CN105254321B - Ceramic/metal connection method based on Ni B/Ti Transient liquid phase reaction in-situs - Google Patents

Abstract

A ceramic/metal connection method based on Ni-B/Ti instantaneous liquid-phase in-situ reaction relates to a brazing connection method. The invention aims to solve the problems of low strength and poor stability of existing ceramic/metal joints. Ceramic/metal connection method of the present invention is as follows: use the method for electroplating or electroless plating to deposit Ni-B amorphous alloy on the surface of Ni foil, make (Ni/Ni-B) composite foil, (Ni/ Ni‑B) The composite foil and Ti foil are placed between the metal to be welded and the ceramic to form the part to be welded, and put into a vacuum pressure sintering furnace for welding, which completes the ceramic/metal connection. The method can in-situ generate TiB whisker reinforcements in ceramic/metal welds, effectively relieves joint stress and improves joint strength. The shear strength of the joint obtained by using the method can reach 92-136MPa, and the joint strength is increased by 43%-72%. The method can be used in the field of ceramic/metal brazing connections.

Description

Ceramic/Metal Joining Method Based on Ni-B/Ti Transient Liquid Phase In-Situ Reaction

technical field

The invention relates to a ceramic/metal connection method based on Ni-B/Ti transient liquid-phase in-situ reaction.

Background technique

Ceramics have many excellent properties such as low density, high strength, wear resistance, high temperature resistance, and corrosion resistance. They are very promising structural materials in industrial fields such as military equipment, atomic energy, chemical industry, and automobiles. However, since ceramics do not have a dislocation system that can slip, it has high hardness, high brittleness, and is not easy to process and shape. In order to solve this problem, ceramics and metals are often connected in the industry, and the two are prepared into composite components to exert the excellent properties of ceramics and metals. Welding is the most commonly used method to connect ceramics and metals. It uses heat or pressure to make the materials to be welded form interatomic diffusion and bonding. Currently commonly used ceramic/metal welding methods include brazing, diffusion welding, self-propagating reaction joining, transient liquid phase (TLP) diffusion joining, laser/electron beam welding, etc. However, regardless of the connection method, it is necessary to consider the residual stress caused by the different physical properties of ceramics and metals. In recent years, researchers have mainly improved the performance of the joint through the composition design and process optimization of the welding intermediate layer, the most representative of which is the composite solder method. In this method, the active Ag-Cu-Ti solder is used as a matrix, and a certain proportion of ceramic particles, refractory metal particles or short fibers are mixed in as the second phase reinforcement. The physical properties of the middle layer of the weld are adjusted by using the high modulus and low thermal expansion coefficient of the reinforcement itself to reduce the difference in thermal expansion coefficient between the weld and the ceramic interface, thereby relieving the residual stress of the joint of dissimilar materials. The composite solder method is a simple and practical method, but it also has some problems in practical application: First, the mechanical mixing of the active solder and the reinforcing phase will cause the reinforcing phase to be unevenly distributed inside the weld and easy to agglomerate; Secondly, the complex chemical reaction between the reinforcing phase and the active solder is easy to form brittle intermetallic compounds, which is not good for the performance of the joint; thirdly, the addition of the reinforcing phase will reduce the fluidity and wettability of the active solder, and it is easy to produce Holes, lack of welding and other defects.

Contents of the invention

Aiming at the shortcomings of the above-mentioned background technology, the present invention discloses a ceramic/metal connection method based on Ni-B/Ti instantaneous liquid-phase in-situ reaction.

The method of the present invention adopts two layers of Ti intermediate layer foil and one layer of Ni/Ni-B composite foil as the welding intermediate layer, and the thicknesses of the two kinds of Ti intermediate layer foils are titanium foil ①: 10 μm to 50 μm and titanium foil ②: 50 ～150μm, the thickness of the initial Ni interlayer foil is 50～100μm, and the welding process is carried out according to the following steps:

1. Use 800#, 1000#, 1200#, 1500# sandpaper to polish the surface of the metal substrate, then immerse in acetone solution for ultrasonic cleaning for 5 minutes, and dry it for later use; Ultrasonic cleaning for 5 minutes, dry for later use;

2. Take the Ti and Ni interlayer foils, first immerse them in acetone solution and ultrasonically clean them for 5 minutes, then soak them in the deoxidation film solution for 10-15 minutes for deoxidation film treatment, then take out the Ti and Ni interlayer foils and wash them with clean water Rinse well and dry for later use; the deoxidized film solution is composed of HF with a mass percentage of 2% to 5%, _HNO3 with a mass percentage of 20% to 45%, and the remainder of water;

3. Take the Ni intermediate layer foil with a thickness of 50 μm to 100 μm in step 2, immerse it in an acetone solution and ultrasonically clean it for 5 minutes, and then deposit a Ni-B amorphous alloy layer with a thickness of 1 μm to 5 μm on one side of the Ni intermediate layer foil to obtain Ni/Ni-B composite foil; then wash the Ni/Ni-B composite foil with clear water and dry it for later use; wherein, the B content of the Ni-B amorphous alloy layer is 3wt.%～6wt.% ;

4. Take the ceramics and metals processed in step 1, the Ti intermediate layer foil processed in step 2, and the Ni/Ni-B composite foil obtained in step 3 and assemble them into pieces to be welded in a stacked manner. The assembly sequence is: metal/Ni-B composite foil Ti interlayer foil/Ni/Ni-B composite foil/Ti interlayer foil/ceramics; place the parts to be welded in a vacuum diffusion welding furnace, apply a pressure of 5-10MPa, and evacuate to 5×10 ^-4 ~1×10 ^-3 Pa, then heat up the vacuum diffusion welding furnace to 900°C at a speed of 30°C/min, hold for 5 minutes, then raise the temperature to 950-1000°C at a speed of 10°C/min, hold for 5-30 minutes, and then Cool down to 300°C at a rate of 5°C/min, and finally the weldment is cooled to room temperature with the furnace to complete the ceramic/metal connection based on Ni-B/Ti instantaneous liquid phase in-situ reaction; among them, Ni/Ni-B The Ni-B amorphous alloy layer of the composite foil is close to the ceramic side, and the thickness ratio of the total thickness of the two Ti interlayer foils to the Ni interlayer foil thickness not including the Ni-B amorphous alloy layer is 1:( 1.0～2.5).

The present invention comprises following beneficial effect:

The principle of the method of the present invention: there are two reaction interfaces of Ti/Ni and Ti/Ni-B in the welding intermediate layer, and when the temperature is higher than 942°C, the two interfaces generate eutectic transient liquid phase through Ti-Ni contact reaction. For the Ti/Ni-B reaction interface, B atoms gradually and uniformly enter the liquid phase with the dissolution of Ni, and react with Ti as follows:

Ti+B→TiB Δ _r G＝-163200+5.9TJ/mol

TiB is a fine acicular ceramic whisker with high modulus and low coefficient of thermal expansion. As a reinforcement, it can effectively adjust the overall thermal expansion coefficient of the weld and reduce joint stress. Since the reaction to generate TiB reinforcement is generated in situ during the welding process, the problems of uneven mixing and easy agglomeration of reinforcements in the composite solder method are avoided, and the joint structure and mechanical properties are improved. In addition, the in-situ reaction of TiB in the present invention only occurs in the instantaneous liquid phase region of the weld. Since the in-situ reaction rate is closely related to the dissolution rate of the Ni-B layer and the B content of the Ni-B layer, it can be controlled by the connection process and Ni -B layer composition control to precisely tune TiB growth.

Tests show that, using the method of the present invention to connect GH99 alloy and Al ₂ O ₃ ceramics, the shear strength of the prepared GH99/Ti/(Ni/Ni-B)/Ti/Al ₂ O ₃ joint can reach 92-136 MPa, which is higher than that of the previous The joint strength of GH99/Ti/Ni/Ti/Al ₂ O ₃ using in-situ reaction is increased by 43%-72%.

The existing patent (Application No.: 201010215105. Publication No.: CN101863677A) also proposes a method for in-situ self-generated TiB whiskers to improve the strength of ceramic brazed joints. The difference between the present invention and the existing patents is that the present invention adopts the method of electroplating or chemical plating to prepare the Ni-B amorphous alloy layer, and uses the Ni-B amorphous alloy layer as the boron source for in-situ reaction. The method of the invention can control the generation position and density of TiB, which is beneficial to improve the performance of the joint. Compared with the joint prepared by the reference document, the shear strength of the joint prepared by the invention is increased by about 20% to 40%.

Description of drawings

Fig. 1 is a schematic diagram of the assembly method of the ceramic/metal parts to be welded according to the present invention.

detailed description

Specific embodiment one: The ceramic/metal connection method based on Ni-B/Ti instantaneous liquid phase in situ reaction of the present embodiment, it is to carry out according to the following steps:

1. Use 800#, 1000#, 1200#, 1500# sandpaper to polish the surface of the metal substrate, then immerse in acetone solution for ultrasonic cleaning for 5 minutes, and dry it for later use; Ultrasonic cleaning for 5 minutes, dry for later use;

2. Take the Ti and Ni interlayer foils, first immerse them in acetone solution and ultrasonically clean them for 5 minutes, then soak them in the deoxidation film solution for 10-15 minutes for deoxidation film treatment, then take out the Ti and Ni interlayer foils and wash them with clean water Rinse well and dry for later use; the deoxidized film solution is composed of HF with a mass percentage of 2% to 5%, _HNO3 with a mass percentage of 20% to 45%, and the remainder of water;

3. Take the Ni intermediate layer foil with a thickness of 50 μm to 100 μm in step 2, immerse it in an acetone solution and ultrasonically clean it for 5 minutes, and then deposit a Ni-B amorphous alloy layer with a thickness of 1 μm to 5 μm on one side of the Ni intermediate layer foil to obtain Ni/Ni-B composite foil; then wash the Ni/Ni-B composite foil with clear water and dry it for later use; wherein, the B content of the Ni-B amorphous alloy layer is 3wt.%～6wt.% ;

4. Take the ceramics and metals processed in step 1, the Ti intermediate layer foil processed in step 2, and the Ni/Ni-B composite foil obtained in step 3 and assemble them into pieces to be welded in a stacked manner. The assembly sequence is: metal/Ni-B composite foil Ti interlayer foil/Ni/Ni-B composite foil/Ti interlayer foil/ceramics; place the parts to be welded in a vacuum diffusion welding furnace, apply a pressure of 5-10MPa, and evacuate to 5×10 ^-4 ~1×10 ^-3 Pa, then heat up the vacuum diffusion welding furnace to 900°C at a speed of 30°C/min, hold for 5 minutes, then raise the temperature to 950-1000°C at a speed of 10°C/min, hold for 5-30 minutes, and then Cool down to 300°C at a rate of 5°C/min, and finally the weldment is cooled to room temperature with the furnace to complete the ceramic/metal connection based on Ni-B/Ti instantaneous liquid phase in-situ reaction; among them, Ni/Ni-B The Ni-B amorphous alloy layer of the composite foil is close to the ceramic side, and the thickness ratio of the total thickness of the two-layer Ti interlayer foil to the Ni interlayer foil thickness not including the Ni-B amorphous alloy layer is 1:( 1.0～2.5).

Specific embodiment 2: The difference between this embodiment and specific embodiment 1 is that the Ni-B amorphous alloy layer deposited on the surface of the Ni intermediate layer foil side described in step 3 refers to the use of electroless nickel-boron alloy plating method Or electroplating nickel-boron alloy method for deposition. Others are the same as in the first embodiment.

Specific embodiment three: the difference between this embodiment and specific embodiment one is: the conditions of the electroless nickel-boron alloy plating method are: the electroless plating solution contains NiCl·6H ₂ O with a concentration of 5 g/L, and a concentration of 7 g/L L of NaC ₂ H ₃ O ₂ , C ₂ H ₁₀ BN with a concentration of 1g/L and PbCl ₂ with a concentration of 10-50mg/L; the pH of the electroless plating solution is 4, the temperature of the electroless plating solution is 59-81°C, and the chemical The deposition time is 5-30 minutes. Others are the same as in the first embodiment.

Embodiment 4: The difference between this embodiment and Embodiment 1 is that the conditions of the electroless nickel-boron alloy plating method are: the electroless plating solution contains NiCl·6H ₂ O with a concentration of 5 g/L, and a concentration of 7 g/L. L of NaC ₂ H ₃ O ₂ , C ₂ H ₁₀ BN with a concentration of 1g/L and PbCl ₂ with a concentration of 10-50mg/L; the pH of the electroless plating solution is 4, the temperature of the electroless plating solution is 65-80°C, and the chemical The deposition time is 5-20 minutes. Others are the same as in the first embodiment.

Embodiment 5: The difference between this embodiment and Embodiment 1 is that the conditions of the electroplating nickel-boron alloy method are: the electroplating solution contains NiSO ₄ ·6H ₂ O with a concentration of 240g/L and a concentration of 5g/L NiCl·6H ₂ O, H ₃ BO ₃ with a concentration of 30g/L and C ₂ H ₁₀ BN with a concentration of 3g/L; the pH of the electroplating solution is 3.5, the temperature of the electroplating solution is 44-46°C, and the current density is 0.5 ～1.5A/dm ² , the electroplating time is 10～60min. Others are the same as in the first embodiment.

Embodiment 6: The difference between this embodiment and Embodiment 1 is that the conditions of the electroplating nickel-boron alloy method are: the electroplating solution contains NiSO ₄ ·6H ₂ O with a concentration of 240g/L and a concentration of 5g/L NiCl·6H ₂ O, H ₃ BO ₃ with a concentration of 30g/L and C ₂ H ₁₀ BN with a concentration of 3g/L; the pH of the electroplating solution is 3.5, the temperature of the electroplating solution is 45-46°C, and the current density is 0.8 ～1.2A/dm ² , the electroplating time is 10～50min. Others are the same as in the first embodiment.

Embodiment 7: The difference between this embodiment and Embodiment 1 is that the solution for removing the oxide film is composed of HF with a mass percentage of 2% to 4%, and HF with a mass percentage of 20% to 40%. HNO ₃ and the balance of water. Others are the same as in the first embodiment.

Embodiment 8: This embodiment is different from Embodiment 1 in that: the B content of the Ni—B amorphous alloy layer is 3wt.%˜5wt.%. Others are the same as in the first embodiment.

Embodiment 9: This embodiment is different from Embodiment 1 in that: the B content of the Ni-B amorphous alloy layer is 4wt.%. Others are the same as in the first embodiment.

Embodiment 10: The difference between this embodiment and Embodiment 1 is that in step 4, place the workpiece to be welded in a vacuum diffusion welding furnace, apply a pressure of 5 to 10 MPa, and evacuate to 5×10 ^-4 to 1× 10 ^-3 Pa, then raise the temperature of the vacuum diffusion welding furnace to 900°C at a speed of 30°C/min, keep it for 5 minutes, then raise the temperature to 980-1000°C at a speed of 10°C/min, hold it for 5-20 minutes, and then heat it at 5°C /min speed down to 300 ℃, and finally the weldment is cooled to room temperature with the furnace. Others are the same as in the first embodiment.

Embodiment 11: The difference between this embodiment and Embodiment 1 is that the thickness of the Ti interlayer foil on the side near the ceramic in the assembly to be welded in step 4 is 50-150 μm; the thickness of the Ti interlayer foil near the metal side is The thickness of the layer foil is 10-50 μm. Others are the same as in the first embodiment.

Embodiment 12: This embodiment differs from Embodiment 1 in that: the thickness of the Ti interlayer foil on the ceramic side of the piece to be welded in step 4 is 50-120 μm; the thickness of the Ti interlayer foil on the metal side is The thickness of the layer foil is 20-50 μm. Others are the same as in the first embodiment.

Specific Embodiment Thirteen: The difference between this embodiment and specific embodiment 1 is that the thickness of the Ti interlayer foil on the side near the ceramic in the assembly to be welded in step 4 is 50-100 μm; the thickness of the Ti interlayer foil near the metal side Layer foil thickness is 30 ~ 50μm. Others are the same as in the first embodiment.

Embodiment 14: The difference between this embodiment and Embodiment 1 is that in step 3, take the Ni interlayer foil with a thickness of 60 μm to 100 μm in step 2, immerse it in an acetone solution and ultrasonically clean it for 5 minutes, and then clean it on the Ni interlayer A Ni-B amorphous alloy layer with a thickness of 1 μm to 4 μm is deposited on one side of the foil to obtain a Ni/Ni-B composite foil. Others are the same as in the first embodiment.

Embodiment 15: The difference between this embodiment and Embodiment 1 is that in Step 3, take the Ni interlayer foil with a thickness of 60 μm to 80 μm and process it in Step 2, immerse it in an acetone solution and ultrasonically clean it for 5 minutes, and then clean it on the Ni interlayer A Ni-B amorphous alloy layer with a thickness of 1 μm to 3 μm is deposited on one side of the foil to obtain a Ni/Ni-B composite foil. Others are the same as in the first embodiment.

Embodiment 16: The difference between this embodiment and Embodiment 1 is that in step 3, take the Ni interlayer foil with a thickness of 70 μm and process in step 2, immerse it in acetone solution and ultrasonically clean it for 5 minutes, and then clean it on the Ni interlayer foil Deposit a Ni-B amorphous alloy layer with a thickness of 2 μm on one side to obtain a Ni/Ni-B composite foil. Others are the same as in the first embodiment.

The content of the present invention is not limited to the content of the above-mentioned embodiments, and a combination of one or several specific embodiments can also achieve the purpose of the invention.

Verify the beneficial effects of the present invention by the following examples:

Example 1

The ceramic/metal connection method based on Ni-B/Ti transient liquid phase in situ reaction of this embodiment is carried out according to the following steps:

1. Chemically clean the surface of GH99 alloy, Al ₂ O ₃ ceramics and welding intermediate layer materials 50μm thick Ti foil and 50μm thick Ni foil; use 800#, 1000#, 1200#, 1500# sandpaper to polish the surface of GH99 alloy , then immerse in acetone solution for ultrasonic cleaning for 5 minutes, and dry for later use; for Al ₂ O ₃ ceramics, use 1200# and 1500# diamond discs to polish the surface, immerse in acetone solution for ultrasonic cleaning for 5 minutes, and dry for later use;

2. Take the Ti intermediate layer foil and the Ni intermediate layer foil, first immerse them in acetone solution for ultrasonic cleaning for 5 minutes, then soak them in the deoxidizing film solution for 10-15 minutes for deoxidizing film treatment, and then take out the Ti intermediate layer foil and the Ni intermediate layer foil are rinsed with clear water, and dried for later use; the deoxidized film solution is composed of HF with a mass percentage of 2% to ₅ %, HNO with a mass percentage of 45% and the remainder water composition;

Three, the Ni interlayer foil of 50 μm in thickness after step two treatment is immersed in an acetone solution and ultrasonically cleaned for 5 minutes, and then deposits a 2 μm thick Ni-B amorphous alloy layer on one side of the Ni interlayer foil to obtain Ni/ Ni-B composite foil; then wash the Ni/Ni-B composite foil with clear water and dry it for later use; wherein, the B content of the Ni-B amorphous alloy layer is 5wt.%;

4. Take the Al ₂ O ₃ ceramics processed in step 1, GH99 alloy, the Ti interlayer foil processed in step 2, and the Ni/Ni-B composite foil obtained in step 3 to assemble the parts to be welded in a stacked manner, the assembly sequence It is: GH99/Ti(50μm)/(Ni/Ni-B)/Ti(50μm)/Al ₂ O ₃ ; wherein, the Ni-B amorphous alloy layer of the Ni/Ni-B composite foil is close to the ceramic side, The ratio of the total thickness of the two layers of Ti foil to the thickness of the Ni intermediate layer foil (not including the thickness of the Ni-B amorphous alloy layer) is 1.0:2.0; place the workpiece to be welded in a vacuum diffusion welding furnace and apply a pressure of 5 MPa , and evacuate to 1×10 ^-3 Pa, then raise the temperature of the vacuum diffusion welding furnace to 900°C at a speed of 30°C/min, keep it for 5 minutes, then raise the temperature to 980°C at a speed of 10°C/min, hold it for 5 minutes, and then The temperature was lowered to 300°C at a rate of 5°C/min, and finally the welded piece was cooled to room temperature with the furnace to complete the ceramic/metal connection based on Ni-B/Ti instantaneous liquid phase in-situ reaction.

The chemical deposition condition of the present embodiment is:

The electroless plating solution contains NiCl·6H ₂ O with a concentration of 5g/L, NaC ₂ H ₃ O ₂ with a concentration of 7g/L, C ₂ H ₁₀ BN with a concentration of 1g/L and PbCl with a concentration of 10-50mg/L ₂ ; The pH of the electroless plating solution is 4, the temperature of the electroless plating solution is 60° C., and the electroless deposition time is 10 minutes.

The method in this example connects GH99 alloy and Al ₂ O ₃ ceramics, and the shear strength of the prepared GH99/Ti/(Ni/Ni-B)/Ti/Al ₂ O ₃ joint can reach 92-128 MPa, which is higher than that without in-situ reaction GH99/Ti/Ni/Ti/Al ₂ O ₃ joint strength increased by 43% to 57%.

Example 2

The ceramic/metal connection method based on Ni-B/Ti transient liquid phase in situ reaction of this embodiment is carried out according to the following steps:

1. Chemically clean the surface of GH99 alloy, Al ₂ O ₃ ceramics and welding intermediate layer materials 50μm thick Ti foil and 50μm thick Ni foil; use 800#, 1000#, 1200#, 1500# sandpaper to polish the surface of GH99 alloy , then immerse in acetone solution for ultrasonic cleaning for 5 minutes, and dry for later use; for Al ₂ O ₃ ceramics, use 1200# and 1500# diamond discs to polish the surface, immerse in acetone solution for ultrasonic cleaning for 5 minutes, and dry for later use;

2. Take the Ti intermediate layer foil and the Ni intermediate layer foil, first immerse them in acetone solution for ultrasonic cleaning for 5 minutes, then soak them in the deoxidizing film solution for 10-15 minutes for deoxidizing film treatment, and then take out the Ti intermediate layer foil and the Ni intermediate layer foil are rinsed with clear water, and dried for later use; the deoxidized film solution is composed of HF with a mass percentage of 2% to ₅ %, HNO with a mass percentage of 45% and the remainder water composition;

Three, the Ni interlayer foil of 50 μm in thickness after step 2 treatment is immersed in an acetone solution and ultrasonically cleaned for 5 min, and then deposited a 3 μm thick Ni-B amorphous alloy layer on one side of the Ni interlayer foil to obtain Ni/ Ni-B composite foil; then wash the Ni/Ni-B composite foil with clear water and dry it for later use; wherein, the B content of the Ni-B amorphous alloy layer is 5wt.%;

4. Take the Al ₂ O ₃ ceramics processed in step 1, GH99 alloy, the Ti interlayer foil processed in step 2, and the Ni/Ni-B composite foil obtained in step 3 to assemble the parts to be welded in a stacked manner, the assembly sequence It is: GH99/Ti(50μm)/(Ni/Ni-B)/Ti(50μm)/Al ₂ O ₃ ; wherein, the Ni-B amorphous alloy layer of the Ni/Ni-B composite foil is close to the ceramic side, The ratio of the total thickness of the two layers of Ti foil to the thickness of the Ni intermediate layer foil (not including the thickness of the Ni-B amorphous alloy layer) is 1.0:2.0; place the workpiece to be welded in a vacuum diffusion welding furnace and apply a pressure of 5 MPa , and evacuate to 1×10 _- ³ Pa, then raise the temperature of the vacuum diffusion welding furnace to 900°C at a speed of 30°C/min, keep it for 5 minutes, then raise the temperature to 980°C at a speed of 10°C/min, hold it for 5 minutes, and then The temperature was lowered to 300°C at a rate of 5°C/min, and finally the welded piece was cooled to room temperature with the furnace to complete the ceramic/metal connection based on Ni-B/Ti instantaneous liquid phase in-situ reaction.

The electrodeposition conditions of this embodiment are: the electroplating solution contains NiSO ₄ 6H ₂ O with a concentration of 240g/L, NiCl 6H ₂ O with a concentration of 5g/L, H ₃ BO ₃ with a concentration of 30g/L and a concentration of 3g/L of C ₂ H ₁₀ BN; the pH of the electroplating solution is 3.5, the temperature of the electroplating solution is 45°C, the current density is 1A/dm ² , and the electroplating time is 10min.

The method in this example connects GH99 alloy and Al ₂ O ₃ ceramics, and the shear strength of the prepared GH99/Ti/(Ni/Ni-B)/Ti/Al ₂ O ₃ joint can reach 93-120 MPa, which is higher than that without in-situ reaction GH99/Ti/Ni/Ti/Al ₂ O ₃ joint strength increased by 43% to 55%.

Example 3

The ceramic/metal connection method based on Ni-B/Ti transient liquid phase in situ reaction of this embodiment is carried out according to the following steps:

1. Surface chemical cleaning of GH99 alloy, Al ₂ O ₃ ceramics and welding intermediate layer materials 20μm thick Ti foil, 100μm thick Ti foil, and 80μm thick Ni foil; use 800#, 1000#, 1200#, Polish the surface with 1500# sandpaper, then immerse in acetone solution for ultrasonic cleaning for 5 minutes, and dry it for later use; for Al ₂ O ₃ ceramics, use 1200# and 1500# diamond discs to polish the surface, immerse in acetone solution for ultrasonic cleaning for 5 minutes, and dry it for later use;

2. Take the Ti intermediate layer foil and the Ni intermediate layer foil, first immerse them in acetone solution for ultrasonic cleaning for 5 minutes, then soak them in the deoxidizing film solution for 10-15 minutes for deoxidizing film treatment, and then take out the Ti intermediate layer foil and the Ni intermediate layer foil are rinsed with clear water, and dried for later use; the deoxidized film solution is composed of HF with a mass percentage of 2% to ₅ %, HNO with a mass percentage of 45% and the remainder water composition;

Three, the Ni interlayer foil of 80 μm in thickness after step 2 treatment is immersed in an acetone solution and ultrasonically cleaned for 5 min, and then deposited a 2 μm thick Ni-B amorphous alloy layer on one side of the Ni interlayer foil to obtain Ni/ Ni-B composite foil; then wash the Ni/Ni-B composite foil with clear water and dry it for later use; wherein, the B content of the Ni-B amorphous alloy layer is 5wt.%;

4. Take the Al ₂ O ₃ ceramics processed in step 1, GH99 alloy, the Ti interlayer foil processed in step 2, and the Ni/Ni-B composite foil obtained in step 3 to assemble the parts to be welded in a stacked manner, the assembly sequence It is: GH99/Ti(20μm)/(Ni/Ni-B)/Ti(100μm)/Al ₂ O ₃ ; wherein, the Ni-B amorphous alloy layer of the Ni/Ni-B composite foil is close to the ceramic side, The ratio of the total thickness of the two-layer Ti intermediate layer foil to the thickness of the Ni intermediate layer foil (not including the thickness of the Ni-B amorphous alloy layer) is 1.0:1.5; the parts to be welded are placed in a vacuum diffusion welding furnace and applied 5MPa pressure, and evacuate to 1×10 ^-3 Pa, then raise the temperature of the vacuum diffusion welding furnace to 900°C at a speed of 30°C/min, keep it for 5min, then raise the temperature to 980°C at a speed of 10°C/min, and keep it for 5min , and then cooled down to 300°C at a rate of 5°C/min, and finally the weldment was cooled to room temperature with the furnace, and the ceramic/metal connection based on Ni-B/Ti instantaneous liquid phase in-situ reaction was completed.

The chemical deposition condition of the present embodiment is:

The electroless plating solution contains NiCl·6H ₂ O with a concentration of 5g/L, NaC ₂ H ₃ O ₂ with a concentration of 7g/L, C ₂ H ₁₀ BN with a concentration of 1g/L and PbCl with a concentration of 10-50mg/L ₂ ; The pH of the electroless plating solution is 4, the temperature of the electroless plating solution is 60° C., and the electroless deposition time is 10 minutes.

The method in this example connects GH99 alloy and Al ₂ O ₃ ceramics, and the shear strength of the prepared GH99/Ti/(Ni/Ni-B)/Ti/Al ₂ O ₃ joint can reach 95-136 MPa, which is higher than that without in-situ reaction GH99/Ti/Ni/Ti/Al ₂ O ₃ joint strength increased by 45% to 72%.

Example 4

The ceramic/metal connection method based on Ni-B/Ti transient liquid phase in situ reaction of this embodiment is carried out according to the following steps:

1. Surface chemical cleaning of GH99 alloy, Al ₂ O ₃ ceramics and welding intermediate layer materials 20μm thick Ti foil, 100μm thick Ti foil, and 80μm thick Ni foil; use 800#, 1000#, 1200#, Polish the surface with 1500# sandpaper, then immerse in acetone solution for ultrasonic cleaning for 5 minutes, and dry it for later use; for Al ₂ O ₃ ceramics, use 1200# and 1500# diamond discs to polish the surface, immerse in acetone solution for ultrasonic cleaning for 5 minutes, and dry it for later use;

2. Take the Ti intermediate layer foil and the Ni intermediate layer foil, first immerse them in acetone solution for ultrasonic cleaning for 5 minutes, then soak them in the deoxidizing film solution for 10-15 minutes for deoxidizing film treatment, and then take out the Ti intermediate layer foil and the Ni intermediate layer foil are rinsed with clear water, and dried for later use; the deoxidized film solution is composed of HF with a mass percentage of 2% to ₅ %, HNO with a mass percentage of 45% and the remainder water composition;

Three, the Ni interlayer foil of 80 μm in thickness after step 2 treatment is immersed in an acetone solution and ultrasonically cleaned for 5 min, and then deposited a 2 μm thick Ni-B amorphous alloy layer on one side of the Ni interlayer foil to obtain Ni/ Ni-B composite foil; then wash the Ni/Ni-B composite foil with clear water and dry it for later use; wherein, the B content of the Ni-B amorphous alloy layer is 5wt.%;

4. Take the Al ₂ O ₃ ceramics processed in step 1, GH99 alloy, the Ti interlayer foil processed in step 2, and the Ni/Ni-B composite foil obtained in step 3 to assemble the parts to be welded in a stacked manner, the assembly sequence It is: GH99/Ti(20μm)/(Ni/Ni-B)/Ti(100μm)/Al ₂ O ₃ ; wherein, the Ni-B amorphous alloy layer of the Ni/Ni-B composite foil is close to the ceramic side, The ratio of the total thickness of the two layers of Ti foil to the thickness of the Ni intermediate layer foil (not including the thickness of the Ni-B amorphous alloy layer) is 1.0:1.5; place the workpiece to be welded in a vacuum diffusion welding furnace and apply a pressure of 5 MPa , and evacuate to 1×10 ^-3 Pa, then raise the temperature of the vacuum diffusion welding furnace to 900°C at a speed of 30°C/min, keep it for 5 minutes, then raise the temperature to 1000°C at a speed of 10°C/min, hold it for 15 minutes, and then The temperature was lowered to 300°C at a rate of 5°C/min, and finally the welded piece was cooled to room temperature with the furnace to complete the ceramic/metal connection based on Ni-B/Ti instantaneous liquid phase in-situ reaction.

The chemical deposition condition of the present embodiment is:

The electroless plating solution contains NiCl·6H ₂ O with a concentration of 5g/L, NaC ₂ H ₃ O ₂ with a concentration of 7g/L, C ₂ H ₁₀ BN with a concentration of 1g/L and PbCl with a concentration of 10-50mg/L ₂ ; The pH of the electroless plating solution is 4, the temperature of the electroless plating solution is 60° C., and the electroless deposition time is 10 minutes.

The method in this example connects GH99 alloy and Al ₂ O ₃ ceramics, and the shear strength of the prepared GH99/Ti/(Ni/Ni-B)/Ti/Al ₂ O ₃ joint can reach 98-132 MPa, which is higher than that without in-situ reaction GH99/Ti/Ni/Ti/Al ₂ O ₃ joint strength increased by 48% to 70%.

Example 5

The ceramic/metal connection method based on Ni-B/Ti transient liquid phase in situ reaction of this embodiment is carried out according to the following steps:

1. Surface chemical cleaning of metal Nb, SiC ceramics and welding intermediate layer materials 20μm thick Ti foil, 100μm thick Ti foil, and 80μm thick Ni foil; use 800#, 1000#, 1200#, 1500# sandpaper for metal Nb Polish the surface, then immerse in acetone solution for ultrasonic cleaning for 5 minutes, and dry it for later use; for SiC ceramics, use 1200# and 1500# diamond discs to polish the surface, immerse in acetone solution for ultrasonic cleaning for 5 minutes, and dry it for later use;

2. Take the Ti intermediate layer foil and the Ni intermediate layer foil, first immerse them in acetone solution for ultrasonic cleaning for 5 minutes, then soak them in the deoxidizing film solution for 10-15 minutes for deoxidizing film treatment, and then take out the Ti intermediate layer foil and the Ni intermediate layer foil are rinsed with clear water, and dried for later use; the deoxidized film solution is composed of HF with a mass percentage of 2% to ₅ %, HNO with a mass percentage of 45% and the remainder water composition;

Three, the Ni interlayer foil of 80 μm in thickness after step 2 treatment is immersed in an acetone solution and ultrasonically cleaned for 5 min, and then deposited a 2 μm thick Ni-B amorphous alloy layer on one side of the Ni interlayer foil to obtain Ni/ Ni-B composite foil; then wash the Ni/Ni-B composite foil with clear water and dry it for later use; wherein, the B content of the Ni-B amorphous alloy layer is 5wt.%;

4. Take the SiC ceramics processed in step 1, metal Nb, the Ti intermediate layer foil processed in step 2, and the Ni/Ni-B composite foil obtained in step 3 to assemble the parts to be welded in a stacked manner. The assembly sequence is: Nb /Ti(20μm)/(Ni/Ni-B)/Ti(100μm)/SiC; Among them, the Ni-B amorphous alloy layer of the Ni/Ni-B composite foil is close to the ceramic side, and the two-layer Ti foil The ratio of the total thickness to the thickness of the Ni intermediate layer foil (not including the thickness of the Ni-B amorphous alloy layer) is 1.0:1.5; place the workpiece to be welded in a vacuum diffusion welding furnace, apply a pressure of 5 MPa, and evacuate to 1 ×10 ^-3 Pa, then raise the temperature of the vacuum diffusion welding furnace to 900°C at a speed of 30°C/min, keep it for 5 minutes, then raise it to 1000°C at a speed of 10°C/min, hold it for 15 minutes, and then heat it at a speed of 5°C/min The temperature is lowered to 300° C., and finally the welded part is cooled to room temperature with the furnace to complete the ceramic/metal connection based on the Ni-B/Ti instantaneous liquid phase in-situ reaction.

The chemical deposition condition of the present embodiment is:

The electroless plating solution contains NiCl·6H ₂ O with a concentration of 5g/L, NaC ₂ H ₃ O ₂ with a concentration of 7g/L, C ₂ H ₁₀ BN with a concentration of 1g/L and PbCl with a concentration of 10-50mg/L ₂ ; The pH of the electroless plating solution is 4, the temperature of the electroless plating solution is 60° C., and the electroless deposition time is 10 minutes.

The method of this embodiment connects metal Nb and SiC ceramics, and the shear strength of the prepared Nb/Ti/(Ni/Ni-B)/Ti/SiC joint can reach 82-130 MPa, which is higher than that of Nb/Ti/Ni without in-situ reaction. /Ti/SiC joint strength increased by 35% to 56%.

Claims (10)

1. the ceramic/metal connection method based on Ni-B/Ti Transient liquid phase reaction in-situs, it is characterised in that it is according to following step It is rapid to carry out：

First, acetone soln ultrasound is then immersed in using 800#, 1000#, 1200#, 1500# sand paper polishing surface to metallic matrix 5min is cleaned, is dried standby；To ceramic matrix using 1200# and 1500# diamond disks polishing surface, immersion acetone soln surpasses Sound cleans 5min, dries standby；

2nd, Ti, Ni intermediate layer paillon foil are taken, is dipped in acetone soln is cleaned by ultrasonic 5min first, oxide film dissolving is put into afterwards Solution soaks 10~15min and carries out oxide film dissolving processing, then takes out Ti, Ni intermediate layer paillon foil and is rinsed well with clear water, is dried It is standby；HF that it is 2%~5% by weight/mass percentage composition that described oxide film dissolving solution, which is, weight/mass percentage composition be 20%~ 45% HNO₃Constituted with the water of surplus；

3rd, it is ultrasonic cleaning in the Ni intermediate layers paillon foil of 50 μm~100 μm step 2 processing, immersion acetone soln to take thickness 5min, the Ni-B amorphous alloy layers of 1 μm~5 μ m-thicks are deposited in Ni intermediate layers paillon foil side, Ni/Ni-B composite foils are obtained afterwards； Then Ni/Ni-B composite foils are cleaned using clear water, dried standby；Wherein, the B content of described Ni-B amorphous alloy layers is 3wt.%~6wt.%；

4th, the Ni/ for taking Ti intermediate layers paillon foil and step 3 after ceramics, metal, the step 2 processing of step one processing to obtain Ni-B composite foils are assembled into part to be welded to stack mode, and assembling sequence is：Metal/Ti intermediate layers paillon foil/Ni/Ni-B composite insulating foils Piece/Ti intermediate layers paillon foil/ceramics；Part to be welded is placed in Vacuum diffusion bonding furnace, applies 5~10MPa pressure, and be evacuated to 5 ×10^-4~1 × 10^-3Pa, is then warming up to 900 DEG C by Vacuum diffusion bonding furnace with 30 DEG C/min speed, is incubated 5min, then with 10 DEG C/min speed is warming up to 950~1000 DEG C, is incubated 5~30min, then is cooled to 300 DEG C with 5 DEG C/min speed, most Weldment cools to room temperature with the furnace afterwards, completes the described connection of the ceramic/metal based on Ni-B/Ti Transient liquid phase reaction in-situs； Wherein, the Ni-B amorphous alloy layers of Ni/Ni-B composite foils are close to ceramic side, the gross thickness of two layers of Ti intermediate layers paillon foil with not The thickness proportion of Ni intermediate layers foil thickness comprising Ni-B amorphous alloy layers is 1：(1.0~2.5).

2. the ceramic/metal connection method according to claim 1 based on Ni-B/Ti Transient liquid phase reaction in-situs, it is special Levy and be that the surface deposition Ni-B amorphous alloy layers in Ni intermediate layers paillon foil side described in step 3 refer to use chemical plating Ni-b alloy method or plating ni-b alloy method are deposited.

3. the ceramic/metal connection method according to claim 2 based on Ni-B/Ti Transient liquid phase reaction in-situs, it is special Levy and be that the sedimentary condition of described chemical nickel boron alloy method is：Chemical plating solution contains the NiCl that concentration is 5g/L₂· 6H₂O, concentration are 7g/L NaC₂H₃O₂, concentration be 1g/L C₂H₁₀The BN and PbCl that concentration is 10~50mg/L₂；Chemical plating is molten Liquid pH is 4, and chemical plating solution temperature is 59~81 DEG C, and the chemical deposition time is 5~30min.

4. the ceramic/metal connection method according to claim 3 based on Ni-B/Ti Transient liquid phase reaction in-situs, it is special Levy and be that the sedimentary condition of described chemical nickel boron alloy method is：Chemical plating solution contains the NiCl that concentration is 5g/L₂· 6H₂O, concentration are 7g/L NaC₂H₃O₂, concentration be 1g/L C₂H₁₀The BN and PbCl that concentration is 10~50mg/L₂；Chemical plating is molten Liquid pH is 4, and chemical plating solution temperature is 65~80 DEG C, and the chemical deposition time is 5~20min.

5. the ceramic/metal connection method according to claim 2 based on Ni-B/Ti Transient liquid phase reaction in-situs, it is special Levy and be that the sedimentary condition of described plating ni-b alloy method is：Electroplating solution contains the NiSO that concentration is 240g/L₄·6H₂O、 Concentration is 5g/L NiCl₂·6H₂O, concentration are 30g/L H₃BO₃With the C that concentration is 3g/L₂H₁₀BN；Electroplating solution pH is 3.5, electroplating solution temperature is 44~46 DEG C, and current density is 0.5~1.5A/dm², electroplating time is 10~60min.

6. the ceramic/metal connection method according to claim 5 based on Ni-B/Ti Transient liquid phase reaction in-situs, it is special Levy and be that the sedimentary condition of described plating ni-b alloy method is：Electroplating solution contains the NiSO that concentration is 240g/L₄·6H₂O、 Concentration is 5g/L NiCl₂·6H₂O, concentration are 30g/L H₃BO₃With the C that concentration is 3g/L₂H₁₀BN；Electroplating solution pH is 3.5, electroplating solution temperature is 45~46 DEG C, and current density is 0.8~1.2A/dm², electroplating time is 10~50min.

7. the ceramic/metal connection method according to claim 1 based on Ni-B/Ti Transient liquid phase reaction in-situs, it is special Levy be described oxide film dissolving solution be 2%~4% by weight/mass percentage composition HF, weight/mass percentage composition be 20%~ 40% HNO₃Constituted with the water of surplus.

8. the ceramic/metal connection method according to claim 1 based on Ni-B/Ti Transient liquid phase reaction in-situs, it is special Levy and be the B content of described Ni-B amorphous alloy layers for 3wt.%~5wt.%.

9. the ceramic/metal connection method according to claim 1 based on Ni-B/Ti Transient liquid phase reaction in-situs, it is special Levy and be in step 4 part to be welded being placed in Vacuum diffusion bonding furnace, apply 5~10MPa pressure, and be evacuated to 5 × 10^-4~1 ×10^-3Pa, is then warming up to 900 DEG C with 30 DEG C/min speed by Vacuum diffusion bonding furnace, is incubated 5min, then with 10 DEG C/min's Speed is warming up to 980~1000 DEG C, is incubated 5~20min, then is cooled to 300 DEG C with 5 DEG C/min speed, last weldment with Stove is cooled to room temperature.

10. the ceramic/metal connection method according to claim 1 based on Ni-B/Ti Transient liquid phase reaction in-situs, it is special It is 50~150 μm to levy the Ti intermediate layers foil thickness in the part to be welded for being to be assembled in step 4 close to ceramics side；Close to gold The Ti intermediate layers foil thickness for belonging to side is 10~50 μm.