WO2017071463A1 - 铝件表面微刻蚀方法、铝件复合体及其制备方法 - Google Patents

铝件表面微刻蚀方法、铝件复合体及其制备方法 Download PDF

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Publication number
WO2017071463A1
WO2017071463A1 PCT/CN2016/101719 CN2016101719W WO2017071463A1 WO 2017071463 A1 WO2017071463 A1 WO 2017071463A1 CN 2016101719 W CN2016101719 W CN 2016101719W WO 2017071463 A1 WO2017071463 A1 WO 2017071463A1
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micro
treatment
aluminum
etching
aluminum member
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PCT/CN2016/101719
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English (en)
French (fr)
Inventor
唐国军
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欧朋达科技(深圳)有限公司
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Publication of WO2017071463A1 publication Critical patent/WO2017071463A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/20—Acidic compositions for etching aluminium or alloys thereof

Definitions

  • the present invention belongs to the technical field of materials, and in particular, to a micro-etching method for an aluminum member surface, an aluminum member composite body, and a preparation method thereof.
  • a metal composite material is a multiphase solid material in which a metal is combined with other materials having different physical properties and chemical properties.
  • One of the advantages of metal composites is the composite effect of their properties, that is, several different properties combined in one material to make them work together.
  • the design of one of the most suitable composite materials can be designed according to the requirements of use. Among them, aluminum composite materials such as aluminum plastic or resin composite materials are particularly prominent, and their composite lightweight requirements can be designed to meet the requirements of light and thin materials, and the corresponding mechanical properties can be obtained in most industries.
  • the existing aluminum plastic or resin composite material since it has a metal decorative layer or a support layer, and a resin or plastic layer as a support layer or a decorative layer, the resin or plastic layer is sprayed, injection molded or The method of stamping is connected to the metal layer, and the self-weight is small, and the same quality has a high quality appearance, and thus is widely used in various fields.
  • the object of the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide a surface micro-etching method for aluminum parts, to solve the harsh process conditions of the existing chemical etching method, complicated reagents, and metal parts such as aluminum parts.
  • the holes formed on the surface are relatively single, so that the bonding force between the metal and the resin or plastic is not ideal.
  • Another object of the present invention is to provide an aluminum member composite and a method for preparing the same, which solves the technical problem that the bonding force between the metal and the resin or plastic in the existing metal resin or plastic composite material is not ideal.
  • an embodiment of the present invention provides a method for micro-etching a surface of an aluminum member, comprising the following steps:
  • the aluminum member is sequentially subjected to a degreasing treatment, a neutralization treatment, and a pretreatment of an alkali etching treatment;
  • micro-etching process is performed by placing the pre-treated aluminum member in a micro-etching solution for micro-etching, and the micro-etching liquid comprises:
  • an embodiment of the present invention provides an aluminum member composite body, including an aluminum member and a plastic member combined with the aluminum member, wherein the aluminum member is a surface micro-etching method of the aluminum member according to the present invention.
  • the treated aluminum member is coated with an adhesive on at least the surface on which the micropores are etched and bonded to the plastic member.
  • an embodiment of the present invention provides a method for preparing an aluminum component composite, comprising the following steps: [0017] The surface of the aluminum component is processed according to the microetching method of the present invention, and the surface etching is obtained. Microporous aluminum parts
  • a plastic member or a resin member is formed or pressed on the surface of the aluminum member provided with the adhesive layer.
  • the surface micro-etching method of the aluminum piece of the present invention can effectively control the surface of the aluminum part by controlling the active component of the etching liquid and sequentially performing micro-etching and reaming treatment on the aluminum piece.
  • the micro-etching treatment enables various micropores to appear on the surface of the aluminum member, and can effectively control the micropore diameter to meet the requirements of the later processes such as injection molding, thereby effectively enhancing the relationship between the aluminum member and other materials or members such as resin or plastic. Bond strength.
  • the preparation method is easy to control, low in equipment requirements, stable in product quality, effective in improving production efficiency and reducing production cost.
  • the above-mentioned aluminum member composite of the present invention adopts the aluminum member treated by the surface etching method of the aluminum member of the present invention as a metal member, and bonds it to the plastic member or the resin member, since the surface of the aluminum member is diverse and conforms to the later stage.
  • the micropores required in the process such as injection molding, and therefore, the metal member and the plastic member or the resin member in the aluminum member composite of the present invention can be firmly bonded, thereby imparting excellent structural firmness and lightweight properties to the aluminum member composite of the present invention.
  • As well as the corresponding mechanical properties it is possible to prepare a lightweight and thin product as needed, which expands its application range.
  • the method for preparing the aluminum member composite of the present invention is directly formed or pressed directly after the step of forming a bonding layer on the aluminum member treated by the micro-etching method based on the aluminum member treated by the micro-etching method on the surface of the aluminum member.
  • the plastic member or the resin member so that the prepared aluminum member composite has excellent structural firmness and light performance and corresponding mechanical properties.
  • the preparation process conditions are easy to control, the equipment requirements are low, the product quality is stable, the production efficiency is effectively improved, and the production cost is reduced.
  • the weight percentages of the components mentioned in the description of the embodiments of the present invention may not only indicate the proportional relationship between the weights of the components, but also the specific content of each component, and therefore, as long as it is according to the present invention Real
  • the content of each component of the pharmaceutical composition in the specification of the invention is enlarged or reduced in proportion to the scope of the specification of the embodiment of the present invention.
  • the weights described in the description of the embodiments of the present invention may be ⁇ ⁇ , mg , g , kg , etc., which are well known in the art, and may of course be regarded as weight percentages.
  • An embodiment of the present invention provides a method for micro-etching a surface of an aluminum member with easy process control and forming multiple micropores
  • the aluminum surface micro-etching method comprises the following steps:
  • Step S01 sequentially removing the aluminum member by degreasing treatment, neutralization treatment, and alkali etching treatment;
  • Step S02 performing micro-etching on the surface of the pre-treated aluminum member to form micropores on the surface of the aluminum member;
  • Step S03 performing micropore washing treatment and reaming treatment on the micropores formed on the surface of the aluminum member.
  • the aluminum member in the above step S01 may be a cast or an intermediate member or the like, and in addition, the aluminum member may be a pure aluminum member or an aluminum alloy member.
  • the aluminum piece in the step S01 can effectively remove the oil stains and dust adhering to the surface of the aluminum piece, and the same can ensure that the surface of the aluminum part can be fully infiltrated by the subsequent treatment liquid, and the obtained Uniform processing.
  • the aluminum material is degreased in the step S01 by placing the aluminum member in a degreasing liquid for treatment.
  • the degreasing liquid comprises 20- 50 ml/L of MICRO CLEAN 302
  • the degreaser is an aqueous solution containing 20-50 ml/L of MICRO CLEAN 302.
  • the process conditions of the degreasing treatment are: temperature: 55-65 ° C; daytime: 2.5-10 mi n.
  • the MICRO CLEAN 302 contains a component comprising 45% by weight of sodium pyrophosphate, 35% by weight of sodium borate, and 20% by weight of sodium sulfate.
  • the MICRO CLEAN 302 is in a solid state during the specific use, and the solution can be formulated as needed during use.
  • the degreasing liquid may further comprise other ZTE aluminum cleaning agents.
  • the degreasing liquid comprises a mixture of sodium phosphate and sodium carbonate, in a specific embodiment, The concentration ratio of sodium phosphate to sodium carbonate is 20 g/L : (10-15) g/L.
  • the degreasing liquid may also be a mixture of MICRO CLEAN 302, other neutral aluminum cleaning agents.
  • the neutralization treatment in the step SOI is for removing the ash-removed and residual degreaser residues from the degreased aluminum member.
  • the neutralization process is to place the degreased aluminum member in a neutralizing solution; in a specific embodiment, the neutralizing solution comprises a 70-150 ml/L MICRO NEO PRO In a particular embodiment, the neutralizing solution is an aqueous solution containing 70-150 ml/L of MICRO NEO PRO.
  • the process conditions of the neutralization process are: temperature: 10-35 ° C; daytime: 0.5-2 min.
  • the ingredients contained in PRO are: 67% nitric acid.
  • the polyferric sulfate is 10%, and the balance is a solvent.
  • the solvent is water.
  • the neutralization solution can also be made of nitric acid or sulfuric acid, but the effect is not as good as MIC RO NEO PRO.
  • the alkali etching treatment in the step S01 is to further remove the oxide layer on the surface of the aluminum member. Therefore, in an embodiment, the alkali etching treatment is performed by placing the degreased aluminum member in an alkali solution for alkaline etching; in a specific embodiment, the alkali solution includes 50-70 ml/L. MICRO ETC 05, in a specific embodiment, the lye is an aqueous solution containing 50-70 ml/L of MICRO ETC 05. In a further embodiment, the process conditions of the alkali etching treatment are: temperature: 45-60 ° C; daytime: 0.5-2 min. Through the control of the lye and alkali etching process conditions, the oxide layer on the surface of the aluminum part can be effectively removed, and a high-quality aluminum surface is obtained, which provides a good foundation for the subsequent processing.
  • the composition of the MICRO ETC 05 is: sodium hydroxide 50% or potassium hydroxide 50% or ammonia water 80%, and the balance is a solvent.
  • the solvent is water. .
  • the micro-etching process in the above step S02 is to cause the aluminum on the surface of the aluminum member to be etched to leave micropores, so that the surface of the aluminum member forms an uneven rough surface having pits.
  • the micro-etching process is performed by placing the pre-treated aluminum member in a micro-etching solution for micro-etching.
  • the micro-etching solution comprises: sulfuric acid 180 g/L -200 g/L, MICRO M 150 ml/L -500 ml/L.
  • the microetching solution is an aqueous solution containing 180 g/L to 200 g/L of sulfuric acid and 150 ml/L to 500 ml/L of MICRO M.
  • the process conditions of the microetching process are: temperature: 18 -20 ° C; daytime: 5-15 min; voltage: 10-50 V.
  • a lead plate or an aluminum plate may be used as a cathode plate, such as a cathode plate in a cathode bag.
  • the component contained in the MICRO M includes an inorganic salt.
  • the inorganic salt is 3.5% sodium sulfate, 2% sodium nitrate, and the balance is a solvent.
  • the solvent is water.
  • the aluminum on the surface of the aluminum member becomes aluminum ions and enters the solution, thereby leaving micropores on the surface of the aluminum member, that is, on the surface of the aluminum member. A rough surface with micropores is formed.
  • the micropore space formed by the etching can be diversified to avoid the single hole defects formed by the existing chemical etching method, thereby effectively increasing the bonding strength of the surface of the aluminum member, such as with other materials. Or the bonding strength between components such as resin or plastic.
  • the micropore washing treatment in the above step S03 is for removing impurities and electrolytes in the porous layer of the aluminum member, such as a microetching liquid, so as to prevent the adverse effects of the next step of the implementation of the next step. Therefore, in an embodiment, the microporous washing process is to perform the washing process by placing the aluminum piece subjected to the micro-etching treatment in a microporous cleaning solution.
  • the micropore The cleaning solution includes 150-18 Oml/L of MICRO CLEAN.
  • the microporous cleaning solution is an aqueous solution containing 150-180 ml/L of MICRO CLEAN.
  • the process conditions of the microporous washing treatment are: temperature: 10-30 ° C; daytime: 4-6 min; pH: 10.8-11.5.
  • the component contained in the MICRO CLEAN includes an inorganic salt.
  • the inorganic salt is a concentration of 15% ammonium nitrate, 10% sodium sulfate, and the balance is a solvent.
  • the solvent is water.
  • the reaming treatment in the above step S03 is to enlarge the pore diameter in the porous layer of the cleaned aluminum member, so that the aluminum member has a porous layer suitable for the application of the pore diameter required for the subsequent injection molding process, thereby enhancing the aluminum thereof.
  • the reaming process is performed by placing the aluminum piece after the microporous washing process in a reaming treatment liquid to perform a hole expanding micro-etching process.
  • the expanding The well treatment solution includes 350 ml/L to 450 ml/L of MICRO PURE M2.
  • the reaming treatment solution is an aqueous solution containing 350 ml/L to 450 ml/L of MICRO PURE M2.
  • the process conditions of the reaming treatment are: temperature: 10-30 ° C; daytime: 4-6 min ; pH: 10.5-11.8.
  • the composition of the MICRO PURE M2 comprises sodium hydrogencarbonate, sodium nitrate, ammonium nitrate, sodium gluconate, and in specific embodiments, the sodium hydrogencarbonate, sodium nitrate, ammonium nitrate, glucose
  • the weight ratio of sodium is (10-30) : (5-10) : (15-35) : (12-30).
  • a step of performing a microporous washing treatment on the aluminum member is further included to remove residues in the micropores, such as a reaming treatment liquid or the like.
  • the microporous washing treatment can be directly carried out by referring to the microporous washing treatment process steps and process conditions in step S03.
  • the surface micro-etching method of the aluminum member in the above embodiment of the present invention can effectively control the surface of the aluminum member by controlling the active component of the etching liquid and sequentially performing micro-etching and reaming treatment on the aluminum member.
  • the etching treatment enables various micropores to appear on the surface of the aluminum member, and can effectively control the micropore diameter to meet the requirements of the later processes such as injection molding, thereby effectively enhancing the bonding between the aluminum member and other materials or members such as resin or plastic. strength.
  • the preparation method is easy to control, low in equipment requirements, stable in product quality, effective in improving production efficiency and reducing production cost.
  • the embodiment of the present invention further provides an aluminum member composite body.
  • the aluminum piece composite includes an aluminum piece and a bond member combined with the aluminum piece.
  • the aluminum member in the aluminum member composite is an aluminum member treated by the surface micro-etching method of the aluminum member described above.
  • the bonding member is a plastic member or a resin member.
  • an adhesive layer is coated between the bonding surface of the bonding member and the aluminum member to achieve effective fixed bonding between the two.
  • an adhesive is applied to at least the surface of the aluminum member which is etched with micropores, and is bonded to the plastic member or the resin member.
  • the binder is selected from at least one of the MICRO BONDs.
  • the adhesive can effectively cooperate with the porous film layer on the surface of the aluminum member to achieve a firm bond between the aluminum member and the bonding member, so that the combination of the two is more firm, thereby improving the structural stability of the aluminum member composite of the embodiment of the invention.
  • the active ingredient of the MICRO BON is an ammonia compound.
  • ammonia water, hydrazine hydrate, water-soluble amides, dimethylethanolamine, etc. therefore, the ammonia compound may be one or a mixture of the above.
  • the aluminum member composite is treated with the aluminum member surface micro-etching method described above as a metal member, and is bonded to the plastic member or the resin member, because the surface of the aluminum member is diverse.
  • the metal member and the plastic member or the resin member in the aluminum member composite according to the embodiment of the present invention can be firmly bonded, thereby imparting excellentity to the aluminum member composite of the embodiment of the present invention.
  • the structural firmness and lightweight properties as well as the corresponding mechanical properties make it possible to produce lightweight and thin products as needed, expanding the range of applications.
  • the embodiment of the present invention further provides the method for preparing the aluminum member composite described above.
  • the method for preparing the aluminum member composite comprises the following steps:
  • Step S04 processing the surface of the aluminum member according to the micro-etching method described above to obtain an aluminum member having a micro-hole etched on the surface;
  • Step S05 a step of placing the aluminum member having the surface etched with micropores in a binder solution to form a bonding layer, or directly coating the surface of the aluminum member at least etched with micropores a process of setting a binder;
  • Step S06 forming or pressing a plastic member or a resin member on the surface of the aluminum member provided with the adhesive layer.
  • the method for obtaining the aluminum member in the above step S04 can directly refer to the surface micro-etching method of the aluminum member in the above, and in order to save space, no further details are provided herein.
  • the binder solution in the above step S05 contains 250-350 ml/L of MICRO BOND.
  • the binder solution is an aqueous solution containing 250-350 ml/L of MICRO BOND.
  • the conditions for forming the bonding layer are: temperature: 10-30 ° C; daytime: 4-6 mi n; pH: 10.8-11.8.
  • the formed binder can be sufficiently filled into the micropores of the aluminum member, so that the bonding strength between the bonding layer and the aluminum member is high, when the bonding member is as After the plastic member or the resin member is bonded to the bonding layer, the bonding strength between the bonding member and the aluminum member is effectively enhanced.
  • the adhesive when the adhesive layer is directly coated on the porous surface of the aluminum member by coating, the adhesive may be an aqueous solution containing 250-350 ml/L of MICRO BOND, or may be Other conventional bonding ij, such as epoxy adhesives.
  • the adhesive By forming a bonding layer on the porous surface of the aluminum member by coating, the same can be effectively filled into the micropores of the aluminum member, so that the bonding strength between the bonding layer and the aluminum member is high, when the bonding member is concrete, such as a plastic member. Or after the resin member is bonded to the bonding layer, the bonding member and the aluminum member are effectively enhanced. The strength of the bond.
  • the bonding member is formed, for example, a plastic member or a resin member.
  • the bonding member may be directly formed on the surface of the aluminum member by injection molding, or may be formed into a bonding first. The piece is then directly pressed onto the surface of the bonding layer of the aluminum member to achieve a firm bond between the two.
  • the method for preparing the aluminum member composite is directly formed or pressed after the step of forming a bonding layer on the aluminum member treated by the micro-etching method based on the aluminum member processed by the surface micro-etching method of the aluminum member.
  • the plastic part or the resin part is combined, so that the prepared aluminum part composite has excellent structural firmness and light performance and corresponding mechanical properties.
  • the preparation process conditions are easy to control, the equipment requirements are low, the product quality is stable, the production efficiency is effectively improved, and the production cost is reduced.
  • a method for micro-etching a surface of an aluminum member comprising the following process steps:
  • Degreasing treatment process The purpose is to remove the impurities first, and ensure that the surface of the product can be fully infiltrated by the subsequent treatment liquid to obtain uniform treatment.
  • Equipment Treatment tank: CPVC, PVC, PP or flexible steel tank lined with suitable plastic.
  • Heater It can be heated by steam, titanium heating tube, stainless steel heating tube or quartz electric pen.
  • the oil stain removal management device is used to remove oil stains, and the minimum filtration time is 5-8 cycles per hour.
  • Air agitation Try to stir the bath with filtration.
  • the treatment tank is cleaned. If it is a new tank, it is necessary to carry out prepreg with about 8 hours of acid and alkali.
  • S12. Neutralization Treatment Process The purpose is to remove the ash and residual lye to expose the bright base metal surface.
  • Equipment Treatment tank: CPVC, PVC, PP or flexible steel tank lined with suitable plastic.
  • Air agitation The treatment liquid is preferably equipped with an average and suitable air agitation.
  • the required air is supplied by a low pressure oil-free pump, and the minimum gas volume should be 50 liters / (min. square meters liquid level), and the gas pipe is hard. PVC or other suitable material.
  • the treatment tank is cleaned. If it is a new tank, it is necessary to carry out pre-dip with about 8 hours of acid and alkali.
  • Neutralization treatment process operating parameters Neutralization solution MICRO NEO PR concentration: 70ml / L, neutralization process Temperature: 35 ° C, daytime: 2min;
  • S13 alkali etching treatment process The purpose is to remove the natural oxide film on the surface of the aluminum part to obtain a high quality aluminum surface.
  • Equipment Treatment tank: CPVC, PVC, PP or flexible steel tank lined with suitable plastic.
  • Heater It can be heated with steam, a titanium heating tube, a stainless steel heating tube or a quartz electric pen.
  • Air agitation The treatment liquid is preferably equipped with an average and suitable air agitation.
  • the required air is supplied by a low pressure oil-free pump, and the minimum gas volume should be 70 liters/(min. square meters liquid level), and the gas pipe is hard. PVC or other suitable material.
  • the treatment tank is cleaned. If it is a new tank, it is necessary to carry out pre-dip with about 8 hours of acid and alkali.
  • Alkaline etching treatment working parameters in the alkali etching solution MICRO ETC 05 concentration: 50g / L, alkali etching process temperature: 45 ° C, daytime: 2min;
  • S14 micro-hole etching process The purpose is to form a transparent microporous on the aluminum piece suitable for subsequent processing.
  • Equipment Treatment tank: CPVC, PVC, PP or flexible steel tank lined with suitable plastic.
  • Heater It can be heated by steam, titanium heating tube, stainless steel heating tube or quartz electric pen.
  • Cooling system Anodizing freezer.
  • Air agitation The treatment liquid is preferably equipped with an average and suitable air agitation.
  • the required air is supplied by a low pressure oil-free pump.
  • the minimum gas volume should be 100 liters / (min. square meters liquid level), and the gas pipe is hard. PVC or other suitable material.
  • Power supply High frequency power supply with ripple ratio ⁇ 10%, voltage range 24V.
  • Cathode plate A lead plate or an aluminum plate that is loaded into a cathode bag.
  • the treatment tank is cleaned. If it is a new tank, it is necessary to carry out pre-dip with about 8 hours of acid and alkali.
  • the microporous etching treatment process is an electrochemical etching of an aluminum member in a microporous etching solution, and a lead plate or an aluminum plate loaded in a cathode bag is used as a cathode plate.
  • Microporation working parameters Microporous etching solution concentration: sulfuric acid 180 g / L and MICRO M: 150ml / L, microporous etching process temperature: 18 ° C, daytime: 10min, etching voltage is : 20V.
  • Micropore cleaning treatment step The purpose is to clean the microporous porous layer and the microporous layer after the reaming treatment, and to remove impurities and electrolyte in the pore layer.
  • Treatment tank CPVC, PVC, PP or flexible steel tank is lined with a suitable plastic.
  • Air agitation The treatment liquid is preferably equipped with an average and suitable air agitation.
  • the required air is supplied by a low pressure oil-free pump.
  • the minimum gas volume should be 50 liters / (min. square meters liquid level), and the gas pipe is hard. PVC or other suitable material.
  • Microporous cleaning treatment working parameters Micro CLEAN cleaning solution MICRO CLEAN concentration: 150ml / L, Microporous cleaning process temperature: 30 ° C, daytime: 4min; pH: 10.8-11.5.
  • Reaming Process The purpose is to expand the pores of the cleaned porous membrane to make it more suitable for the subsequent pore size required for injection molding.
  • Treatment tank CPVC, PVC, PP or flexible steel tank lined with suitable plastic.
  • Air agitation The treatment liquid is preferably equipped with an average and suitable air agitation.
  • the required air is supplied by a low pressure oil-free pump.
  • the minimum gas volume should be 50 liters / (min. square meters liquid level), and the gas pipe is hard. PVC or other suitable material.
  • the aluminum piece prepared in the first embodiment has various micropores distributed on the surface thereof, and the micropore diameter is 80-100 nm.
  • a method for micro-etching a surface of an aluminum member comprising the following process steps:
  • Degreasing treatment step The degreasing treatment step in the parameter example 1.
  • Working parameters of degreasing treatment process MICRO CLEAN 302 concentration in degreasing solution: 50g/L, temperature during degreasing treatment: 65°C, daytime: 2.5min;
  • Neutralization treatment process operating parameters Neutralization solution MICRO NEO PR concentration: 150 ml / L, neutralization process temperature: 10 ° C, daytime: 0.5 min;
  • S23 alkali etching treatment step The alkali etching treatment step in the parameter example 1.
  • S24 micro-hole etching treatment process The micro-hole etching treatment process in the parameter embodiment 1.
  • Microporous etching processing parameters Microporous etching solution concentration: sulfuric acid 200g / L and MICRO M:
  • the etching voltage is: 10V.
  • Micropore cleaning treatment step The microporous cleaning treatment step in the parameter example 1.
  • Microporous cleaning process operating parameters Microporous cleaning solution MICRO CLEAN concentration: 180ml / L
  • Microporous cleaning process temperature 10 ° C, daytime: 6 min; pH: 10.8-11.5.
  • the aluminum member prepared in the second embodiment has various micropores distributed on the surface thereof, and has a micropore diameter of 60 to 85 nm.
  • a method for micro-etching a surface of an aluminum member comprising the following process steps:
  • Degreasing treatment process operating parameters Degreased solution MICRO CLEAN 302 concentration: 35g / L, degreasing process temperature: 60 ° C, day: 5 min;
  • Neutralization treatment process operating parameters Neutralization solution MICRO NEO PR concentration: 100ml / L, neutralization process temperature: 20 ° C, daytime: lmin;
  • S33 alkali etching treatment step The alkali etching treatment step in the parameter example 1.
  • Operation parameters of alkali etching treatment process MICRO ETC 05 concentration in alkali etching solution: 60g/L, temperature during alkali etching treatment: 50°C, daytime: lmin;
  • S34 micropore etching treatment process The micropore etching treatment process in the parameter embodiment 1.
  • Microporous etching processing parameters Microporous etching solution concentration: sulfuric acid 190g / L and MICRO M:
  • Micropore cleaning treatment step The microporous cleaning treatment step in the parameter example 1.
  • Microporous cleaning treatment process parameters Microporous cleaning solution MICRO CLEAN concentration: 170ml / L
  • Microporous cleaning process temperature 20 ° C, daytime: 5 min; pH: 10.8-11.5.
  • a method for preparing an aluminum member composite and a preparation method thereof comprising the following process steps:
  • Step S41 treating the surface of the aluminum member according to the micro-etching method of Embodiment 1 to obtain an aluminum member having a micro-hole etched on the surface;
  • Step S42 a step of placing the aluminum member having the surface etched with the micropores in the binder solution to form a bonding layer; specifically, the purpose of forming the adhesion layer: the treatment is performed by reaming and cleaning Hole, strengthen the bonding between the microporous layer and the plastic particles:
  • Treatment tank CPVC, PVC, PP or flexible steel tanks are lined with suitable plastic.
  • Air agitation The treatment liquid is preferably equipped with an average and suitable air agitation.
  • the required air is supplied by a low pressure oil-free pump, and the minimum gas volume should be 50 liters / (min. square meters liquid level), and the gas pipe is hard. PVC or other suitable material.
  • Bonding process operating parameters MICRO BOND concentration in the binder solution: 250-350ml / L, temperature during the reaming process: 10-30 ° C, daytime: 4-6 min; pH: 10.8-11.8 .
  • Step S43 molding a plastic part on the surface of the aluminum piece provided with the adhesive layer.
  • the drawing force of the injection molded plastic part and the aluminum part was determined to be 3000-3300N.

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Abstract

一种铝件表面微刻蚀方法，包括如下步骤：将铝件依次进行除油处理，中和处理和碱蚀处理的预处理；将经预处理后的铝件表面进行微刻蚀处理，实现在铝件表面形成微孔；对铝件表面形成的微孔进行微孔洗涤处理和扩孔处理；其中，微刻蚀处理是将经预处理后的铝件置于微刻蚀液中进行微刻蚀处理，且微刻蚀液包括：硫酸180g/L-200g/L、MICRO M 150ml/L-500ml/L。还公开了一种铝件复合体及一种铝件复合体的制备方法。

Description

说明书 发明名称：铝件表面微刻蚀方法、 铝件复合体及其制备方法 技术领域
[0001] 本发明属于材料技术领域， 具体地说是一种铝件表面微刻蚀方法、 铝件复合体 及其制备方法。
背景技术
[0002] 随着世界电子产品的发展和其他需求轻质材料行业如航空业的发展， 产品向着 轻薄方向延伸。 因此， 对轻质材料的需求越来越大， 而且还对相应材料的相关 机械性能要求也来越高。
[0003] 其中， 铝及其合金由于其质轻， 且具有良好的机械性能得以广发应用。 但是其 依然不能满足当前相关行业对材料的轻薄的追求。 在此背景下金属复合材料应 运而生。
[0004] 金属复合材料是由金属与其他物理性能和化学性能不同的物质组合起来的一种 多相固体材料。 金属复合材料的优点一是其性能的复合效果， 即几种不同性质 结合在一种材料中使它们同吋发挥作用。 二是可根据使用要求来设计一种最合 适的复合材料， 即可设计性。 其中， 铝复合材料如铝塑料或树脂复合材料尤为 突出， 其复合轻质要求， 可以设计成符合要求的轻薄材料， 而且相应的机械性 能能够得到大多行业的要求。
[0005] 在现有的铝塑料或树脂复合材料中， 由于其具有金属装饰层或支持层， 和作为 支撑层或装饰层的树脂或塑料层， 该树脂或塑料层通过喷射、 注射模制或冲压 的方法而连接到金属层上， 自重较小同吋具有较高的质量外观， 因而被广泛地 使用在各个领域。
[0006] 随着铝塑料或树脂复合材料使用范围的扩大， 人们对品质要求的提高， 铝塑料 或树脂复合材料结构的稳固性显得尤为突出， 即塑料或树脂层与金属如铝件之 间的粘结力尤显重要。 为了增强两者之间的结合力， 现有出现了采用激光刻蚀 和化学刻蚀金属件表面， 对金属表面进行改性处理， 以增强两者间的结合力， 但是当前激光改性处理能耗大， 交难控制； 而当前的化学刻蚀法虽然能对金属 件表面刻蚀处理， 但是当前化学刻蚀法工艺条件苛刻， 试剂复杂， 而且金属件 如铝件表面形成的孔较为单一， 使得金属与树脂或塑料之间的结合力不够理想 技术问题
[0007] 本发明的目的在于克服现有技术的上述不足， 提供一种铝件表面微刻蚀方法， 以解决现有化学刻蚀法存在的工艺条件苛刻， 试剂复杂， 而且金属件如铝件表 面形成的孔较为单一， 使得金属与树脂或塑料之间的结合力不够理想的技术问 题。
问题的解决方案
技术解决方案
[0008] 本发明的另一目的在于提供一种铝件复合体及其制备方法， 以解决现有金属树 脂或塑料复合材料中的金属与树脂或塑料之间的结合力不够理想的技术问题。
[0009] 为了实现上述发明目的， 本发明实施例一方面提供了一种铝件表面微刻蚀方法 ， 包括如下步骤：
[0010] 将铝件依次进行除油处理， 中和处理和碱蚀处理的预处理；
[0011] 将经所述预处理后的铝件表面进行微刻蚀处理， 实现在所述铝件表面形成微孔
[0012] 对所述铝件表面形成的所述微孔进行微孔洗涤处理和扩孔处理；
[0013] 其中， 所述微刻蚀处理是将经所述预处理后的铝件置于微刻蚀液中进行微刻蚀 处理， 且所述微刻蚀液包括：
[0014] 硫酸 180 g/L -200g/L、 MICRO M 150 ml/L -500ml/L。
[0015] 另一方面， 本发明实施例提供了一种铝件复合体， 包括铝件和与所述铝件结合 的塑料件， 所述铝件为经上述本发明铝件表面微刻蚀方法处理后的铝件， 且在 所述铝件的至少在刻蚀有微孔的表面涂设有粘结剂， 并与所述塑料件粘合。
[0016] 再一方面， 本发明实施例提供了一种铝件复合体的制备方法， 包括如下步骤： [0017] 按照上述本发明微刻蚀方法对铝件表面进行处理， 获得表面刻蚀有微孔的铝件
[0018] 将所述表面刻蚀有微孔的铝件置于粘结剂溶液中形成粘结层的工序， 或者直接 在所述铝件的至少在刻蚀有微孔的表面涂设粘结剂的工序；
[0019] 在设有粘结层的所述铝件表面形成或压合塑料件或者树脂件。
[0020] 与现有技术相比， 上述本发明铝件表面微刻蚀方法通过对刻蚀液有效成分的控 制并将铝件先后进行微刻蚀和扩孔处理， 能有效对铝件表面进行微刻蚀处理， 使得在铝件表面出现多样的微孔， 并能有效控制微孔孔径符合后期工序如注塑 等工序的要求， 从而能有效增强铝件与其他材料或构件如树脂或塑料间的结合 强度。 另外， 其制备方法工艺易控， 对设备要求低， 产品质量稳定， 有效提高 了生产效率， 降低了生产成本。
[0021] 上述本发明铝件复合体采用本发明铝件表面微刻蚀方法处理后的铝件作为金属 构件， 并将其与塑料件或树脂件粘合， 由于铝件表面具有多样和符合后期工序 如注塑等工序的要求的微孔， 因此， 本发明铝件复合体中的金属构件和塑料件 或树脂件能够牢固结合， 从而赋予本发明铝件复合体优异的结构牢固性和轻质 性能以及相应的机械性能， 从而可被根据需要制备轻质且薄的产品， 扩大了其 应用范围。
发明的有益效果
有益效果
[0022] 上述本发明铝件复合体制备方法直接以铝件表面微刻蚀方法处理的铝件为基础 ， 对经微刻蚀方法处理的铝件形成粘结层的工序后直接形成或压合塑料件或者 树脂件， 从而使得制备的铝件复合体具有优异的结构牢固性和轻质性能以及相 应的机械性能。 而且其制备工艺条件易控， 对设备要求低， 产品质量稳定， 有 效提高了生产效率， 降低了生产成本。
本发明的实施方式
[0023] 为了使本发明的目的、 技术方案及优点更加清楚明白， 以下结合实施例， 对本 发明作进一步详细说明。 应当理解， 此处所描述的具体实施例仅仅用以解释本 发明， 并不用于限定本发明。
[0024] 本发明实施例说明书中所提到的各组分的重量百分比不仅仅可以表示各组分间 重量的比例关系， 也可以指代各组分的具体含量， 因此， 只要是按照本发明实 施例说明书中药物组合物各组分的含量按比例放大或缩小均在本发明实施例说 明书公幵的范围之内。 具体地， 本发明实施例说明书中所述的重量可以是 μ§、 m g、 g、 kg等本领域公知的重量单位， 当然可以看作是重量百分比。
[0025] 本发明实施例提供了一种工艺易控， 形成多样微孔的一种铝件表面微刻蚀方法
。 在一实施例中， 该铝件表面微刻蚀方法包括如下步骤：
[0026] 步骤 S01 : 将铝件依次进行除油处理， 中和处理和碱蚀处理的预处理；
[0027] 步骤 S02: 将经所述预处理后的铝件表面进行微刻蚀处理， 实现在所述铝件表 面形成微孔；
[0028] 步骤 S03: 对所述铝件表面形成的所述微孔进行微孔洗涤处理和扩孔处理。
[0029] 具体地， 上述步骤 S01中的铝件可以是铸造物或中间件等， 另外， 该铝件可以 是纯铝件或者是铝合金构件。
[0030] 由于铝件在前期的成型、 存储及搬运过程中表面会附着一些油污及粉尘， 因此
， 该步骤 S01中的铝件经过除油处理后， 能有效除去粘附在铝件表面的油污及粉 尘等杂物， 同吋还能保障铝件表面能被后续的处理液充分浸润， 已得到均匀一 致的处理。
[0031] 因此， 在一实施例中， 该步骤 S01中对铝件进行除油处理是将所述铝件置于除 油液中进行处理， 在一实施例中， 该除油液包括 20-50ml/L的 MICRO CLEAN 302 ， 在具体实施例中， 该除油液为含 20-50ml/L MICRO CLEAN 302的水溶液。 在 进一步实施例中， 所述除油处理的工艺条件为： 温度： 55-65°C; 吋间： 2.5-10mi n。 通过采用 MICRO CLEAN 302作为除油剂， 并控制其浓度和工艺条件， 能有 效对铝件表面进行清洗除杂处理。 在具体实施例中， 该 MICRO CLEAN 302所含 的成分含有焦磷酸钠 45%wt， 硼酸钠 35% wt， 硫酸钠 20% wt。 在具体使用过程 中， 该 MICRO CLEAN 302常规状态为固体， 在使用过程中可以根据需要进行配 制溶液。
[0032] 在另一实施例中， 该除油液还可以包括其他中兴铝材清洗剂， 如在一实施例中 ， 该除油液包括磷酸钠与碳酸钠的混合物， 在具体实施例中， 磷酸钠与碳酸钠 的浓度比为 20g/L: (10-15) g/L。
[0033] 当然， 除油液还可以是 MICRO CLEAN 302、 其他中性铝材清洗剂的混合物。 [0034] 该步骤 SOI中的中和处理是为了对经除油处理后的铝件进行除去挂灰和残留的 除油剂等残留物。 在一实施例中， 所述中和处理的是将经除油处理后的铝件置 于中和溶液中； 在具体实施例中， 所述中和溶液包括 70-150ml/L的 MICRO NEO PRO； 在具体实施例中， 该中和溶液为含 70-150ml/L MICRO NEO PRO的水溶液 。 在进一步实施例中， 所述中和处理的工艺条件为： 温度： 10-35°C; 吋间： 0.5- 2min。 通过对中和处理液和中和处理工艺条件的控制， 能有效除去铝件表面的 挂灰和残留物， 使得铝件铝件表面能够呈现基本金属表面。
[0035] 在具体实施例中， 该 MICRO NEO
PRO所含的成分为： 硝酸 67%。 多聚硫酸铁 10%， 余量为溶剂， 在具体实施例中 ， 该溶剂为水。 当然， 该中和溶液也可以采用硝酸或者硫酸， 但是效果没有 MIC RO NEO PRO的好。
[0036] 该步骤 S01中的碱蚀处理是为进一步除去铝件表面的氧化物层。 因此， 在一实 施例中， 该碱蚀处理是将经除油处理后的铝件置于碱液中进行碱性刻蚀； 在具 体实施例中， 所述碱液包括50-70ml/L的MICRO ETC 05， 在具体实施例中， 该碱 液为含 50-70ml/L MICRO ETC 05的水溶液。 在进一步实施例中， 所述碱蚀处理 的工艺条件为： 温度： 45-60°C; 吋间： 0.5-2min。 通过对碱液和碱蚀处理工艺条 件的控制， 能有效除去铝件表面的氧化物层， 获得优质的铝材表面， 为后续处 理工艺提供了良好的基础。
[0037] 在具体实施例中， 该 MICRO ETC 05所含的成分为： 氢氧化钠 50%或者氢氧化 钾 50%或者氨水 80%， 余量为溶剂， 在具体实施例中， 该溶剂为水。
[0038] 上述步骤 S02中微刻蚀处理是为了使得铝件表面的铝被腐蚀从而留下微孔， 使 得铝件表面形成不平整的具有凹坑的粗糙表面。 在一实施例中， 该所述微刻蚀 处理是将经所述预处理后的铝件置于微刻蚀液中进行微刻蚀处理。 在具体实施 例中， 所述微刻蚀液包括： 硫酸 180 g/L -200g/L、 MICRO M 150 ml/L -500ml/L 。 在具体实施例中， 该微刻蚀液为含硫酸 180 g/L -200g/L、 MICRO M 150 ml/L -500ml/L的水溶液。 在进一步实施例中， 该微刻蚀处理的工艺条件为： 温度： 18 -20°C; 吋间： 5-15min; 电压： 10-50V。 另外， 在具体微刻蚀处理过程中， 可以 采用铅板或者铝板为阴极板， 如将阴极板装入阴极袋中。 [0039] 在具体实施例中， 该 MICRO M所含的成分包括无机盐， 在具体实施例中， 该 无机盐是浓度为 3.5%硫酸钠、 2%的硝酸钠， 余量为溶剂， 在具体实施例中， 该 溶剂为水。
[0040] 通过对微刻蚀液和微刻蚀处理工艺条件的控制， 使得铝件表面的铝成为铝离子 而进入溶液中， 从而在铝件表面留下微孔， 也即是在铝件表面形成一层具有微 孔的粗糙表面。 再次基础上， 还能使得刻蚀形成的微孔空间多样化， 避免如现 有化学刻蚀方法形成的孔较为单一的缺陷， 这样， 有效增大了铝件表面的结合 强度， 如与其他材料或构件如树脂或塑料间的结合强度。
[0041] 上述步骤 S03中微孔洗涤处理是为了清除铝件多孔层中的杂质及电解质， 如微 刻蚀液， 以便下步工序的实施和避免对下一步工序实施效果的产生不利影响。 因此， 在一实施例中， 所述微孔洗涤处理是将经所述微刻蚀处理后的所述铝件 置于微孔清洗液中进行洗涤处理， 在具体实施例中， 所述微孔清洗液包括 150-18 Oml/L的 MICRO CLEAN。 在具体实施例中， 该微孔清洗液为含 150-180ml/L MICRO CLEAN的水溶液。 在进一步实施例中， 所述微孔洗涤处理的工艺条件为 ： 温度： 10-30°C; 吋间： 4-6min; pH:10.8-11.5。 通过对微孔清洗液和微孔洗涤 处理工艺条件的控制， 使得残留铝件的微孔层中的残留物被充分清除， 从而为 后续工艺步骤的实施和实施效果提供了有效保证。
[0042] 在具体实施例中， 该 MICRO CLEAN所含的成分包括无机盐， 在具体实施例中 ， 该无机盐是浓度为 15%硝酸铵、 10%的硫酸钠， 余量为溶剂， 在具体实施例中 ， 该溶剂为水。
[0043] 上述步骤 S03中的扩孔处理是为了扩大经过清洗后的铝件多孔层中的孔径， 使 得铝件具有适合应用的如后续注塑等工序所需要的孔径的多孔层， 从而增强其 铝件表面的结合强度。 在一实施例中， 所述扩孔处理是将经所述微孔洗涤处理 后的所述铝件置于扩孔处理液中进行扩孔微刻蚀处理， 在具体实施例中， 所述 扩孔处理液包括 350ml/L-450ml/L的 MICRO PURE M2。 在具体实施例中， 该扩孔 处理液为含 350ml/L-450ml/L MICRO PURE M2的水溶液。 在进一步实施例中， 该扩孔处理的工艺条件为： 温度： 10-30°C; 吋间： 4-6min; pH: 10.5-11.8。 通 过对扩孔处理液和扩孔处理工艺条件的控制， 在保证铝件表面多孔层中孔径的 多样性的同吋， 能适度扩大孔径大小， 从而有效增大了铝件与其他结合件之间 的结合强度。
[0044] 在具体实施例中， 该 MICRO PURE M2所含的成分包括碳酸氢钠、 硝酸钠、 硝 酸铵、 葡萄糖酸钠， 在具体实施例中， 该碳酸氢钠、 硝酸钠、 硝酸铵、 葡萄糖 酸钠的重量比为 (10-30) ： (5-10) ： (15-35) :(12-30)。
[0045] 在进一步实施例中， 待该步骤 S03中的扩孔处理之后， 还包括对铝件进行再次 进行微孔洗涤处理的工序， 以除去微孔中残留物， 如扩孔处理液等。 在具体实 施例中， 该微孔洗涤处理可以直接参照步骤 S03中的微孔洗涤处理工艺步骤和工 艺条件进行。
[0046] 右上所述， 上述本发明实施例铝件表面微刻蚀方法通过对刻蚀液有效成分的控 制并将铝件先后进行微刻蚀和扩孔处理， 能有效对铝件表面进行微刻蚀处理， 使得在铝件表面出现多样的微孔， 并能有效控制微孔孔径符合后期工序如注塑 等工序的要求， 从而能有效增强铝件与其他材料或构件如树脂或塑料间的结合 强度。 另外， 其制备方法工艺易控， 对设备要求低， 产品质量稳定， 有效提高 了生产效率， 降低了生产成本。
[0047] 相应地， 在上文所述的铝件表面微刻蚀方法的基础上， 本发明实施例还提供了 一种铝件复合体。 该铝件复合体包括铝件和与所述铝件结合的粘结件。
[0048] 在一实施例中， 所述铝件复合体中的铝件为经上文所述铝件表面微刻蚀方法处 理后的铝件。 在另一实施例中， 该粘结件选用塑料件或者树脂件。
[0049] 另外， 在该粘结件与铝件结合面之间涂设有粘结层， 实现两者有效固定粘合。
即在所述铝件的至少在刻蚀有微孔的表面涂设有粘结剂， 并与所述塑料件或树 脂件粘合。
[0050] 在一实施例中， 该粘结剂选用 MICRO BOND中的至少一种。 该粘结剂能有效 配合铝件表面多孔膜层实现铝件与粘结件之间的牢固结合， 使得两者结合的更 加牢固， 从而提高本发明实施例铝件复合体的结构稳固性能。
[0051] 在具体实施例中， 该 MICRO BON的有效成分是氨系化合物。 如氨水、 水合肼 、 水溶性酰胺类、 二甲基乙醇胺等， 因此， 氨系化合物可以是该些中的一种或 者几种的混合物。 [0052] 因此， 该铝件复合体采用上文所述的铝件表面微刻蚀方法处理后的铝件作为金 属构件， 并将其与塑料件或树脂件粘合， 由于铝件表面具有多样和符合后期工 序如注塑等工序的要求的微孔， 因此， 本发明实施例铝件复合体中的金属构件 和塑料件或树脂件能够牢固结合， 从而赋予本发明实施例铝件复合体优异的结 构牢固性和轻质性能以及相应的机械性能， 从而可被根据需要制备轻质且薄的 产品， 扩大了其应用范围。
[0053] 相应地， 在上文所述的铝件表面微刻蚀方法和铝件复合体基础上， 本发明实施 例还提供了上文所述的铝件复合体的制备方法。 在一实施例中， 该铝件复合体 的制备方法包括如下步骤：
[0054] 步骤 S04: 按照上文所述的微刻蚀方法对铝件表面进行处理， 获得表面刻蚀有 微孔的铝件；
[0055] 步骤 S05: 将所述表面刻蚀有微孔的铝件置于粘结剂溶液中形成粘结层的工序 ， 或者直接在所述铝件的至少在刻蚀有微孔的表面涂设粘结剂的工序；
[0056] 步骤 S06: 在设有粘结层的所述铝件表面形成或压合塑料件或者树脂件。
[0057] 具体地， 上述步骤 S04铝件获取方法可以直接参照上文中的铝件表面微刻蚀方 法， 为了节约篇幅， 在此不再赘述。
[0058] 在一实施例中， 上述步骤 S05所述粘结剂溶液含有 250-350ml/L的 MICRO BOND ， 在具体实施例中， 该粘结剂溶液为含 250-350ml/L MICRO BOND的水溶液。 在 进一步实施例中， 所述形成粘结层工序的条件为： 温度： 10-30°C; 吋间： 4-6mi n; pH:10.8-11.8。 通过对粘结剂溶液和扩孔处理工艺条件的控制， 能使得形成的 粘结剂充分填充至铝件微孔中， 使得粘结层与铝件的结合强度高， 当粘结件具 体的如塑料件或者树脂件与粘结层粘合后， 有效增强了粘结件与铝件之间的结 合强度。
[0059] 在另一实施例中， 当采用涂设的方式直接在铝件的多孔表面涂覆粘结剂吋， 该 粘结剂可以是含 250-350ml/L MICRO BOND的水溶液， 也可以是其他常规的粘结 齐 ij， 如环氧树脂粘结剂。 通过采用涂设的方式在铝件多孔表面形成粘结层， 其 同样能够有效充分填充至铝件微孔中， 使得粘结层与铝件的结合强度高， 当粘 结件具体的如塑料件或者树脂件与粘结层粘合后， 有效增强了粘结件与铝件之 间的结合强度。
[0060] 上述步骤 S06中的形成粘结件具体的如塑料件或者树脂件吋， 在一实施例中， 可以采用注塑的方式在铝件表面直接形成粘结件， 也可以先成型成粘结件， 然 后直接压合在铝件的粘结层表面， 实现两者的牢固结合。
[0061] 因此， 上述铝件复合体制备方法直接以上文铝件表面微刻蚀方法处理的铝件为 基础， 对经微刻蚀方法处理的铝件形成粘结层的工序后直接形成或压合塑料件 或者树脂件， 从而使得制备的铝件复合体具有优异的结构牢固性和轻质性能以 及相应的机械性能。 而且其制备工艺条件易控， 对设备要求低， 产品质量稳定 ， 有效提高了生产效率， 降低了生产成本。
[0062] 现以具体的铝件表面微刻蚀方法和为例， 对本发明作进一步详细说明。
[0063] 实施例 1
[0064] 一种铝件表面微刻蚀方法， 包括如下工艺步骤：
[0065] S11.除油处理工序： 目的是先除去这些杂物， 保障产品表面能被后续的处理液 充分浸润， 以得到均匀一致的处理。
[0066] 设备： 处理槽： CPVC、 PVC、 PP或柔钢槽内衬合适的塑料。
[0067] 加热器： 可以用蒸汽、 钛加热管、 不锈钢加热管或者石英电热笔加热。
[0068] 过滤： 用油污去除管理装置去除油污， 满足每小吋最少过滤 5-8循环。
[0069] 空气搅拌： 尽量用过滤去搅拌槽液。
[0070] 配置槽液：
[0071] 1.将处理槽清洗干净， 如果是新槽， 有必要用酸碱进行一次 8小吋左右的预浸
[0072] 2.在槽内加入 8成的去离子水；
[0073] 3.加入计算量的 MICRO CLEAN 302；
[0074] 4.幵启循环使除油剂完全溶解并混合均匀；
[0075] 5.补充去离子水到设定水位。
[0076] 除油处理工序工作参数： 除油溶液中 MICRO CLEAN 302浓度： 20g/L， 除油处 理过程中温度： 55°C、 吋间： lOmin;
[0077] 另外， 对除油溶液中 MICRO CLEAN 302浓度按照如下方法进行分析： [0078] 取一 250ml锥形瓶， 加入： a. 10ml处理液； b.去离子水 80ml; c. 1ml 指示剂 1205用滴定液 1304进行滴定， 当锥形瓶内溶液由黄色转换为粉红色吋为 终点， 记录滴定量。 计算： 浓度 （g/L) =2.5*滴定量 ml数。
[0079] S12.中和处理工序： 目的是除去挂灰和残留碱液， 以露出光亮基本金属表面。
[0080] 设备： 处理槽： CPVC、 PVC、 PP或柔钢槽内衬合适的塑料。
[0081] 空气搅拌： 处理液最好装置平均且合适的空气搅拌， 所需的空气由低压无油气 泵供应， 其最小气量应达 50公升 / (分钟.平方米液面） ， 气管采用硬质 PVC或 其他合适的材料。
[0082] 配置槽液：
[0083] 1.将处理槽清洗干净， 如果是新槽， 有必要用酸碱进行一次 8小吋左右的预浸
[0084] 2.在槽内加入 6成的去离子水；
[0085] 3.加入计算量的 MICRO NEO PRO；
[0086] 4.幵启空气搅拌使槽液混合均匀；
[0087] 5.补充去离子水到设定水位。
[0088] 中和处理工序工作参数： 中和溶液中 MICRO NEO PR浓度： 70ml/L， 中和处理 过程中温度： 35°C、 吋间： 2min;
[0089] 另外， 对中和溶液中 MICRO NEO PR浓度按照如下方法进行分析：
[0090] 取一 250ml锥形瓶， 加入： a.5ml处理液； b.去离子水 80ml; c. 10ml
指示剂 1172用滴定液 1308进行滴定， 当锥形瓶内溶液由深红色转换为淡黄色吋 为终点， 记录滴定量。 计算： 浓度 （g/L) =2.5*滴定量 ml数。
[0091] S13碱蚀处理工序： 目的是为了去除铝件表层的自然氧化膜， 以得到优质的铝 材表面。
[0092] 设备： 处理槽： CPVC、 PVC、 PP或柔钢槽内衬合适的塑料。
[0093] 加热器： 可以用蒸汽、 钛加热管、 不锈钢加热管或者石英电热笔加热。
[0094] 空气搅拌： 处理液最好装置平均且合适的空气搅拌， 所需的空气由低压无油气 泵供应， 其最小气量应达 70公升 / (分钟.平方米液面） ， 气管采用硬质 PVC或 其他合适的材料。 [0095] 配置槽液：
[0096] 1.将处理槽清洗干净， 如果是新槽， 有必要用酸碱进行一次 8小吋左右的预浸
[0097] 2.在槽内加入 8成的去离子水；
[0098] 3.加入计算量的 MICRO ETC 05；
[0099] 4.幵启空气搅拌使槽液混合均匀；
[0100] 5.补充去离子水到设定水位。
[0101] 碱蚀处理工序工作参数： 碱蚀溶液中 MICRO ETC 05浓度： 50g/L， 碱蚀处理过 程中温度： 45°C、 吋间： 2min;
[0102] 另外， 对碱蚀溶液中 MICRO ETC 05浓度按照如下方法进行分析：
[0103] 取一 250ml锥形瓶， 加入： a.lOml处理液； b.去离子水 20ml; c. 30ml
指示剂 1185; d， 1ml指示剂 1213。 用滴定液 1301进行滴定， 当锥形瓶内溶液由 粉红色转换为无色吋为终点， 记录滴定量。 计算： 浓度 （g/L) =8.05*滴定量。
[0104] S14微孔刻蚀处理工序： 目的是为了是在铝件上生成一层适合进行后续处理的 透明微孔。
[0105] 设备： 处理槽： CPVC、 PVC、 PP或柔钢槽内衬合适的塑料。
[0106] 加热器： 可以用蒸汽、 钛加热管、 不锈钢加热管或者石英电热笔加热。
[0107] 冷却系统： 阳极氧化冷冻机。
[0108] 过滤： 每小吋 5-10次槽液过滤量之耐酸过滤机。
[0109] 空气搅拌： 处理液最好装置平均且合适的空气搅拌， 所需的空气由低压无油气 泵供应， 其最小气量应达 100公升 / (分钟.平方米液面） ， 气管采用硬质 PVC或 其他合适的材料。
[0110] 电源： 波纹率 <10%的高频电源， 电压量程 24V。
[0111] 阴极板： 装入阴极袋之铅板或者铝板。
[0112] 配置槽液：
[0113] 1.将处理槽清洗干净， 如果是新槽， 有必要用酸碱进行一次 8小吋左右的预浸
[0114] 2.在槽内加入 4成的去离子水； [0115] 3.加入计算量的 MICRO M;
[0116] 4.加入计算量的 98%硫酸。
[0117] 5.幵启空气搅拌使槽液混合均匀；
[0118] 6.补充去离子水到设定水位。
[0119] 微孔刻蚀处理工序是将铝件置于微孔刻蚀液中进行电化学刻蚀， 且以装入阴极 袋之铅板或者铝板为阴极板。 微孔化工作参数： 微孔刻蚀液中含浓度： 硫酸 180 g/L和 MICRO M: 150ml/L, 微孔刻蚀处理过程中温度： 18°C、 吋间： 10min， 刻 蚀电压为： 20V。
[0120] 另外， 对微孔刻蚀溶液中 MICRO M浓度按照如下方法进行分析：
[0121] 取一 250ml锥形瓶， 加入： a.移液管取 5毫升工作液 （如混浊请过滤） ； b. 20 毫升的试剂 1181 ; c. l毫升指示剂 1203; d. 80-100毫升的去离子水。 将锥形瓶 内的溶液充分摇动混匀， 此吋溶液呈无色， 然后用滴定液 1302进行滴定， 可以 先放液 15ml， 再缓慢滴定， 滴定的终点为无色变为浅红色， 且 30秒内不变色。
(读数称为 A值）
[0122] 在微孔刻蚀处理过程中对游离铝离子的分析： 取一 250ml锥形瓶， 加入： a.移 液管取 5毫升工作液 （如混浊请过滤） ； b. 1毫升的试剂 1203; c. 80-100毫升的 去离子水。 将锥形瓶内的溶液充分摇动混匀， 此吋溶液呈无色， 然后用滴定液 1302进行滴定， 可以先放液 15ml， 再缓慢滴定， 滴定的终点为无色变为浅红色 ， 且 30秒内不变色。 （读数称为 B值）
[0123] 计算： 铝离子的浓度 (g/L)=1.75* (B-A) 。
[0124] S15.微孔清洗处理工序： 目的是为了是清洗微孔化后的多孔层及扩孔处理后的 微孔层， 清除孔层中的杂质及电解质。
[0125] 设备：
[0126] 处理槽： CPVC、 PVC、 PP或柔钢槽内衬合适的塑料。
[0127] 空气搅拌： 处理液最好装置平均且合适的空气搅拌， 所需的空气由低压无油气 泵供应， 其最小气量应达 50公升 / (分钟.平方米液面） ， 气管采用硬质 PVC或其 他合适的材料。
[0128] 配置槽液： [0129] 1.在微孔化槽中加入 2/3的去离子水，
[0130] 2.加入计算量的 MICRO CLEAN;
[0131] 3.幵启空气搅拌使槽液混合均匀；
[0132] 4.补充去离子水到设定水位。
[0133] 微孔清洗处理工序工作参数： 微孔清洗溶液中 MICRO CLEAN浓度： 150ml/L ， 微孔清洗处理过程中温度： 30°C、 吋间： 4min; pH: 10.8-11.5。
[0134] 另外， 对微孔清洗溶液只需管控 pH
值， 无需进行浓度的测试。 只可添加 MICRO CLEAN进行提升 pH值。
[0135] S16.扩孔处理工序： 目的是为了用于扩大经过清洗的多孔皮膜孔， 使之更适合 后续的注塑所需孔径。
[0136] 设备：
[0137] 处理槽： CPVC、 PVC、 PP或柔钢槽内衬合适的塑料。
[0138] 空气搅拌： 处理液最好装置平均且合适的空气搅拌， 所需的空气由低压无油气 泵供应， 其最小气量应达 50公升 / (分钟.平方米液面） ， 气管采用硬质 PVC或其 他合适的材料。
[0139] 配置槽液：
[0140] 1.在微孔化槽中加入 1/2的去离子水，
[0141] 2.加入计算量的 MICRO PURE M2;
[0142] 3.幵启空气搅拌使槽液混合均匀；
[0143] 4.补充去离子水到设定水位。
[0144] 扩孔处理工序工作参数： 扩孔处理溶液中 MICRO PURE M2浓度： 350ml/L， 扩 孔处理过程中温度： 10。C、 吋间： 6min; pH: 10.5-11.8。
[0145] 另外， 在扩孔处理过程中， 对扩孔处理溶液只需管控 pH值， 无需进行浓度的 测试。 只可添加 MICRO PURE M2进行提升 pH值。
[0146] 经测得， 本实施例 1制备的铝件表面分布多样的微孔， 微孔孔径为 80-100nm。
[0147] 实施例 2
[0148] 一种铝件表面微刻蚀方法， 包括如下工艺步骤：
[0149] S21.除油处理工序： 参数实施例 1中除油处理工序。 [0150] 除油处理工序工作参数： 除油溶液中 MICRO CLEAN 302浓度： 50g/L， 除油处 理过程中温度： 65°C、 吋间： 2.5min;
[0151] S22.中和处理工序： 参数实施例 1中中和处理工序。
[0152] 中和处理工序工作参数： 中和溶液中 MICRO NEO PR浓度： 150ml/L， 中和处 理过程中温度： 10°C、 吋间： 0.5min;
[0153] S23碱蚀处理工序： 参数实施例 1中碱蚀处理工序。
[0154] 碱蚀处理工序工作参数： 碱蚀溶液中 MICRO ETC 05浓度： 70g/L， 碱蚀处理过 程中温度： 60。C、 吋间： 0.5min;
[0155] S24微孔刻蚀处理工序： 参数实施例 1中微孔刻蚀处理工序。
[0156] 微孔刻蚀处理工作参数： 微孔刻蚀液中含浓度： 硫酸 200g/L和 MICRO M:
500ml/L， 微孔刻蚀处理过程中温度： 20°C、 吋间： 15min， 刻蚀电压为： 10V。
[0157] S25.微孔清洗处理工序： 参数实施例 1中微孔清洗处理工序。
[0158] 微孔清洗处理工序工作参数： 微孔清洗溶液中 MICRO CLEAN浓度： 180ml/L
， 微孔清洗处理过程中温度： 10°C、 吋间： 6min; pH: 10.8-11.5。
[0159] S26.扩孔处理工序： 参数实施例 1中扩孔处理工序。
[0160] 扩孔处理工序工作参数： 扩孔处理溶液中 MICRO PURE M2浓度： 450ml/L， 扩孔处理过程中温度： 30°C、 吋间： 4min; pH: 10.5-11.8。
[0161] S27.微孔清洗处理工序： 参照步骤 S25。
[0162] 经测得， 本实施例 2制备的铝件表面分布多样的微孔， 微孔孔径为 60-85nm。
[0163] 实施例 3
[0164] 一种铝件表面微刻蚀方法， 包括如下工艺步骤：
[0165] S31.除油处理工序： 参数实施例 1中除油处理工序。
[0166] 除油处理工序工作参数： 除油溶液中 MICRO CLEAN 302浓度： 35g/L， 除油处 理过程中温度： 60°C、 吋间： 5min;
[0167] S32.中和处理工序： 参数实施例 1中中和处理工序。
[0168] 中和处理工序工作参数： 中和溶液中 MICRO NEO PR浓度： 100ml/L， 中和处 理过程中温度： 20°C、 吋间： lmin;
[0169] S33碱蚀处理工序： 参数实施例 1中碱蚀处理工序。 [0170] 碱蚀处理工序工作参数： 碱蚀溶液中 MICRO ETC 05浓度： 60g/L， 碱蚀处理过 程中温度： 50°C、 吋间： lmin;
[0171] S34微孔刻蚀处理工序： 参数实施例 1中微孔刻蚀处理工序。
[0172] 微孔刻蚀处理工作参数： 微孔刻蚀液中含浓度： 硫酸 190g/L和 MICRO M:
300ml/L， 微孔刻蚀处理过程中温度： 19°C、 吋间： 6min， 刻蚀电压为： 50V。
[0173] S35.微孔清洗处理工序： 参数实施例 1中微孔清洗处理工序。
[0174] 微孔清洗处理工序工作参数： 微孔清洗溶液中 MICRO CLEAN浓度： 170ml/L
， 微孔清洗处理过程中温度： 20°C、 吋间： 5min; pH: 10.8-11.5。
[0175] S36.扩孔处理工序： 参数实施例 1中扩孔处理工序。
[0176] 扩孔处理工序工作参数： 扩孔处理溶液中 MICRO PURE M2浓度： 400ml/L， 扩孔处理过程中温度： 20。C、 吋间： 5min; pH: 10.5-11.8。
[0177] S37.微孔清洗处理工序： 参照步骤 S25。
[0178] 经测得， 本实施例 3制备的铝件表面分布多样的微孔， 微孔孔径为 25-45nm [0179] 实施例 4
[0180] 一种铝件复合体的制备方法及其制备方法， 包括如下工艺步骤：
[0181] 步骤 S41 : 按照实施例 1微刻蚀方法对铝件表面进行处理， 获得表面刻蚀有微孔 的铝件；
[0182] 步骤 S42: 将所述表面刻蚀有微孔的铝件置于粘结剂溶液中形成粘结层的工序 ； 具体地， 形成粘连层的目的： 处理经过扩孔并清洗过之微孔， 加强微孔层与 塑料粒子间的结合力：
[0183] 设备：
[0184] 处理槽： CPVC、 PVC、 PP或柔钢槽内衬合适的塑料。
[0185] 空气搅拌： 处理液最好装置平均且合适的空气搅拌， 所需的空气由低压无油气 泵供应， 其最小气量应达 50公升 / (分钟.平方米液面） ， 气管采用硬质 PVC或其 他合适的材料。
[0186] 粘结溶液配置槽液：
[0187] 1.在微孔化槽中加入 1/2的去离子水，
[0188] 2.加入计算量的 MICRO BOND; [0189] 3.幵启空气搅拌使槽液混合均匀；
[0190] 4.补充去离子水到设定水位。
[0191] 粘结处理工序工作参数： 粘结剂溶液中 MICRO BOND浓度： 250-350ml/L， 扩 孔处理过程中温度： 10-30°C、 吋间： 4-6min; pH: 10.8-11.8。
[0192] 另外， 在扩孔处理过程中， 对扩孔处理溶液只需管控 pH值， 无需进行浓度的 测试。 只可添加 MICRO BOND进行提升 pH值。
[0193] 步骤 S43: 在设有粘结层的所述铝件表面注塑塑料件。
[0194] 经测定， 注塑塑料件与铝件的拉拔力 3000-3300N。
[0195] 以上所述仅为本发明的较佳实施例而已， 并不用以限制本发明， 凡在本发明的 精神和原则之内所作的任何修改、 等同替换和改进等， 均应包含在本发明的保 护范围之内。

Claims

权利要求书
一种铝件表面微刻蚀方法， 包括如下步骤：
将铝件依次进行除油处理， 中和处理和碱蚀处理的预处理； 将经所述预处理后的铝件表面进行微刻蚀处理， 实现在所述铝件表面 形成微孔；
对所述铝件表面形成的所述微孔进行微孔洗涤处理和扩孔处理； 其中， 所述微刻蚀处理是将经所述预处理后的铝件置于微刻蚀液中进 行微刻蚀处理， 且所述微刻蚀液包括：
硫酸 180 g/L -200g/L、 MICRO M 150 ml/L -500ml/L。
根据权利要求 1所述的铝件表面微刻蚀方法， 其特征在于： 所述微刻 蚀处理的工艺条件为：
温度： 18-20°C; 吋间： 10-15min; 电压： 19-20V。
根据权利要求 1所述的铝件表面微刻蚀方法， 其特征在于： 所述扩孔 处理是将经所述微孔洗涤处理后的所述铝件置于扩孔处理液中进行扩 孔微刻蚀处理， 其中， 所述扩孔处理液包括 350ml/L-450ml/L的 MICR 0 PURE M2。
根据权利要求 3所述的铝件表面微刻蚀方法， 其特征在于： 所述扩孔 处理的工艺条件为：
温度： 10-30°C; 吋间： 4-6min; pH: 10.5-11.8。
根据权利要求 1-4任一所述的铝件表面微刻蚀方法， 其特征在于： 所 述微孔洗涤处理是将经所述微刻蚀处理后的所述铝件置于微孔清洗液 中进行洗涤处理， 其中， 所述微孔清洗液包括 150-180ml/L的 MICRO CLEAN。
根据权利要求 5所述的铝件表面微刻蚀方法， 其特征在于： 所述微孔 洗涤处理的工艺条件为：
温度： 10-30°C; 吋间： 4-6min; pH:10.8-11.5。
根据权利要求 1-4、 6任一所述的铝件表面微刻蚀方法， 其特征在于： 所述除油处理是将所述铝件置于除油液中进行处理， 其中， 所述除油 液包括 20-50ml/L的 MICRO CLEAN 302、 其他中性铝材清洗剂中的至 少一种； 和 /或
所述中和处理的是将经所述除油处理后的铝件置于中和溶液中； 其中 ， 所述中和溶液包括 70-150ml/L的 MICRO NEO PRO、 硝酸、 硫酸中 的至少一种； 和 /或
所述碱蚀处理是将经所述中和处理后的铝件置于碱液中进行碱性刻蚀
； 其中， 所述碱液包括 50-70ml/L的 MICRO ETC 05。
根据权利要求 7所述的铝件表面微刻蚀方法， 其特征在于： 所述除油 处理的工艺条件为： 温度： 55-65°C; 吋间： 2.5-10min;
所述中和处理的工艺条件为： 温度： 10-35°C; 吋间： 0.5-2min; 所述碱蚀处理的工艺条件为： 温度： 45-60°C; 吋间： 0.5-2min。 一种铝件复合体， 包括铝件和与所述铝件结合的塑料件或者树脂件， 所述铝件为经权利要求 1-8任一所述铝件表面微刻蚀方法处理后的铝 件， 且在所述铝件的至少在刻蚀有微孔的表面涂设有粘结剂， 并与所 述塑料件或树脂件粘合。
根据权利要求 9所述的铝件表面微刻蚀方法， 其特征在于： 所述粘结 齐 lj为 MICRO BOND。
一种铝件复合体的制备方法， 包括如下步骤：
按照如权利要求 1-8任一所述的微刻蚀方法对铝件表面进行处理， 获 得表面刻蚀有微孔的铝件；
将所述表面刻蚀有微孔的铝件置于粘结剂溶液中形成粘结层的工序， 或者直接在所述铝件的至少在刻蚀有微孔的表面涂设粘结剂的工序； 在设有粘结层的所述铝件表面形成或压合塑料件或者树脂件。
根据权利要求 11所述的铝件复合体的制备方法， 其特征在于： 所述粘 结剂溶液含有 250-350ml/L的 MICRO BOND, 且所述形成粘结层工序 的条件为：
温度： 10-30°C; 吋间： 4-6min; pH:10.8-11.8。
PCT/CN2016/101719 2015-10-28 2016-10-11 铝件表面微刻蚀方法、铝件复合体及其制备方法 WO2017071463A1 (zh)

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