Method for preparing carbon fiber cloth reinforced aluminum matrix composite sheet by semi-solid casting and rolling method

Abstract

A method for preparing carbon fiber cloth reinforced aluminum matrix composite sheet by semi-solid casting and rolling method belongs to the field of metal material casting. The present invention provides a high-quality and short-process preparation method for preparing carbon fiber woven cloth reinforced aluminum matrix composite sheet by semi-solid casting and rolling method. By using the casting and rolling method to continuously provide pressure, driving the semi-solid slurry of aluminum alloy to continuously infiltrate the nickel-plated carbon fiber woven cloth and form a firm bond with it. It breaks through the barrier of insufficient wettability between the fiber reinforcement and the matrix existing in the traditional composite sheet manufacturing, and obtains a high-quality composite effect based on a short-process in a non-closed space.

Description

Technical Field

[0001] The present invention belongs to the field of metal material casting, and particularly relates to a method for preparing carbon fiber cloth reinforced aluminum matrix composite plates by semi-solid casting and rolling method. Background Art

[0002] Carbon fiber reinforced aluminum matrix composite is a composite material with aluminum or aluminum alloy as the matrix and carbon fiber as the reinforcement. It has the advantages of light weight, high strength, good electrical and thermal conductivity, non-absorbing moisture, non-aging, etc., and has become an ideal material under the background of energy conservation, emission reduction, low carbon and environmental protection, and has great application potential in modern industry, especially in high-tech fields. Among them, carbon fiber cloth refers to a two-dimensional woven cloth with different fiber arrangement directions obtained by weaving treatment based on continuous unidirectional fibers. This reinforcement form can effectively avoid the large number of fiber fractures, and also has the ability of multi-directional synchronous strengthening, and can be designed specifically according to the actual service environment for fiber arrangement, to ensure the lightweight effect of the material to a greater extent, which is an ideal form of fiber implantation.

[0003] In the traditional casting composite method of carbon fiber reinforced aluminum matrix composite, due to the large density difference between carbon and aluminum, it is difficult for carbon fibers to be evenly distributed, and the wetting ability of aluminum melt to carbon fibers is extremely poor, and the infiltration process between the two often can only be forced to complete by an external driving force. The currently commonly used infiltration driving mechanisms can be divided into: 1. Relying on the forced pressing effect of the matrix on the carbon fiber in a closed mold; 2. Relying on the impact effect of the matrix movement on the carbon fiber in a non-closed environment. The former has strong infiltration ability and high interface controllability, but has a long production cycle and limited product size; the latter has a short production process, but poor infiltration ability and difficult to guarantee the composite quality. In addition, when preparing carbon fiber cloth reinforced aluminum matrix composite plates, due to its own structural limitations, the preparation process often needs to have higher matrix penetration ability and stronger fiber protection ability.

[0004] Based on the above situation, developing a high-quality and short-process preparation technology for carbon fiber woven cloth reinforced aluminum matrix composite plates has become an urgent problem to be solved to promote the wide practical application of this ideal lightweight material. Summary of the Invention

[0005] Aiming at the problem that the existing preparation processes of carbon fiber reinforced aluminum matrix composite plates cannot take into account both composite quality and production efficiency, the present invention proposes a high-quality and short-process preparation method for preparing carbon fiber woven cloth reinforced aluminum matrix composite plates by semi-solid casting and rolling method. The casting and rolling method is used to continuously provide pressure to drive the semi-solid slurry of aluminum alloy to continuously infiltrate the nickel-plated carbon fiber woven cloth and form a firm bond with it. The purpose is to break the barrier of insufficient wettability between the fiber reinforcement and the matrix existing in the traditional composite plate manufacturing, and to obtain a high-quality composite effect based on a short-process in a non-closed space.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing a carbon fiber cloth reinforced aluminum matrix composite plate by semi-solid casting and rolling method, wherein the carbon fiber cloth is a carbon fiber woven cloth, and the method comprises the following steps:

[0008] Step 1: Surface metallization of carbon fiber woven cloth:

[0009] Step 1.1. Surface degumming: Under atmospheric environment, calcine the carbon fiber woven cloth at 450°C - 500°C for 30 min - 45 min;

[0010] Step 1.2. Surface degreasing: Use a ternary alkaline aqueous solution containing 55 g / L - 65 g / L NaOH, 15 g / L - 25 g / L Na2CO3 and 35 g / L - 45 g / L Na3PO4 at 70°C - 80°C as the degreasing agent, and carry out degreasing treatment on the degummed carbon fiber woven cloth for 20 min - 40 min under the action of ultrasonic vibration, and then wash the degreased carbon fiber woven cloth until there is no degreasing agent residue on the surface;

[0011] Step 1.3. Surface etching: Use an aqueous solution containing 50 g / L - 70 g / L H2SO4 and 200 g / L - 300 g / L (NH4)2S2O8 at 40°C - 60°C as the etching agent, and carry out etching treatment on the degreased carbon fiber woven cloth for 15 min - 20 min under the action of ultrasonic vibration, and then wash the etched carbon fiber woven cloth until there is no etching agent residue on the surface;

[0012] Step 1.4. Surface sensitization: Place the etched carbon fiber woven cloth in a sensitizing solution containing 10 g / L - 20 g / L SnCl2 and 30 mL / L - 40 mL / L HCl at 30°C - 40°C for 25 min - 30 min of ultrasonic vibration treatment to form a uniform Sn2(OH)3Cl adsorption layer on its surface, and then wash the surface-sensitized carbon fiber woven cloth until there is no sensitizing solution residue on the surface;

[0013] Step 1.5. Surface activation: Use an aqueous solution containing 0.5 g / L - 1 g / L PdCl2 and 10 mL / L - 20 mL / L HCl as the activation solution, and carry out activation treatment on the surface-sensitized carbon fiber woven cloth at 50°C - 70°C for 25 min - 30 min, and then wash the activated carbon fiber woven cloth until there is no activation solution residue on the surface;

[0014] Step 1.6. Surface Deposition: Using a plating solution with 15 g / L - 20 g / L NiSO4·6H2O as the main salt, 15 g / L - 20 g / L NaH2PO2·H2O as the reducing agent, 15 mL / L - 20 mL / L lactic acid as the stabilizer, and 1 g / L - 3 g / L sodium dodecylbenzenesulfonate as the dispersant, deposition is carried out at pH = 3.5 - 4.5 and 70°C - 80°C for 30 min - 120 min to obtain a nickel-plated carbon fiber woven fabric;

[0015] Step 2: Preparation of semi-solid aluminum alloy matrix:

[0016] Step 2.1. Material Selection: Select aluminum alloy raw materials with corresponding components according to requirements;

[0017] Step 2.2. Melting: The aluminum alloy raw materials are melted using an induction furnace. After complete melting, they are stirred evenly with a graphite stirring paddle to obtain the corresponding aluminum alloy liquid; among them, the melting temperature is 40°C - 60°C higher than the liquidus of the aluminum alloy with the corresponding components;

[0018] Step 2.3. Preparation of aluminum alloy semi-solid slurry: After the aluminum alloy liquid obtained in Step 2.2 is subjected to refining and degassing treatment, it is cooled. When the temperature of the aluminum alloy liquid is 10°C higher than the melting point, mechanical stirring is applied and cooling continues. After obtaining an aluminum alloy semi-solid slurry with a solid fraction of 25% - 40%, the stirring is stopped and it is kept warm waiting for casting and rolling; among them, the stirring speed of the mechanical stirring is 1500 r / min, and the stirring time depends on the specific cooling rate;

[0019] Step 3: Semi-solid casting and rolling composite of nickel-plated carbon fiber woven fabric and aluminum alloy matrix:

[0020] Step 3.1. After preheating the nickel-plated carbon fiber woven fabric at 350°C - 400°C, it is introduced into the preheating chamber in front of the casting and rolling machine, passed through the center of the rolls, and kept in a tensioned state;

[0021] Step 3.2. Using a flat-injection double-roll casting and rolling equipment; the aluminum alloy semi-solid slurry is introduced into the preheating chamber in front of the casting and rolling machine. After being measured by the temperature measuring system, casting and rolling start; after the aluminum alloy semi-solid slurry passes through the diversion groove and the casting nozzle, it enters between the rolls from the preheating chamber, so that both the upper and lower layers of the nickel-plated carbon fiber woven fabric are aluminum alloy semi-solid slurry, and it is tightly combined with the carbon fiber woven fabric placed in advance through the rolls under the pressing force applied by the rolls to obtain a carbon fiber reinforced aluminum matrix composite sheet; among them, the distance between the rolls is 4 mm, and the rolling speed is 3 r / min - 5 r / min.

[0022] In a method for preparing a carbon fiber reinforced aluminum matrix composite sheet by a semi-solid casting and rolling method according to the present invention, in Step 3, the raw materials for the semi-solid casting and rolling composite are the nickel-plated carbon fiber woven fabric prepared in Step 1 and the aluminum alloy semi-solid slurry prepared in Step 2.

[0023] The key technical point of the present invention lies in: The present invention has developed a method for preparing carbon fiber woven fabric reinforced aluminum matrix composite plates by semi-solid casting and rolling method.

[0024] Firstly, the surface of the carbon fiber woven fabric is metallized. Through the coordinated control of various process parameters in the pre-plating treatment and plating treatment, a complete, uniform and dense nickel plating layer is obtained on the carbon fiber woven fabric. Secondly, semi-solid state is adopted as the existence form of aluminum alloy during the composite process. On the one hand, a large amount of latent heat of solidification has been released, which is beneficial to the rapid formation of the solid skeleton and ensures the effective transfer of stress in the non-closed space. On the other hand, the semi-solid aluminum alloy slurry has good fluidity, can efficiently fill the fiber voids, and provides good guarantee for the tissue integrity of the fibers. Finally, relying on the mechanical force of the rotation of the rolling mill, the semi-solid matrix can be forced to continuously infiltrate the nickel-plated carbon fiber woven fabric. During the rolling and infiltration process, the liquid part in the semi-solid aluminum alloy slurry becomes the main filling material inside the infiltrated carbon fibers. Based on the law of interfacial solute redistribution, the interfacial structure of carbon fiber - aluminum alloy can be effectively controlled.

[0025] The beneficial effects of the present invention are as follows:

[0026] By applying rolling pressure to the semi-solid aluminum alloy slurry in the present invention, the upper and lower layers are both semi-solid aluminum alloy slurry (the state where the solid is suspended in the melt in the form of spherical crystals), and the middle is the nickel-plated carbon fiber woven fabric, enabling the semi-solid aluminum alloy slurry to perform bilateral synchronous forced infiltration on the nickel-plated carbon fiber woven fabric and form a firm interfacial bond, thereby realizing the high-quality and short-process preparation of large-size carbon fiber woven fabric reinforced aluminum matrix composite plates. The method provided by the present invention can match the corresponding solid fraction based on semi-solid aluminum alloy slurries with different compositions, thereby ensuring the stable distribution and structural integrity of carbon fibers during the casting and rolling process. The prepared carbon fiber woven fabric reinforced aluminum matrix composite plates can fully exert the designability of structure and performance, and to a greater extent ensure the lightweight effect of the material.

[0027] A method for preparing carbon fiber woven fabric reinforced aluminum matrix composite plates by semi-solid casting and rolling method proposed by the present invention integrates theoretical research and preparation process, realizes the full infiltration of aluminum matrix into carbon fibers, and successfully prepares composite plates with good combination of reinforcing phase and matrix. The present invention has the advantages of simple process, short process, low cost, remarkable effect, etc., and is expected to provide a feasible way for the large-scale production of such composite materials in China. Brief Description of the Drawings

[0028] Figure 1 It is a schematic structural diagram of the device for obtaining semi-solid aluminum alloy slurry in the present invention.

[0029] Figure 2This is a schematic diagram of the device for the semi-solid casting and rolling method in the present invention.

[0030] Among them, 1 - semi-solid aluminum alloy slurry; 2 - stirring paddle; 3 - heat preservation system; 4 - carbon fiber preheating system; 5 - nickel-plated carbon fiber woven cloth; 6 - temperature measurement system; 7 - rolling roll; 8 - runner; 9 - casting nozzle. Specific implementation mode

[0031] The method for preparing carbon fiber reinforced aluminum matrix composite plates by the semi-solid casting and rolling method of the present invention is applicable to the following embodiments, but is not limited to the following embodiments.

[0032] The present invention uses the semi-solid casting and rolling method to cast and roll-composite the carbon fiber woven cloth and the aluminum alloy matrix. Among them, the stirring device for the semi-solid aluminum alloy slurry is as Figure 1 shown, and is composed of a heat preservation system 3 and a stirring paddle 2, and is used for preparing the semi-solid aluminum alloy slurry 1. The casting and rolling device for the semi-solid aluminum alloy slurry and the carbon fiber woven cloth is as Figure 2 shown, and is composed of a rolling roll 7, a casting nozzle 9, a runner 8, a heat preservation system 3, a temperature measurement system 6 and a carbon fiber preheating system 4. The heat preservation system 3 is on both sides of the runner 8 to ensure that the temperature before casting and rolling is between the solid-liquid two-phase regions; the temperature measurement system 6 measures the real-time temperature of the semi-solid aluminum alloy slurry 1 at the runner; the nickel-plated carbon fiber woven cloth 5 first passes through the carbon fiber preheating system 4 and then passes through the runner 8 in parallel. After the semi-solid aluminum alloy slurry 1 fills the runner, under the mechanical pressure of the rolling roll 7, a rolling pressure is applied to the semi-solid aluminum alloy slurry 1. During the pressing process, the uppermost layer and the lowermost layer are both the semi-solid aluminum alloy slurry 1 (the state where the solid is suspended in the melt in the form of spherulites), and the middle is the nickel-plated carbon fiber woven cloth, so that the semi-solid aluminum alloy slurry 1 performs forced infiltration on the nickel-plated carbon fiber woven cloth and forms a firm interfacial bond to achieve casting and rolling.

[0033] In the method provided by the present invention, the semi-solid aluminum alloy slurry is directly transformed from a semi-solid state to a solid state under the combined action of the rapid cooling and pressure provided by the rolling roll, and at the same time as the rapid solidification occurs, it penetrates into its interior synchronously from both sides of the carbon fiber cloth, and achieves a firm combination with it.

[0034] In the method for preparing carbon fiber woven cloth reinforced aluminum matrix composite plates by the semi-solid casting and rolling method provided by the present invention, the aluminum alloy raw materials are selected and prepared according to needs.

[0035] Next, taking commercial aluminum alloy ingots of different grades as raw materials, the technical solution of the present invention will be further described in conjunction with the accompanying drawings.

[0036] Example 1:

[0037] In this example, carbon fiber woven cloth reinforced aluminum matrix composite plates are prepared with 2024 aluminum alloy as the matrix, and the steps are as follows:

[0038] Step 1: Surface metallization of carbon fiber woven fabric.

[0039] Step 1.1. Surface degumming: Burn the carbon fiber woven fabric at 450 °C - 500 °C for 30 min - 45 min in an atmospheric environment.

[0040] Step 1.2. Surface degreasing: Use a ternary alkaline aqueous solution at 70 °C - 80 °C containing 55 g / L - 65 g / L NaOH, 15 g / L - 25 g / L Na2CO3, and 35 g / L - 45 g / L Na3PO4 as the degreasing agent, and perform degreasing treatment on the degummed carbon fiber woven fabric for 20 min - 40 min under ultrasonic vibration, then wash the degreased carbon fiber woven fabric until there is no degreasing agent residue on the surface.

[0041] Step 1.3. Surface etching: Use an aqueous solution at 40 °C - 60 °C containing 50 g / L - 70 g / L H2SO4 and 200 g / L - 300 g / L (NH4)2S2O8 as the etching agent, and perform etching treatment on the degreased carbon fiber woven fabric for 15 min - 20 min under ultrasonic vibration, then wash the etched carbon fiber woven fabric until there is no etching agent residue on the surface.

[0042] Step 1.4. Surface sensitization: Place the etched carbon fiber woven fabric in a sensitizing solution at 30 °C - 40 °C containing 10 g / L - 20 g / L SnCl2 and 30 mL / L - 40 mL / L HCl for 25 min - 30 min of ultrasonic vibration treatment to form a uniform Sn2(OH)3Cl adsorption layer on its surface, then wash the surface-sensitized carbon fiber woven fabric until there is no sensitizing solution residue on the surface.

[0043] Step 1.5. Surface activation: Use an aqueous solution containing 0.5 g / L - 1 g / L PdCl2 and 10 mL / L - 20 mL / L HCl as the activation solution, and perform activation treatment on the surface-sensitized carbon fiber woven fabric at 50 °C - 70 °C for 25 min - 30 min, then wash the activated carbon fiber woven fabric until there is no activation solution residue on the surface.

[0044] Step 1.6. Surface deposition: Use a plating solution with 15 g / L - 20 g / L NiSO4·6H2O as the main salt, 15 g / L - 20 g / L NaH2PO2·H2O as the reducing agent, 15 mL / L - 20 mL / L lactic acid as the stabilizer, and 1 g / L - 3 g / L sodium dodecylbenzenesulfonate as the dispersant, and perform deposition at pH = 3.5 - 4.5 and 70 °C - 80 °C for 30 min - 120 min to obtain a surface nickel-plated carbon fiber woven fabric.

[0045] Step 2: Preparation of semi-solid aluminum alloy matrix.

[0046] Step 2.1. Material selection: Select commercial 2024 aluminum alloy ingots.

[0047] Step 2.2. Melting: Use a high-frequency induction furnace to melt the aluminum alloy ingots. After complete melting, stir evenly with a graphite stirring paddle to obtain aluminum alloy liquid. Among them, the melting temperature is 700 °C.

[0048] Step 2.3. Preparation of aluminum alloy semi-solid slurry: After refining and degassing the aluminum alloy liquid obtained in Step 2.2, use a graphite stirring paddle to stir to obtain an aluminum alloy semi-solid slurry with a solid fraction of 35%, then stop stirring and wait for casting and rolling. Among them, the stirring speed of mechanical stirring is 1500 r / min, and the stirring time depends on the specific cooling rate.

[0049] Step 3: Semi-solid casting and rolling composite of nickel-plated carbon fiber woven fabric and aluminum alloy matrix.

[0050] Step 3.1. After preheating the surface nickel-plated carbon fiber woven fabric in a resistance furnace at 350 °C - 400 °C, introduce it into the preheating chamber in front of the casting and rolling machine, pass through the center of the rolls, and keep it in a tensioned state.

[0051] Step 3.2. Use a flat-injection double-roll casting and rolling equipment. Introduce the aluminum alloy semi-solid slurry prepared in Step 2 into the preheating chamber in front of the casting and rolling machine. After measuring the temperature by the temperature measuring system, start casting and rolling. After the aluminum alloy semi-solid slurry passes through the diversion groove and the casting nozzle, it enters between the rolls from the preheating chamber, so that both the upper and lower layers of the nickel-plated carbon fiber woven fabric are aluminum alloy semi-solid slurry, and it is tightly combined with the carbon fiber woven fabric placed through the rolls in advance by the pressing force applied by the rolls. The aluminum alloy semi-solid slurry directly changes from a semi-solid state to a solid state, and a carbon fiber-reinforced aluminum matrix composite plate is obtained. Among them, the distance between the rolls is 4 mm, and the rolling speed is 4 r / min.

[0052] Example 2:

[0053] In this example, a carbon fiber woven fabric-reinforced aluminum matrix composite plate is prepared with 5083 aluminum alloy as the matrix, and the steps are as follows:

[0054] Step 1: Surface metallization of carbon fiber woven fabric.

[0055] Step 1.1. Surface degumming: Burn the carbon fiber woven fabric at 450 °C - 500 °C for 30 min - 45 min in an atmospheric environment.

[0056] Step 1.2. Surface degreasing: Use a ternary alkaline aqueous solution at 70°C - 80°C containing 55 g / L - 65 g / L NaOH, 15 g / L - 25 g / L Na2CO3, and 35 g / L - 45 g / L Na3PO4 as the degreasing agent. Under the action of ultrasonic vibration, perform degreasing treatment on the carbon fiber woven fabric after degumming for 20 min - 40 min, and then wash the degreased carbon fiber woven fabric until there is no residue of the degreasing agent on the surface.

[0057] Step 1.3. Surface etching: Use an aqueous solution at 40°C - 60°C containing 50 g / L - 70 g / L H2SO4 and 200 g / L - 300 g / L (NH4)2S2O8 as the etching agent. Under the action of ultrasonic vibration, perform etching treatment on the carbon fiber woven fabric after surface degreasing for 15 min - 20 min, and then wash the etched carbon fiber woven fabric until there is no residue of the etching agent on the surface.

[0058] Step 1.4. Surface sensitization: Place the etched carbon fiber woven fabric in a sensitizing solution at 30°C - 40°C containing 10 g / L - 20 g / L SnCl2 and 30 mL / L - 40 mL / L HCl for 25 min - 30 min of ultrasonic vibration treatment to form a uniform Sn2(OH)3Cl adsorption layer on its surface, and then wash the surface-sensitized carbon fiber woven fabric until there is no residue of the sensitizing solution on the surface.

[0059] Step 1.5. Surface activation: Use an aqueous solution containing 0.5 g / L - 1 g / L PdCl2 and 10 mL / L - 20 mL / L HCl as the activation solution. Under the temperature condition of 50°C - 70°C, perform activation treatment on the surface-sensitized carbon fiber woven fabric for 25 min - 30 min, and then wash the activated carbon fiber woven fabric until there is no residue of the activation solution on the surface.

[0060] Step 1.6. Surface deposition: Use a plating solution with 15 g / L - 20 g / L NiSO4·6H2O as the main salt, 15 g / L - 20 g / L NaH2PO2·H2O as the reducing agent, 15 mL / L - 20 mL / L lactic acid as the stabilizer, and 1 g / L - 3 g / L sodium dodecylbenzenesulfonate as the dispersant. Perform deposition at pH = 3.5 - 4.5 and 70°C - 80°C for 30 min - 120 min to obtain a carbon fiber woven fabric with a nickel-plated surface.

[0061] Step 2: Preparation of semi-solid aluminum alloy matrix.

[0062] Step 2.1 Material selection: Select a commercial 5083 aluminum alloy ingot.

[0063] Step 2.2 Melting: The aluminum alloy ingot is melted in a high-frequency induction furnace. After complete melting, it is stirred evenly with a graphite stirring paddle to obtain aluminum alloy liquid. Among them, the melting temperature is 680 °C.

[0064] Step 2.3 Preparation of aluminum alloy semi-solid slurry: After the aluminum alloy liquid obtained in Step 2.2 is subjected to refining and degassing treatment, it is stirred with a graphite stirring paddle to obtain an aluminum alloy semi-solid slurry with a solid fraction of 30%, and then the stirring is stopped and waiting for casting and rolling. Among them, the stirring speed of mechanical stirring is 1500 r / min, and the stirring time depends on the specific cooling rate.

[0065] Step 3: Semi-solid casting and rolling composite of nickel-plated carbon fiber woven fabric and aluminum alloy matrix.

[0066] Step 3.1 After the surface nickel-plated carbon fiber woven fabric is preheated at 350 °C - 400 °C through a resistance furnace, it is introduced into the preheating chamber in front of the casting and rolling machine and passes through the center of the rolls to make it in a tensioned state.

[0067] Step 3.2 Use a flat-casting double-roll casting and rolling equipment. The aluminum alloy semi-solid slurry prepared in Step 2 is introduced into the preheating chamber in front of the casting and rolling machine. After being measured by the temperature measurement system, the casting and rolling starts. After the aluminum alloy semi-solid slurry passes through the diversion groove and the casting nozzle, it enters between the rolls from the preheating chamber, so that both the upper and lower layers of the nickel-plated carbon fiber woven fabric are aluminum alloy semi-solid slurry, and it is tightly combined with the carbon fiber woven fabric placed through the rolls in advance by the pressing force applied by the rolls. The aluminum alloy semi-solid slurry directly changes from semi-solid to solid state to obtain a carbon fiber reinforced aluminum matrix composite sheet. Among them, the distance between the rolls is 4 mm, and the rolling speed is 4 r / min.

[0068] Example 3:

[0069] In this example, a carbon fiber woven fabric reinforced aluminum matrix composite sheet is prepared with 4A01 aluminum alloy as the matrix, and the steps are as follows:

[0070] Step 1: Surface metallization of carbon fiber woven fabric.

[0071] Step 1.1 Surface degumming: In an atmospheric environment, the carbon fiber woven fabric is calcined at 450 °C - 500 °C for 30 min - 45 min.

[0072] Step 1.2 Surface degreasing: A ternary alkaline aqueous solution containing 55 g / L - 65 g / L NaOH, 15 g / L - 25 g / L Na2CO3, and 35 g / L - 45 g / L Na3PO4 at 70 °C - 80 °C is used as the degreasing agent. Under the action of ultrasonic vibration, the degummed carbon fiber woven fabric is subjected to degreasing treatment for 20 min - 40 min, and then the degreased carbon fiber woven fabric is washed until there is no degreasing agent residue on the surface.

[0073] Step 1.3 Surface etching: Using an aqueous solution at 40°C - 60°C containing 50 g / L - 70 g / L H2SO4 and 200 g / L - 300 g / L (NH4)2S2O8 as the etchant, perform an etching treatment on the degreased carbon fiber woven fabric for 15 min - 20 min under ultrasonic vibration, and then wash the etched carbon fiber woven fabric until there is no etchant residue on the surface.

[0074] Step 1.4 Surface sensitization: Place the etched carbon fiber woven fabric in a sensitizing solution containing 10 g / L - 20 g / L SnCl2 and 30 mL / L - 40 mL / L HCl at 30°C - 40°C for 25 min - 30 min of ultrasonic vibration treatment to form a uniform Sn2(OH)3Cl adsorption layer on its surface, and then wash the surface-sensitized carbon fiber woven fabric until there is no sensitizing solution residue on the surface.

[0075] Step 1.5 Surface activation: Using an aqueous solution containing 0.5 g / L - 1 g / L PdCl2 and 10 mL / L - 20 mL / L HCl as the activation solution, perform an activation treatment on the surface-sensitized carbon fiber woven fabric at 50°C - 70°C for 25 min - 30 min, and then wash the activated carbon fiber woven fabric until there is no activation solution residue on the surface.

[0076] Step 1.6 Surface deposition: Using a plating solution with 15 g / L - 20 g / L NiSO4·6H2O as the main salt, 15 g / L - 20 g / L NaH2PO2·H2O as the reducing agent, 15 mL / L - 20 mL / L lactic acid as the stabilizer, and 1 g / L - 3 g / L sodium dodecylbenzenesulfonate as the dispersant, perform deposition for 30 min - 120 min at pH = 3.5 - 4.5 and 70°C - 80°C to obtain a nickel-plated carbon fiber woven fabric on the surface.

[0077] Step 2: Preparation of semi-solid aluminum alloy matrix.

[0078] Step 2.1 Material selection: Select a commercial 4A01 aluminum alloy ingot.

[0079] Step 2.2 Melting: Use a high-frequency induction furnace to melt the aluminum alloy ingot, and after complete melting, stir evenly with a graphite stirring paddle to obtain aluminum alloy liquid. Among them, the melting temperature is 710°C.

[0080] Step 2.3 Preparation of aluminum alloy semi-solid slurry: After performing a refining and degassing treatment on the aluminum alloy liquid obtained in Step 2.2, use a graphite stirring paddle to stir to obtain an aluminum alloy semi-solid slurry with a solid fraction of 25%, then stop stirring and wait for casting and rolling. Among them, the stirring speed of mechanical stirring is 1500 r / min, and the stirring time depends on the specific cooling rate.

[0081] Step 3: Semi-solid casting and rolling composite of nickel-plated carbon fiber woven fabric and aluminum alloy matrix.

[0082] Step 3.1 After preheating the surface nickel-plated carbon fiber woven fabric in a resistance furnace at 350°C - 400°C, it is introduced into the preheating chamber in front of the casting and rolling mill, passes through the center of the rolls, and is kept in a tensioned state.

[0083] Step 3.2 Use a flat-injection double-roll casting and rolling equipment. The aluminum alloy semi-solid slurry prepared in Step 2 is introduced into the preheating chamber in front of the casting and rolling mill. After being measured by the temperature measurement system, casting and rolling start. After the aluminum alloy semi-solid slurry passes through the diversion groove and the casting nozzle, it enters between the rolls from the preheating chamber, so that both the upper and lower layers of the nickel-plated carbon fiber woven fabric are aluminum alloy semi-solid slurry. Through the pressing force applied by the rolls, it is closely combined with the carbon fiber woven fabric placed in advance through the rolls. The aluminum alloy semi-solid slurry directly changes from semi-solid to solid, and a carbon fiber reinforced aluminum matrix composite sheet is obtained. Among them, the distance between the rolls is 4 mm, and the rolling speed is 4 r / min.

[0084] Example 4:

[0085] In this example, a carbon fiber woven fabric reinforced aluminum matrix composite sheet is prepared with 3003 aluminum alloy as the matrix. The steps are as follows:

[0086] Step 1: Surface metallization of carbon fiber woven fabric.

[0087] Step 1.1 Surface degumming: In an atmospheric environment, the carbon fiber woven fabric is burned at 450°C - 500°C for 30 min - 45 min.

[0088] Step 1.2 Surface degreasing: Use a ternary alkaline aqueous solution at 70°C - 80°C containing 55 g / L - 65 g / L NaOH, 15 g / L - 25 g / L Na2CO3, and 35 g / L - 45 g / L Na3PO4 as the degreasing agent. Under the action of ultrasonic vibration, the degummed carbon fiber woven fabric is degreased for 20 min - 40 min, and then the degreased carbon fiber woven fabric is washed until there is no degreasing agent residue on the surface.

[0089] Step 1.3 Surface etching: Use an aqueous solution at 40°C - 60°C containing 50 g / L - 70 g / L H2SO4 and 200 g / L - 300 g / L (NH4)2S2O8 as the etching agent. Under the action of ultrasonic vibration, the surface degreased carbon fiber woven fabric is etched for 15 min - 20 min, and then the etched carbon fiber woven fabric is washed until there is no etching agent residue on the surface.

[0090] Step 1.4 Surface sensitization: Place the etched carbon fiber woven fabric in a sensitizing solution containing 10 g / L - 20 g / L SnCl2 and 30 mL / L - 40 mL / L HCl at 30°C - 40°C for 25 min - 30 min of ultrasonic vibration treatment to form a uniform Sn2(OH)3Cl adsorption layer on its surface, and then wash the surface-sensitized carbon fiber woven fabric until there is no residual sensitizing solution on the surface.

[0091] Step 1.5 Surface activation: Use an aqueous solution containing 0.5 g / L - 1 g / L PdCl2 and 10 mL / L - 20 mL / L HCl as the activation solution, and carry out 25 min - 30 min of activation treatment on the surface-sensitized carbon fiber woven fabric at a temperature of 50°C - 70°C, and then wash the activated carbon fiber woven fabric until there is no residual activation solution on the surface.

[0092] Step 1.6 Surface deposition: Use a plating solution with 15 g / L - 20 g / L NiSO4·6H2O as the main salt, 15 g / L - 20 g / L NaH2PO2·H2O as the reducing agent, 15 mL / L - 20 mL / L lactic acid as the stabilizer, and 1 g / L - 3 g / L sodium dodecylbenzenesulfonate as the dispersant, and carry out deposition for 30 min - 120 min at pH = 3.5 - 4.5 and 70°C - 80°C to obtain a carbon fiber woven fabric with a nickel-plated surface.

[0093] Step 2: Preparation of semi-solid aluminum alloy matrix.

[0094] Step 2.1 Material selection: Select a commercial 3003 aluminum alloy ingot.

[0095] Step 2.2 Melting: Use a high-frequency induction furnace to melt the aluminum alloy ingot, and stir evenly with a graphite stirring paddle after complete melting to obtain aluminum alloy liquid. Among them, the melting temperature is 700°C.

[0096] Step 2.3 Preparation of semi-solid aluminum alloy slurry: After the aluminum alloy liquid obtained in Step 2.2 is subjected to refining and degassing treatment, use a graphite stirring paddle to stir to obtain a semi-solid aluminum alloy slurry with a solid fraction of 35%, then stop stirring and wait for casting and rolling. Among them, the stirring speed of mechanical stirring is 1500 r / min, and the stirring time depends on the specific cooling rate.

[0097] Step 3: Semi-solid casting and rolling composite of nickel-plated carbon fiber woven fabric and aluminum alloy matrix.

[0098] Step 3.1 After preheating the nickel-plated carbon fiber woven fabric at 350°C - 400°C through a resistance furnace, introduce it into the preheating chamber in front of the casting and rolling machine, pass through the center of the rolling rolls, and make it in a tensioned state.

[0099] Step 3.2: Use a flat-injection twin-roll casting and rolling equipment. Import the aluminum alloy semi-solid slurry prepared in Step 2 into the preheating chamber in front of the casting and rolling mill. After measuring the temperature with the temperature measuring system, start casting and rolling. After the aluminum alloy semi-solid slurry passes through the diversion groove and the casting nozzle, it enters between the rolls from the preheating chamber, so that both the upper and lower layers of the nickel-plated carbon fiber woven cloth are aluminum alloy semi-solid slurry. Through the pressing force applied by the rolls, it is tightly combined with the carbon fiber woven cloth placed through the rolls in advance. The aluminum alloy semi-solid slurry directly transforms from the semi-solid state to the solid state, and a carbon fiber reinforced aluminum matrix composite plate is obtained. Among them, the distance between the rolls is 4 mm, and the rolling speed is 4 r / min.

[0100] Example 5:

[0101] In this example, a carbon fiber woven cloth reinforced aluminum matrix composite plate is prepared with 7075 aluminum alloy as the matrix. The steps are as follows:

[0102] Step 1: Surface metallization of the carbon fiber woven cloth.

[0103] Step 1.1 Surface degumming: Burn the carbon fiber woven cloth at 450 °C - 500 °C for 30 min - 45 min in the atmospheric environment.

[0104] Step 1.2 Surface degreasing: Use a ternary alkaline aqueous solution at 70 °C - 80 °C containing 55 g / L - 65 g / L NaOH, 15 g / L - 25 g / L Na2CO3, and 35 g / L - 45 g / L Na3PO4 as the degreasing agent. Under the action of ultrasonic vibration, carry out a 20 min - 40 min degreasing treatment on the degummed carbon fiber woven cloth, and then wash the degreased carbon fiber woven cloth until there is no degreasing agent residue on the surface.

[0105] Step 1.3 Surface etching: Use an aqueous solution at 40 °C - 60 °C containing 50 g / L - 70 g / L H2SO4 and 200 g / L - 300 g / L (NH4)2S2O8 as the etching agent. Under the action of ultrasonic vibration, carry out a 15 min - 20 min etching treatment on the surface-degreased carbon fiber woven cloth, and then wash the etched carbon fiber woven cloth until there is no etching agent residue on the surface.

[0106] Step 1.4 Surface sensitization: Place the etched carbon fiber woven cloth in a sensitizing solution at 30 °C - 40 °C containing 10 g / L - 20 g / L SnCl2 and 30 mL / L - 40 mL / L HCl for 25 min - 30 min of ultrasonic vibration treatment to form a uniform Sn2(OH)3Cl adsorption layer on its surface, and then wash the surface-sensitized carbon fiber woven cloth until there is no sensitizing solution residue on the surface.

[0107] Step 1.5 Surface activation: An aqueous solution containing 0.5 g / L - 1 g / L PdCl2 and 10 mL / L - 20 mL / L HCl is used as the activation solution. Under the temperature condition of 50°C - 70°C, the surface-sensitized carbon fiber woven fabric is subjected to an activation treatment for 25 min - 30 min, and then the activated carbon fiber woven fabric is washed until there is no residual activation solution on the surface.

[0108] Step 1.6 Surface deposition: A plating solution with 15 g / L - 20 g / L NiSO4·6H2O as the main salt, 15 g / L - 20 g / L NaH2PO2·H2O as the reducing agent, 15 mL / L - 20 mL / L lactic acid as the stabilizer, and 1 g / L - 3 g / L sodium dodecylbenzenesulfonate as the dispersant is used. Deposition is carried out at pH = 3.5 - 4.5 and 70°C - 80°C for 30 min - 120 min to obtain a carbon fiber woven fabric with a nickel-plated surface.

[0109] Step 2: Preparation of semi-solid aluminum alloy matrix.

[0110] Step 2.1 Material selection: Select a commercial 7075 aluminum alloy ingot.

[0111] Step 2.2 Melting: The aluminum alloy ingot is melted using a high-frequency induction furnace and stirred evenly with a graphite stirring paddle after complete melting to obtain aluminum alloy liquid. Among them, the melting temperature is 680°C.

[0112] Step 2.3 Preparation of aluminum alloy semi-solid slurry: After the aluminum alloy liquid obtained in Step 2.2 is subjected to refining and degassing treatment, it is stirred with a graphite stirring paddle to prepare an aluminum alloy semi-solid slurry with a solid fraction of 40%, and then the stirring is stopped and waiting for casting and rolling. Among them, the stirring speed of mechanical stirring is 1500 r / min, and the stirring time depends on the specific cooling rate.

[0113] Step 3: Semi-solid casting and rolling composite of nickel-plated carbon fiber woven fabric and aluminum alloy matrix.

[0114] Step 3.1 After preheating the nickel-plated carbon fiber woven fabric through a resistance furnace at 350°C - 400°C, it is introduced into the preheating chamber in front of the casting and rolling machine and passes through the center of the rolls to keep it in a tensioned state.

[0115] Step 3.2: Use a flat-injection twin-roll casting and rolling equipment. The aluminum alloy semi-solid slurry prepared in Step 2 is introduced into the preheating chamber in front of the casting and rolling mill. After being measured by the temperature measuring system, the casting and rolling starts. After the aluminum alloy semi-solid slurry passes through the diversion groove and the casting nozzle, it enters between the rolls from the preheating chamber, so that both the upper and lower layers of the nickel-plated carbon fiber woven fabric are aluminum alloy semi-solid slurry. Through the pressing force applied by the rolls, it is tightly combined with the carbon fiber woven fabric placed in advance through the rolls. The aluminum alloy semi-solid slurry directly transforms from the semi-solid state to the solid state, and a carbon fiber reinforced aluminum matrix composite plate is obtained. Among them, the distance between the rolls is 4 mm, and the rolling speed is 4 r / min.

[0116] In the method for preparing a carbon fiber reinforced aluminum matrix composite plate by semi-solid casting and rolling provided by the present invention, the reinforcing phase selects a carbon fiber woven fabric instead of unidirectional carbon fibers, which avoids the problem of uneven distribution caused by the flow of the aluminum alloy semi-solid slurry to the carbon fibers during semi-solid casting and rolling, and ensures that the mechanical properties of the cast plate in the warp and weft directions are equivalent. At the same time, in the present invention, nickel plating on the surface of the carbon fiber realizes surface metallization, and the nickel plating treatment solves the problem of insufficient wettability between the surface of the carbon fiber woven fabric and the aluminum alloy semi-solid slurry. At the same time, the nickel coating has more excellent oxidation resistance at high temperatures, is not prone to peeling or degradation, and can effectively ensure the structural integrity and stable distribution of the carbon fiber woven fabric. Based on the simultaneous infiltration and composite of the carbon fiber woven fabric tensioned from both sides by the aluminum alloy semi-solid slurry, the present invention realizes the high-quality, short-process and continuous preparation of the carbon fiber reinforced aluminum matrix composite plate.

Claims

1. A method for preparing carbon fiber cloth reinforced aluminum matrix composite sheets by semi-solid casting and rolling method, characterized in that, The carbon fiber cloth is a carbon fiber woven cloth, and the method includes the following steps: Step 1: Surface metallization of the carbon fiber woven cloth: Step 1.

1. Surface degumming: Burn the carbon fiber woven cloth in an atmospheric environment; Step 1.

2. Surface degreasing: Use a ternary alkaline aqueous solution as the degreasing agent, and under the action of ultrasonic vibration, carry out a degreasing treatment on the degummed carbon fiber woven cloth in the degreasing agent for 20 min - 40 min, and then wash the degreased carbon fiber woven cloth until there is no residue of the degreasing agent on the surface; Step 1.

3. Surface etching: Ultrasonically treat the degreased carbon fiber woven cloth in an etching agent at 40°C - 60°C, then carry out an etching treatment for 15 min - 20 min, and then wash the etched carbon fiber woven cloth until there is no residue of the etching agent on the surface; Step 1.

4. Surface sensitization: Place the etched carbon fiber woven cloth in a sensitizing solution at 30°C - 40°C for 25 min - 30 min of ultrasonic vibration treatment, and a uniform Sn2(OH)3Cl adsorption layer is formed on the surface of the carbon fiber woven cloth, and then wash the surface-sensitized carbon fiber woven cloth until there is no residue of the sensitizing solution on the surface; Step 1.

5. Surface activation: Carry out an activation treatment on the surface-sensitized carbon fiber woven cloth at 50°C - 70°C for 25 min - 30 min, and then wash the activated carbon fiber woven cloth until there is no residue of the activation solution on the surface; Step 1.

6. Surface deposition: Deposit the activated carbon fiber woven cloth in a plating solution to obtain a carbon fiber woven cloth with a nickel-plated surface; Step 2: Preparation of the semi-solid aluminum alloy matrix: Step 2.

1. Material selection: Select aluminum alloy raw materials with corresponding components according to needs; Step 2.

2. Melting: Use an induction furnace to melt the aluminum alloy raw materials, and after complete melting, stir evenly with a graphite stirring paddle to obtain the corresponding aluminum alloy liquid; Step 2.

3. Preparation of the aluminum alloy semi-solid slurry: After carrying out a refining and degassing treatment on the aluminum alloy liquid obtained in Step 2.2, cool it down, then apply mechanical stirring and continue to cool down. After obtaining an aluminum alloy semi-solid slurry with a solid fraction of 25% - 40%, stop stirring and keep it warm waiting for casting and rolling; among them, the stirring speed of the mechanical stirring is 1500 r / min, and the stirring time depends on the specific cooling rate; Step 3: Semi-solid casting and rolling composite of the nickel-plated carbon fiber woven cloth and the aluminum alloy matrix: Step 3.

1. After preheating the carbon fiber woven cloth with a nickel-plated surface, introduce it into the preheating chamber in front of the casting and rolling machine, pass through the center of the rolling rolls, and make it in a tensioned state; Step 3.

2. Use a flat-injection double-roll casting and rolling device; Introduce the aluminum alloy semi-solid slurry into the preheating chamber in front of the casting and rolling machine. After measuring the temperature by the temperature measuring system, start casting and rolling; After the aluminum alloy semi-solid slurry passes through the diversion groove and the casting nozzle, it enters between the rolling rolls from the preheating chamber. The upper and lower layers of the nickel-plated carbon fiber woven cloth are both aluminum alloy semi-solid slurries. Through the pressing force applied by the rolling rolls, it is tightly combined with the carbon fiber woven cloth placed in advance through the rolling rolls. The aluminum alloy semi-solid slurry directly changes from a semi-solid state to a solid state to obtain a carbon fiber-reinforced aluminum matrix composite sheet; among them, the distance between the rolling rolls is 4 mm, and the rolling speed is 3 r / min - 5 r / min; In step 2.2, the smelting temperature is 40°C - 60°C higher than the liquidus temperature of the aluminum alloy ingot; In step 2.3, stirring is applied when the temperature of the aluminum alloy liquid is cooled to 10°C higher than the melting point; In step 3.1, the preheating temperature is 350°C - 400°C.

2. The method for preparing a carbon fiber cloth reinforced aluminum matrix composite sheet by semi-solid casting and rolling according to claim 1, characterized in that The ternary alkaline aqueous solution contains 55 g / L - 65 g / L NaOH, 15 g / L - 25 g / L Na2CO3, and 35 g / L - 45 g / L Na3PO4; The etchant is an aqueous solution containing 50 g / L - 70 g / L H2SO4 and 200 g / L - 300 g / L (NH4)2S2O8; The sensitizing solution contains 10 g / L - 20 g / L SnCl2 and 30 mL / L - 40 mL / L HCl; The activating solution is an aqueous solution containing 0.5 g / L - 1 g / L PdCl2 and 10 mL / L - 20 mL / L HCl; In the plating solution, 15 g / L - 20 g / L NiSO4·6H2O is used as the main salt, 15 g / L - 20 g / L NaH2PO2·H2O is used as the reducing agent, 15 mL / L - 20 mL / L lactic acid is used as the stabilizer, and 1 g / L - 3 g / L sodium dodecylbenzenesulfonate is used as the dispersant.

3. The method for preparing a carbon fiber cloth reinforced aluminum matrix composite sheet by semi-solid casting and rolling according to claim 1, characterized in that In step 1.1, the calcination temperature is 450°C - 500°C, and the calcination time is 30 min - 45 min.

4. The method for preparing a carbon fiber cloth reinforced aluminum matrix composite sheet by semi-solid casting and rolling according to claim 1, characterized in that, In step 1.6, during the deposition process, pH = 3.5 - 4.5, the temperature is 70°C - 80°C, and the deposition time is 30 min - 120 min.

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