CN103862748B - A kind of aluminium alloy and polyphenylene sulfide thermal resin composite and preparation method thereof - Google Patents

Abstract

The invention provides an aluminum alloy and polyphenylene sulfide thermal resin composite material and a preparation method thereof. The composite material is composed of an aluminum alloy component and a polyphenylene sulfide thermal resin. The surface pretreatment, strong alkali etching treatment, film forming treatment and micropore expansion treatment are carried out, and then the polyphenylene sulfide thermal resin coating and pressing treatment is carried out on the surface of the aluminum alloy component with expansion micropores, and the aluminum alloy is combined into one plastic composites. In the present invention, uniform micropores are obtained by phosphoric acid film-forming treatment on the surface of the aluminum alloy member, and then the micropores are expanded, and then polyphenylene sulfide thermal resin is coated and pressed on the surface of the aluminum alloy member and the expanded micropores. treatment, the bonding force between the two is greatly increased, and an aluminum-plastic composite material with good bonding performance is made, and the surface-coated and pressed polyphenylene sulfide thermal resin will not peel off from the aluminum alloy component, which can truly Effectively protect the metal casings of electronic equipment and household appliances.

Description

A kind of aluminum alloy and polyphenylene sulfide thermal resin composite material and preparation method thereof

technical field

The invention belongs to the technical field of metal composite materials, and relates to an aluminum alloy composite material, in particular to an aluminum alloy and polyphenylene sulfide thermal resin composite material and a preparation method thereof.

Background technique

In recent years, with the diversification of people's demand for the appearance of electronic products, the appearance quality of electronic products is constantly changing. The single metal or plastic casing of electronic products can no longer meet the diversified market needs. Combined electronic product casings have become people's new favorite. At present, some of the more popular electronic product bodies on the market are the products of the combination technology of aluminum alloy surface treatment and resin polymer. For a long time, surface treatment researchers have been researching ways to combine aluminum alloys and resin polymers without using adhesives, but with little success. resin polymer

The patent application of CN200380104500 of Japan Taisei Plats Co., Ltd. discloses a "machine manufacturing method for a composite of aluminum alloy and resin polymer", and the composite of aluminum alloy and resin composition involved has a surface roughness of 5-5. 50 μm or more, aluminum alloy shaped objects with fine recesses or protrusions of 1 μm or less on the surface, which are fixed with the aforementioned recesses or protrusions, and have a vertical and horizontal average linear expansion coefficient of 2 to 4×10 ^-5 ℃ ^-1 A composite body composed of a thermoplastic resin composition mainly composed of butylene phthalate resin or polyphenylene sulfide. Although the bonding force of the composite can meet the requirements of a certain quality, the process is still time-consuming and labor-intensive, especially because it is an aluminum alloy shape with a surface roughness of 5-50 μm or more and fine concave or convex parts below 1 μm on the surface. Compounding the thermoplastic resin on the surface of the component still makes the thermoplastic resin composition easy to peel off from the aluminum alloy shape under the impact of external force, and cannot really effectively protect the metal casing of electronic equipment and household appliances.

Contents of the invention

Based on the above reasons, the purpose of the present invention is to provide a preparation method of aluminum alloy and polyphenylene sulfide thermal resin composite material, which produces uniform micropores by phosphoric acid film-forming treatment on the surface of aluminum alloy components, and then applies To expand the capacity, and then carry out polyphenylene sulfide thermal resin coating and pressing treatment on the surface of the aluminum alloy member and the expanded micropores to make an aluminum-plastic composite material with good bonding performance, which solves the problem of aluminum-plastic composite surface preparation. The above-mentioned problems that the process is prone to occur.

The technical solution adopted in the present invention is an aluminum alloy and polyphenylene sulfide thermal resin composite material, which is characterized in that the composite material is composed of aluminum alloy components and polyphenylene sulfide thermal resin. Surface pretreatment, strong alkali etching treatment, film formation treatment and micropore expansion treatment are carried out successively on the surface of aluminum alloy components, and then polyphenylene sulfide thermal resin coating and pressing treatment is carried out on the surface of aluminum alloy components with expanded micropores, combined Become an integrated aluminum-plastic composite material.

The preparation method of aluminum alloy and polyphenylene sulfide thermal resin composite material of the present invention, the preparation method comprises the following steps:

Step 1: Perform surface pretreatment on the aluminum alloy components according to the conventional process, the process includes: degreasing, double washing, neutralization, and double washing;

Step 2, strong alkali etching treatment, the process includes: alkali etching, double washing, neutralization, double washing, technological process and related parameters:

Among them, the alkali etching liquid uses sodium hydroxide with a purity of 98%, the liquid concentration is 50-70 (g/L), the temperature is 50-70°C, and the soaking time is 10-30 seconds;

Deashing agent with a neutralizing liquid concentration of 200-300 (g/L), at room temperature, for 5-10 seconds;

The rest of the process is conventional, and the surface of the aluminum alloy component is alkali-etched to a surface densely covered with micropores;

Step 3, micropore expansion treatment, the process includes: film forming treatment E1, triple water washing, cleaning treatment E2, combination treatment E3, cleaning treatment E4, process flow and related parameters:

Among them, the film-forming treatment E1 solution uses phosphoric acid film-forming agent with a concentration of 180-220 (g/L), the temperature is 18-22°C, and the soaking time is 480-600 seconds;

For cleaning treatment E2 and E4, potassium phosphate cleaning agent with a concentration of 1.0-3.0 (g/L) is used, at room temperature, and the soaking time is 60-120 seconds;

Film-forming treatment is performed on the surface of aluminum alloy components that have been etched into dense micropores to form a continuous non-porous film barrier layer with a thickness of 0.01-0.015 μm. The processing voltage of film-forming treatment E1: DC voltage 20±1V, 480～ 600 seconds;

For combined treatment of E3 liquid medicine, potassium acetate binder with a concentration of 1.6-2.6 (g/L) is used, at room temperature, and the soaking time is 60-120 seconds;

Soak the aluminum alloy components with dense micropores, so that the dense micropores under the film barrier layer will have an expansion effect, forming pores for adsorbing nano-scale polyphenylene sulfide thermal resin;

The rest of the process is conventional;

Step 4, coating treatment E5, the process includes: coating treatment E5, single water washing, double washing, hot water washing;

Among them, the E5 drug solution for coating treatment uses a mixed solution coating agent of potassium carbonate and potassium bicarbonate with a concentration of 3.0-5.0 (g/L) and a ratio of 1:1, at room temperature, and the soaking time is 60-120 seconds;

The rest of the process is conventional, using pure water to carry out;

Step 5, drying treatment, put it into a drying furnace, the temperature is: 50-70°C, and the drying time is: 10-15 minutes;

Step 6, resin coating and pressing treatment, dissolving nano-scale polyphenylene sulfide thermal resin at 250-300°C for 5-25 minutes, and then coating the surface of the aluminum alloy component in the forming mold Press and form nano-scale polyphenylene sulfide thermal resin, the mold temperature is controlled at 100-130°C, the thickness of nano-scale polyphenylene sulfide thermal resin is 0.4-1.0mm, and finally aluminum alloy and polyphenylene sulfide thermal resin are obtained Combined aluminum-plastic composite components.

The preparation method of aluminum alloy and polyphenylene sulfide thermal resin composite material according to the present invention is also characterized in that,

The surface of the designated part where the aluminum alloy member is combined with the polyphenylene sulfide thermal resin is the entire surface of the aluminum alloy member, or the surface of the designated part combined is a partial surface of the aluminum alloy member.

The aluminum alloy and polyphenylene sulfide thermal resin composite material and the preparation method thereof of the present invention are quite different from other aluminum-plastic material composite processes. It produces uniform micropores by phosphoric acid film-forming treatment on the surface of aluminum alloy components, and then micropores are formed on the micropores. The pores are expanded, and then polyphenylene sulfide thermal resin coating is performed on the surface of the aluminum alloy member and the expanded micropores to make an aluminum-plastic composite material with good bonding performance. Through the preparation method of the present invention, it can be The bonding force between the aluminum alloy component and the polyphenylene sulfide nano-thermal resin is greatly increased, good bonding performance is achieved, and performance tests in various aspects of surface treatment and injection molding process can be satisfied. The composite component formed by aluminum alloy components and polyphenylene sulfide thermal resin, under the action of external impact, the surface-coated polyphenylene sulfide thermal resin will not peel off from the aluminum alloy components, and can truly protect electronic equipment , Household appliances metal shell for effective protection, its good combination characteristics will become a new bright spot in the industry.

Description of drawings

Fig. 1a-Fig. 1d are schematic diagrams of the progress of the preparation process of the aluminum alloy and polyphenylene sulfide thermal resin composite material of the present invention.

Figure 2 is an enlarged view of uniform micropores produced by phosphoric acid treatment of the aluminum alloy of the present invention;

Fig. 3 is an enlarged view of micropore volume expansion after aluminum alloy bonding treatment in the present invention.

In the figure, 1. Aluminum alloy component, 2. Barrier layer, 3. Porous layer, 4. Nanoscale polyphenylene sulfide thermal resin.

detailed description

The present invention will be described in detail in conjunction with the accompanying drawings and specific embodiments.

An aluminum alloy and polyphenylene sulfide thermal resin composite material, the composite material is composed of aluminum alloy components and polyphenylene sulfide thermal resin, through surface pretreatment, strong alkali Etching treatment, film forming treatment and micropore expansion treatment, and then polyphenylene sulfide thermal resin coating treatment on the surface of the aluminum alloy component with expansion micropores, and combined into an integrated aluminum-plastic composite material.

The preparation method of aluminum alloy and polyphenylene sulfide thermal resin composite material of the present invention comprises the following steps:

Step 1: Perform surface pretreatment on the aluminum alloy components according to the conventional process, the process includes: degreasing, double washing, neutralization, and double washing;

Step 2, strong alkali etching treatment, the process includes: alkali etching, double washing, neutralization, double washing; process flow and related parameters:

Among them, the alkali etching liquid uses sodium hydroxide with a purity of 98%, the liquid concentration is 50-70 (g/L), the temperature is 50-70°C, and the soaking time is 10-30 seconds;

Deashing agent with a neutralizing liquid concentration of 200-300 (g/L), at room temperature, for 5-10 seconds;

The rest of the process is conventional, and the surface of the aluminum alloy component is alkali-etched to a surface densely covered with micropores;

Step 3, micropore expansion treatment, the process includes: film forming treatment E1, triple water washing, cleaning treatment E2, combination treatment E3, cleaning treatment E4; process flow and related parameters:

Among them, the film-forming treatment E1 solution uses phosphoric acid film-forming agent with a concentration of 180-220 (g/L), the temperature is 18-22°C, and the soaking time is 480-600 seconds;

For cleaning treatment E2 and E4, potassium phosphate cleaning agent with a concentration of 1.0-3.0 (g/L) is used, at room temperature, and the soaking time is 60-120 seconds;

Film-forming treatment is performed on the surface of aluminum alloy components that have been etched into dense micropores to form a continuous non-porous film barrier layer with a thickness of 0.01-0.015 μm. The processing voltage of film-forming treatment E1: DC voltage 20±1V, 480～ 600 seconds;

For combined treatment of E3 liquid medicine, potassium acetate binder with a concentration of 1.6-2.6 (g/L) is used, at room temperature, and the soaking time is 60-120 seconds;

Soak the aluminum alloy components with dense micropores, so that the dense micropores under the film barrier layer will have an expansion effect, forming pores for adsorbing nano-scale polyphenylene sulfide thermal resin;

The rest of the process is conventional;

Step 4, coating treatment E5, the process includes: coating treatment E5, single water washing, double washing, hot water washing;

Among them, the E5 drug solution for coating treatment uses a mixed solution coating agent of potassium carbonate and potassium bicarbonate with a concentration of 3.0-5.0 (g/L) and a ratio of 1:1, at room temperature, and the soaking time is 60-120 seconds;

The rest of the process is conventional, using pure water to carry out;

Step 5, drying treatment, put it into a drying furnace, the temperature is: 50-70°C, and the drying time is: 10-15 minutes;

Step 6, resin coating and pressing treatment, dissolving nano-scale polyphenylene sulfide thermal resin at 250-300°C for 5-25 minutes, and then coating the surface of the aluminum alloy component in the forming mold Press and form nano-scale polyphenylene sulfide thermal resin, the mold temperature is controlled at 100-130°C, the thickness of nano-scale polyphenylene sulfide thermal resin is 0.4-1.0mm, and finally aluminum alloy and polyphenylene sulfide thermal resin are obtained Combined aluminum-plastic composite components.

The preparation method of the aluminum alloy and polyphenylene sulfide thermal resin composite material of the present invention, the surface of the specified part where the aluminum alloy component is combined with the polyphenylene sulfide thermal resin is the entire surface of the aluminum alloy component, or the surface of the specified part of the combination is the local surface of the aluminum alloy member.

In the preparation method of the aluminum alloy and polyphenylene sulfide thermal resin composite material of the present invention, the processed aluminum alloy components are first subjected to surface treatment pretreatment operations according to conventional processes. The previous treatment process includes: process includes: oil removal, double Combined washing, neutralization, double washing. The degreasing process can remove the oil stains left in the metal forming process, and the neutralization process can be used to remove the residual chemical liquid of the pre-treatment, so as to avoid affecting the post-process operation. Then, through the alkaline etching process of the strong alkali etching process, the slight billet front that appears on the surface of the aluminum alloy component is removed, and the outer surface of the product is evenly etched, so that the surface of the aluminum alloy component is alkali-etched into a surface densely covered with micropores.

After the pretreatment and strong alkali etching process, the aluminum alloy components are subjected to micropore expansion treatment. The micropore expansion treatment process includes: film formation treatment E1, triple water washing, cleaning treatment E2, combination treatment E3, cleaning treatment E4 .

During the whole process of micropore expansion treatment, as shown in Fig. 1a, through the first stage of micropore expansion treatment, film formation treatment E1, the DC voltage is 20±1V, and the duration is 480-600 seconds. Within a few to ten seconds of the start of power-on, the voltage rises sharply to the maximum value with time, and this value is called the critical voltage (or formation voltage). It will form a continuous non-porous film barrier layer 2 on the surface of the aluminum alloy member 1. This film has a high resistance, so as the film layer becomes thicker, the resistance increases and the cell voltage rises sharply and linearly. The appearance of the non-porous film barrier layer 2 hinders the continuous thickening of the film layer, and its thickness is proportional to the formation voltage and inversely proportional to the dissolution rate of the oxide film in the electrolyte. Generally, the thickness of the thin film barrier layer is about 0.01-0.015 μm. The characteristic of this section is that the formation rate of the oxide film is much faster than the dissolution rate. The critical voltage is greatly affected by the temperature of the electrolyte. The higher the temperature, the stronger the dissolution effect of the electrolyte on the film layer, and the thinner the non-porous film barrier layer 2, the lower the critical voltage.

In the second stage of micropore expansion treatment, as shown in Figure 1b, membrane pores appear, and after the anode potential reaches the highest value, it begins to decline, and the decline range is 10% to 15% of the maximum value. This is due to the dissolution of the electrolyte on the film layer, causing holes to be formed in the thinnest part of the oxide film, the resistance drops, and the voltage also drops. After the oxide film has pores, the electrochemical reaction can continue, and the oxide film continues to grow to form the porous layer 3 .

The third stage of micropore volume expansion treatment: as shown in Figure 1c, the porous layer 3 appearing on the film barrier layer is thickened. The characteristic of this stage is that the voltage starts to stabilize after about 20 seconds of oxidation time. At this time, the formation speed and dissolution speed of the barrier layer reach a balance, and its thickness remains unchanged, but the oxidation reaction does not stop, and the formation and dissolution of the oxide film continue at the bottom of each hole, moving from the bottom of the hole to the inside of the metal. As time goes on, the pores deepen to form pores and pore walls. Due to the existence of the electrolyte in the pores, the conductive ions can flow unimpeded here. Therefore, during the establishment of the porous layer, the resistance value does not change much, and the voltage does not change significantly, which is reflected in the characteristic curve. . During the anodic oxidation process, due to the influence of various factors, the temperature of the solution is continuously increased, and the corrosion effect on the film layer of aluminum alloy components is also increased. Not only the bottom of the hole, but also the film layer at the hole and the outer film layer The corrosion rate increases, so that the growth of the thickness of the porous layer 3 becomes slower. When the corrosion rate of the orifice film layer is equal to the film formation rate at the bottom of the hole, the thickness of the porous layer 3 will not continue to increase. The longer the equilibrium comes, the thicker the oxide film will be. In the growth process of the oxide film, electroosmosis plays an important role, so that the electrolyte is continuously renewed in the film pores. The reason for electroosmosis can be explained as: the surface of the hydrated oxide film in the electrolyte is negatively charged, and the surrounding solution is close to the positively charged ions. Due to the influence of the potential difference, the charged particles are relatively Electroosmosis occurs on the solid wall, that is, the positively charged liquid layer close to the hole wall flows to the outside of the hole, while the external fresh electrolyte flows into the hole along the central axis of the hole, which promotes the continuous renewal of the electrolyte in the hole, so that the hole Deepen and expand, as shown in Figure 1c.

After the aluminum alloy component 1 has undergone micropore expansion treatment, perform cleaning treatment E2: use a potassium phosphate cleaning agent to perform the first cleaning treatment on the aluminum alloy component with dense honeycomb crystal pores on the surface, so as to remove the residual acid in the micropores. The solution is cleaned up so that the subsequent process can be combined with treatment E3.

Combined treatment E3 liquid medicine uses potassium acetate binder with a concentration of 1.6-2.6 (g/L), at room temperature, and the soaking time is 60-120 seconds. Through the combined treatment E3 process, the cleaned dense micropores of the aluminum alloy components are subjected to combined soaking treatment, so that the dense micropores can produce an amplification effect and facilitate the adsorption of nano-plastic micromolecules.

Subsequent cleaning treatment E4: same as cleaning treatment E2: use potassium phosphate cleaning agent to clean the dense micropores treated with the combined chemical solution to facilitate the post-process coating treatment E5.

Coating treatment E5 chemical solution adopts potassium carbonate and potassium bicarbonate mixed solution coating agent with a concentration of 3.0-5.0 (g/L) and a ratio of 1:1, at room temperature, and the soaking time is 60-120 seconds. The dense micropores on the surface of aluminum alloy components will be completely enlarged after being soaked in E5 chemical solution for coating treatment, so that the performance of combining nano-plastics will be greatly improved.

After the coating treatment E5 process is completed, put the aluminum alloy component into a drying furnace for drying, the drying temperature is 50-70° C., and the drying time is 10-15 minutes.

Finally, the resin coating and pressing treatment is carried out. Firstly, the nano-scale polyphenylene sulfide thermal resin is dissolved at 250-300°C for 5-25 minutes, and then the aluminum alloy components are put into the forming mold and placed on the aluminum alloy. The surface of the specified part of the component is coated with compression-formed nano-scale polyphenylene sulfide thermal resin 4, the mold temperature is controlled at 100-130°C, and the thickness of the pressure-formed nano-scale polyphenylene sulfide thermal resin 4 coated is 0.4-1.0 mm, the aluminum-plastic composite member combined with aluminum alloy and polyphenylene sulfide thermal resin is finally obtained, as shown in Figure 1d.

In the preparation method of the aluminum alloy and polyphenylene sulfide thermal resin composite material of the present invention, the surface of the designated part where the aluminum alloy component is combined with the polyphenylene sulfide thermal resin is the overall surface of the aluminum alloy component, and the surface of the combined designated part can also be aluminum alloy. The partial surface of the alloy component forms a unique artistic effect of the coexistence of aluminum alloy and plastic.

The above-described embodiment is only an example of the present invention, and is not used to limit the implementation and scope of rights of the present invention. All equivalent changes and modifications made according to the content described in the patent protection scope of the present application shall be included in the application of the present invention. within the scope of the patent.

Claims (3)

1. A preparation method of aluminum alloy and polyphenylene sulfide thermal resin composite material, characterized in that, the preparation method may further comprise the steps: Step 1: Perform surface pretreatment on the aluminum alloy components according to the conventional process, the process includes: degreasing, double washing, neutralization, and double washing; Step 2, strong alkali etching treatment, the process includes: alkali etching, double washing, neutralization, double washing; process flow and related parameters: Among them, the alkali etching liquid uses sodium hydroxide with a purity of 98%, the liquid concentration is 50-70g/L, the temperature is 50-70°C, and the soaking time is 10-30 seconds; Neutralize the ash remover with a liquid concentration of 200-300g/L, at room temperature, for 5-10 seconds; The rest of the process is conventional, and the surface of the aluminum alloy component is alkali-etched to a surface densely covered with micropores; Step 3, micropore expansion treatment, the process includes: film forming treatment E1, triple water washing, cleaning treatment E2, combination treatment E3, cleaning treatment E4; process flow and related parameters: Among them, the film-forming treatment E1 solution uses phosphoric acid film-forming agent with a concentration of 180-220g/L, the temperature is 18-22°C, and the soaking time is 480-600 seconds; For cleaning treatment E2 and E4, potassium phosphate cleaning agent with a concentration of 1.0-3.0g/L is used, at room temperature, and the soaking time is 60-120 seconds; Film-forming treatment is performed on the surface of aluminum alloy components that have been etched into dense micropores to form a continuous non-porous film barrier layer with a thickness of 0.01-0.015 μm. The processing voltage of film-forming treatment E1: DC voltage 20±1V, 480～ 600 seconds; Combined treatment with E3 liquid medicine uses potassium acetate binder with a concentration of 1.6-2.6g/L, at room temperature, and the soaking time is 60-120 seconds; Soak the aluminum alloy components with dense micropores, so that the dense micropores under the film barrier layer will have an expansion effect, and form adsorption nano-polyphenylene sulfide thermal resin pores; The rest of the process is conventional; Step 4, coating treatment E5, the process includes: coating treatment E5, single water washing, double washing, hot water washing; Among them, the E5 drug solution for coating treatment uses a mixed solution coating agent of potassium carbonate and potassium bicarbonate with a concentration of 3.0-5.0 g/L and a ratio of 1:1, at room temperature, and the soaking time is 60-120 seconds; The rest of the process is conventional, using pure water to carry out; Step 5, drying treatment, put it into a drying furnace, the temperature is: 50-70°C, and the drying time is: 10-15 minutes; Step 6, resin coating and pressing treatment, dissolving the nano-polyphenylene sulfide thermal resin at 250-300°C for 5-25 minutes, and then coating and pressing the surface of the aluminum alloy component in the forming mold. Synthetic nano-polyphenylene sulfide thermal resin, the mold temperature is controlled at 100-130°C, the thickness of nano-polyphenylene sulfide thermal resin is 0.4-1.0mm, and finally the aluminum alloy and polyphenylene sulfide thermal resin are combined into one aluminum-plastic composite components. 2. The preparation method of aluminum alloy and polyphenylene sulfide thermal resin composite material according to claim 1, characterized in that, the surface of the designated part where the aluminum alloy component is combined with polyphenylene sulfide thermal resin is aluminum alloy The overall surface of the component, or the surface of the specified part of the combination is the partial surface of the aluminum alloy component. 3. An aluminum alloy and polyphenylene sulfide thermal resin composite material, characterized in that it is prepared by the preparation method as claimed in claim 1 or 2.