching solution etching.It is laser scored that the method for the preferred indentation of the present invention is that laser engraving is formed, laser engraving can adopt and well known to a person skilled in the art various laser engraving machine, the present invention does not limit, preferably the power of laser engraving is 10 ~ 80w further, speed is 100 ~ 3000mm/s, frequency is 20 ~ 80kHz, engraving machine is put on the surface of the metal base through pre-treatment need carved after setting engraving parameter, at the pattern designed by metallic substrate surface carve, thus the obtained impressed metal base of surperficial tool.
Pre-treatment is the pretreatment procedure carried out metal surface that those skilled in the art commonly use, and generally comprises and carries out mechanical grinding or grinding removal surface significantly foreign matter, then carry out degreasing, cleaning to the processing wet goods that metal surface adheres to.Preferably, pre-treatment comprises polishes to metal surface, such as, can be: first adopt 100-400 object sand paper or put it in polishing machine and make the micron-sized aperture of generation to metal surface polishing.Then carry out the steps such as oil removing, the first washing, alkali cleaning, the second washing, neutralization, the 3rd washing successively, in ultrasonic wave, clean this metal with the various solvents that those skilled in the art commonly use, scavenging period 0.5-2h, remove the greasy dirt of metal surface; Then metal is placed in acid/alkaline aqueous solution, under Ultrasonic Conditions, washs metal surface.Described solvent can be ethanol or acetone.Described acid/alkaline aqueous solution is various acid/alkaline aqueous solutions that those skilled in the art commonly use, such as: can be hydrochloric acid, sulfuric acid, NaOH, potassium hydroxide etc.In the present invention, preferably carry out alkali cleaning with absolute ethyl alcohol by the sodium hydrate aqueous solution immersing 30-70g/L, temperature 40-80 DEG C after metal degreasing after washing wiped clean again, after 1 ~ 5min, taking-up is clean with deionized water rinsing, the HNO of rear 10-30%
3in carrying out and dedust, cleaner with deionized water rinsing.
Need metal base the present invention of pre-treatment not limit, can select according to product, such as, when metal base is aluminum alloy base material, aluminum alloy base material can use the various aluminium alloys of industrial standard 1000-7000 series matter or die casting level; Metal base described in the present invention be those skilled in the art commonly use various shapes, structure metal base, the present invention is not particularly limited.The various shapes of metal base, structure, complete by machining.
The present invention is preferred, also comprises and process in impressed for tool metal base immersion etching liquid after step S1 before step S2 injection moulding.By etching liquid, the impressed metal base of tool is corroded again, the spill cutting interior surface of metallic substrate surface and indentation is corroded, male and fomale(M&F) is formed in metal surface, in metallic substrate surface, the spill cutting bottom surface of indentation and side wall surface, form pit or micropore, the bowl configurations of pore space structure or surfaces collapse is particularly formed at the spill cutting side wall surface of indentation, optimize the pore space structure of spill cutting inside, during injection moulding, resin can enter metallic substrate surface simultaneously, in the spill cutting bottom surface of indentation and the micropore of side wall surface, not only improve the bonded area of resin and metal body, improve the resin of melting to the compactedness on metal body surface, and form resin and the horizontal and vertical solid of metal body and fill and combine, thus adhesion is improved greatly,
Etching liquid the present invention do not limit, and be generally the solution that can carry out corroding to metal pore-creating, the preferred etching liquid of the present invention is the acid solution that can corrode metal base.Preferred acidic solution is selected from one or more in hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid.H in preferred acidic solution
+concentration is 0.3-5mol/L, can be single acid solution, also can be composite solution, and can be such as aqueous hydrochloric acid solution, in aqueous hydrochloric acid solution, the mass percentage concentration of hydrochloric acid be 2wt% ~ 20wt%, more preferably 5wt% ~ 15wt%; Also can be phosphate aqueous solution, in phosphate aqueous solution, the mass percentage concentration of phosphoric acid be 2wt% ~ 30wt%, more preferably 5wt% ~ 20wt%.Optimize the wall construction of spill cutting and the outward appearance of metal base, can corrosion be made evenly, micropore or the pit of formation are more homogeneous, and the binding ability of resin piece and metal base can be made better, there is better tensile strength, the integration of composite metal is combined better.
Also comprise halogen acid salt and/or soluble copper salt in further preferred acidic solution, composition composite solution, optimizes etched surface.
When also comprising halogen acid salt in acid solution, high speed of fulfiling hole and quality can not only be ensured, and the deep-etching of acid to production equipment can be reduced, reduce production cost, prevent the pollution to environment, and ensure production environment.Wherein, solubility halogen acid salt is preferably soluble-salt hydrochlorate, and soluble-salt hydrochlorate the present invention do not limit, the various soluble-salt hydrochlorates that can be known to the skilled person, general and acid does not react, and produces precipitation and gas, and the performance not affecting acid is better.Preferred soluble-salt hydrochlorate is selected from one or more in sodium chloride, potassium chloride or aluminium chloride.Preferably, hydrochloride mass percentage concentration is in an acidic solution 0.1-10wt%, more preferably 1wt%-5wt%, improves the adhesion of metal and resin further.
When also comprising soluble copper salt in acid solution, can further improve speed of fulfiling hole and density.Wherein, soluble copper salt the present invention do not limit, the various soluble copper salts that can be known to the skilled person, the preferred soluble copper salt of the present invention is selected from one or more in copper chloride, copper sulphate or copper nitrate, preferably, soluble copper salt mass percentage concentration is in an acidic solution 0.01%-1%, more preferably 0.01wt%-0.5wt%, improves the adhesion of metal and resin further.
Wherein, immerse process in etching liquid and adopt the mode that well known to a person skilled in the art various immersion process, such as all or part of immersion etc., can multi-disc immersion also can a slice immerse, the present invention does not limit, preferably, immersing the temperature processed in etching liquid is 20-30 DEG C, more preferably 25-30 DEG C, and immersing the time processed in etching liquid is 2-60min, more preferably 2-30min, improves the adhesion of metal and resin further.
The number of times the present invention immersed also does not limit, preferably, immerse process in etching liquid and comprise in repeated multiple times immersion etching liquid and processing, each to immerse the time processed in etching liquid be 1-5min, clean by deionized water after process in each immersion etching liquid, the number of times of immersion can be 2 to 10 times.Cleaning can be put into rinsing bowl to clean 1-5min, or puts into rinsing bowl and place 1-5min.
S2, injection moulding: the impressed metallic substrate surface of tool resin combination being injection-moulded in step S1 gained, obtains metal-resin composite after shaping.Such as the metal base through indentation process can be placed in mould, then resin combination be injected mould and combine with the metal base through indentation process, after shaping, obtain metal-resin composite.
According to the preparation method of metal-resin composite provided by the invention, the method that the preparation method of described resin combination adopts those skilled in the art to commonly use physical blending obtains, mix by resin combination, by double screw extruder extruding pelletization, stand-by.
According to the preparation method of composite metal provided by the invention, filler, fluidity improver can also be added in described resin combination, mix, the resin combination that obtained performance is more excellent, thus make the horizontal, longitudinal of resin combination all have the linear expansion coefficient close with metal base.
Dried metal base is proceeded in mould, integrated treatment is carried out with obtained resin combination, composite metal provided by the invention can be obtained after shaping, in the present invention, described shaping method is injection mo(u)lding, be understandable that, the molding mode of metallo-plastic integration can be made all to can be used for the present invention, be not limited to the mode of injection mo(u)lding.The condition of preferred injection moulding is mould temperature 50 ~ 300 DEG C, nozzle temperature: 200 ~ 450 DEG C, dwell time: 1 ~ 50s, injection pressure: 50 ~ 300MPa, the injection time: 1 ~ 30s, time delay: 1 ~ 30s, cool time: 1 ~ 60s, more preferably mould temperature: 80 ~ 200 DEG C, nozzle temperature is: 200 ~ 350 DEG C, injection pressure is: 90 ~ 140MPa, dwell time: 1 ~ 10s, injection time: 3 ~ 10s, time delay: 15 ~ 30s, cool time: 15 ~ 25s, the thickness of the resin piece of formation is 0.5 ~ 10mm.
Can also carry out some modifications to metal base, such as surface modification treatment before impressed for tool metal base being placed in mould, the present invention preferably includes and impressed for tool metal base is soaked modification in water-soluble polymer.Water-soluble polymer is adsorbed on metal base, stay on metal base after drying, modification is carried out to metal base, it is organism simultaneously, good compatibility is had to resin, by water-soluble polymer, lipophile modification is carried out to metal base, resin is made more easily to enter the score structure of metal base, accelerate entering of casting resin, the adhesion of further raising metal and resin, and improve process efficiency and product yield further, and Polymer adsorption enters in indentation the air can effectively discharged in indentation, and during injection moulding, resin is more easily full of whole indentation.The temperature of preferred immersion modification is 15 DEG C-30 DEG C, more preferably 20-30 DEG C, and the time is 1-20min, more preferably 5-20min, optimizes modification face.Water-soluble polymer the present invention do not limit, the various water-soluble polymers that can be known to the skilled person, immerse in its solution by metal base, can adsorb on metal base, stay on metal base after drying, carry out modification to metal base, preferred water soluble polymer of the present invention is selected from one or more in polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylate, polymethylacrylic acid, poly-methyl acrylate, polyvinyl sulfonic acid, polyvinyl sulfonate, polystyrolsulfon acid or poly styrene sulfonate.Preferably, the concentration of water-soluble polymer is 1wt%-20wt%.
Preparation method of the present invention is simple, the technique of more existing employing adhesive simplifies production procedure, shorten the production time, and more existing nano surface hole injection moulding need adopt the method for acid liquid corrosion also to significantly reduce etching time, breach the restriction of resin types, direct injection moulding is only needed to realize after adopting the inventive method process, simultaneously good by adhesion between the resin piece of the metal-resin composite obtained by preparation method of the present invention and metal base, there is preferably tensile shear strength.
The metal-resin composite that the present invention obtains can directly use, and also can carry out some follow-up post processings as required, such as CNC(Digit Control Machine Tool processing), anodic oxidation, spraying etc., the present invention does not limit.
Below by specific embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment prepares aluminum alloy resin complex;
1, pre-treatment: by thick for commercially available 1mm 5052 aluminium alloy plates, be cut into the rectangular pieces of 15mm*80mm, put it into grinding in polishing machine, afterwards oil removing cleaning is carried out to it, then be alkali cleaning process 10s in the solution of 40g/L by it at 60 DEG C of sodium hydrate contents, clear water puts into the HNO that content is about 6wt% after cleaning
3in in neutralization chamber and 30s, rear clear water is cleaned, and obtains the aluminum alloy sheet through pre-treatment.
2, indentation: the laser work zone above-mentioned aluminum alloy sheet being placed in the LFS20 laser marking machine that Chinese workers' laser makes, laser machine power is regulated to be 20w, speed is 300mm/s, frequency is 20kHz, laser engraving on the face that aluminum alloy sheet needs injection moulding to contact, carve is parallel to the linear spill cutting on aluminium flake base, scoring length is 15mm, width and the degree of depth are 20um, on the face that aluminum alloy sheet needs injection moulding to contact, laser engraving goes out many linear pattern indentations be parallel to each other, adjacent indentations interval 20um, carve about 125 identical indentations on the face that 15mm*5mm is large.
3, etching liquid process: the aqueous hydrochloric acid solution 500ml preparing 6wt% in beaker, put into 25 DEG C of thermostats and be warming up to 25 DEG C, aforementioned gained aluminum alloy sheet 10PCS is immersed, taken out after 1min, put into the beaker that water is housed and soak 1min, once to etch vacuole, to add a bubble be a circulation, circulation like this 5 times, after last water soaking, aluminum alloy sheet is put into 80 DEG C of baking ovens and dry, obtain treated aluminum alloy sheet sample A1.
Employing field emission scanning electron microscope observes the cross section of the aluminum alloy sheet after above-mentioned process, and the spill cutting wall recording indentation has the dark micropore of 0.1-20um, and the aperture of micropore is 0.1-30um.
4, shaping: the aluminum alloy sheet A1 after drying is inserted in injecting molding die, injection moulding contains polyphenylene sulfide (PPS) resin combination of 20wt% glass fibre, and the rear equal demoulding also obtains strong bonded aluminium alloy together and the aluminum alloy resin complex S1 of resin combination after cooling.
Embodiment 2
The method identical with embodiment 1 is adopted to prepare aluminum alloy sheet sample A2 and aluminum alloy resin complex S2, unlike step 2 indentation: the laser work zone above-mentioned aluminum alloy sheet being placed in the LFS20 laser marking machine that Chinese workers' laser makes, laser machine power is regulated to be 20w, speed is 300mm/s, frequency is 20kHz, laser engraving on the face that aluminum alloy sheet needs injection moulding to contact, the spill cutting of carve circle, width and the degree of depth of indentation are 20um, on the face that aluminum alloy sheet needs injection moulding to contact, laser engraving goes out multiple circular concentric indentation, 20um is spaced apart between adjacent circular indentation, carve 70 indentations on the face that 15mm*5mm is large.
Embodiment 3
The method identical with embodiment 1 is adopted to prepare aluminum alloy sheet sample A3 and aluminum alloy resin complex S3, unlike step 2 indentation: the laser work zone above-mentioned aluminum alloy sheet being placed in the LFS20 laser marking machine that Chinese workers' laser makes, laser machine power is regulated to be 20w, speed is 300mm/s, frequency is 20kHz, laser engraving on the face that aluminum alloy sheet needs injection moulding to contact, carve is parallel to the linear pattern spill cutting on aluminium flake base, scoring length is 15mm, width and the degree of depth are 10um, and the indentation pattern of formation is as embodiment 1.
Embodiment 4
The method identical with embodiment 1 is adopted to prepare aluminum alloy sheet sample A4 and aluminum alloy resin complex S4, unlike step 2 indentation: the laser work zone above-mentioned aluminum alloy sheet being placed in the LFS20 laser marking machine that Chinese workers' laser makes, laser machine power is regulated to be 20w, speed is 300mm/s, frequency is 20kHz, laser engraving on the face that aluminum alloy sheet needs injection moulding to contact, carve is parallel to the linear pattern spill cutting on aluminium flake base, scoring length is 15mm, width and the degree of depth are 30um,, the indentation pattern of formation is as embodiment 1.
Embodiment 5
The method identical with embodiment 1 is adopted to prepare aluminum alloy sheet sample A5 and aluminum alloy resin complex S5, unlike the process of step 3 etching liquid: the mixed aqueous solution 500ml preparing the hydrochloric acid of 6wt% and the copper chloride of 0.05wt% in beaker, put into 25 DEG C of thermostats and be warming up to 25 DEG C, aforementioned gained aluminum alloy sheet 10PCS is immersed, taken out after 1min, put into the beaker that water is housed and soak 1min, once to etch vacuole, to add a bubble be a circulation, circulation like this 5 times, after last water soaking, aluminum alloy sheet is put into 80 DEG C of baking ovens and dry.The spill cutting wall adopting the method identical with embodiment 1 to record indentation has the dark micropore of about 0.1-25um, and the aperture of micropore is 0.1-40um.
Embodiment 6
Adopt the method identical with embodiment 1 prepare aluminum alloy sheet sample A6 and aluminum alloy resin complex S6, unlike without etching liquid process namely without step 3, directly by impressed for tool aluminum alloy sheet and resin injection moulding integrated molding.
Comparative example 1
1, pre-treatment: by thick for commercially available 1mm 5052 aluminium alloy plates, be cut into the rectangular pieces of 15mm*80mm, put it into grinding in polishing machine, rear oil removing cleaning is carried out to it, then be alkali cleaning process 10s in the solution of 40g/L by it at 60 DEG C of sodium hydrate contents, clear water puts into HNO after cleaning
3content is about in the neutralization chamber of 6wt% and 30s, and rear clear water is cleaned, and obtains the aluminum alloy sheet through pre-treatment.
2, etching liquid process: aluminum alloy base material being immersed in concentration is in the hydrochloric acid 500ml of 6wt%, put into 25 DEG C of thermostats and be warming up to 25 DEG C, aforementioned gained aluminum alloy sheet 10PCS is immersed, taken out after 1min, put into the beaker that water is housed and soak 1min, once to etch vacuole, to add a bubble be a circulation, circulation like this 5 times, after last water soaking, aluminum alloy sheet is put into 80 DEG C of baking ovens and dry, obtain treated aluminum alloy sheet sample DA1.
3, shaping: the aluminum alloy sheet after drying is inserted in injecting molding die, injection moulding contains polyphenylene sulfide (PPS) resin combination of 20wt% glass fibre, and the rear equal demoulding also obtains strong bonded aluminium alloy together and the aluminum alloy resin complex DS1 of resin combination after cooling.
Performance test:
The adhesion of aluminium alloy and resin: the aluminum alloy resin complex S1-S6 prepare embodiment 1-6 and comparative example 1 and DS1 is fixed on universal testing machine and carries out product extension test, in test result, maximum load can be considered the size of the adhesion between aluminium alloy and resin, and test result is as table 1.
Table 1
| Sample | Adhesion/N |
| S1 | 1253.20 |
| S2 | 1209.71 |
| S3 | 1398.39 |
| S4 | 1134.84 |
| S5 | 1301.68 |
| S6 | 718.35 |
| DS1 | 605.07 |
The aluminum alloy resin complex adhesion prepared of the present invention is strong as can be seen from the table, special can from the multi-direction raising adhesion such as horizontal and vertical after etching liquid process, to the vertical end contact combined, the anti-adhesion such as to fracture is more excellent, and method of the present invention is simple and easy to realize, applied range, for the development of industry is laid a good foundation.
Those skilled in the art easily know; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.Protection scope of the present invention is determined by claims.
Claims (27)
1. a metal-resin composite, is characterized in that, comprising: metal base and resin piece, and some indentations are contained on the surface of described metal base, and described indentation is level and smooth or non-level and smooth line; The width of described indentation is 10-200um, and the degree of depth of described indentation is 1um-200um, and the resin combination forming described resin piece is directly filled in described indentation; Described resin piece is moulding.
2. metal-resin composite according to claim 1, is characterized in that, described indentation is laser scored.
3. metal-resin composite according to claim 1, is characterized in that, described indentation is selected from one or more in straight line, broken line, curve, polygon, circle, spirality or ellipse.
4. metal-resin composite according to claim 3, is characterized in that, the length of described indentation is greater than 1um.
5. metal-resin composite according to claim 3, it is characterized in that, discrete described indentation at the some indentation pattern of the surface composition of metal base, described indentation pattern be selected from straight line, broken line, curve, polygon, circle, spirality, ellipse, array, concentric circles group, sets of parallel or rice font one or more.
6. metal-resin composite according to claim 1, is characterized in that, described indentation comprises multiple, is covered with the surface that metal base need contact with resin piece, and between adjacent two indentations, minimum distance is 1-200um.
7. metal-resin composite according to claim 6, is characterized in that, described indentation is straight line, is parallel to each other between described indentation, and the distance between described parallel indentation is 10-100um.
8. metal-resin composite according to claim 1, is characterized in that, described indentation is the spill cutting formed in metallic substrate surface, and bottom surface and the wall of described spill cutting have micropore or pit.
9. metal-resin composite according to claim 8, is characterized in that, the degree of depth of described micropore or pit is 10nm-100um.
10. metal-resin composite according to claim 1, is characterized in that, described metal is aluminium or aluminium alloy.
11. metal-resin composites according to claim 1, is characterized in that, described resin combination is selected from one or more in polyphenylene sulfide, poly-o-phenylenediamine, polybutylene terephthalate or nylon.
The preparation method of 12. 1 kinds of metal-resin composites as claimed in claim 1, is characterized in that, comprises following steps:
S1, indentation: form some indentations on the surface of the metal base through pre-treatment, obtains the impressed metal base of tool; Described indentation is level and smooth or non-level and smooth line; The width of described indentation is 10-200um, and the degree of depth of described indentation is 1um-200um;
S2, injection moulding: the impressed metallic substrate surface of tool resin combination being injection-moulded in step S1 gained, obtains metal-resin composite after shaping.
13. preparation methods according to claim 12, is characterized in that, the method for described indentation is laser engraving.
14. preparation methods according to claim 13, is characterized in that, the power of described laser engraving is 10-80w, and speed is 100 ~ 3000mm/s, and frequency is 20-80kHz.
15. preparation methods according to claim 12, is characterized in that, also comprise and processing in impressed for tool metal base immersion etching liquid, make the bottom surface of the spill cutting of indentation and wall have micropore or pit after described step S1 before step S2.
16. preparation methods according to claim 15, is characterized in that, described etching liquid is the acid solution that can corrode metal base.
17. preparation methods according to claim 16, is characterized in that, described acid solution is selected from one or more in hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid.
18. preparation methods according to claim 17, is characterized in that, H in described acid solution
+concentration is 0.3-5mol/L.
19. preparation methods according to claim 17, is characterized in that, also comprise halogen acid salt and/or soluble copper salt in described acid solution.
20. preparation methods according to claim 19, is characterized in that, also comprise hydrochloride in described acid solution, and described hydrochloride mass percentage concentration is in an acidic solution 0.1wt%-10wt%.
21. preparation methods according to claim 19, it is characterized in that, also comprise soluble copper salt in described acid solution, described soluble copper salt is selected from one or more in copper chloride, copper sulphate or copper nitrate, and soluble copper salt mass percentage concentration is in an acidic solution 0.01-1wt%.
22. preparation methods according to claim 15, is characterized in that, the temperature processed in described immersion etching liquid is 20-30 DEG C.
23. preparation methods according to claim 15, is characterized in that, the time processed in described immersion etching liquid is 2-60min.
24. preparation methods according to claim 15, is characterized in that, process to comprise repeatedly immersing in etching liquid to process in described immersion etching liquid, and the time processed in each immersion etching liquid is 1-5min, wash in each immersion etching liquid after process.
25. preparation methods according to claim 24, is characterized in that, the number of times of immersion is 2 to 10 times.
26. preparation methods according to claim 12, is characterized in that, described pre-treatment comprises polishes to metal surface, then carry out oil removing, the first washing, alkali cleaning, the second washing, neutralization, the 3rd water-washing step successively.
27. preparation methods according to claim 12, is characterized in that, the condition of described injection moulding is mould temperature 50 ~ 300 DEG C, nozzle temperature: 200 ~ 450 DEG C, dwell time: 1 ~ 50s, injection pressure: 50 ~ 300MPa, the injection time: 1 ~ 30s, time delay: 1 ~ 30s, cool time: 1 ~ 60s.
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| CN107953505A (en) * | 2016-10-14 | 2018-04-24 | 比亚迪股份有限公司 | A kind of metal-resin composite and its preparation method and application |
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