Marine metal clad plate and method of making same

Abstract

The application discloses a marine metal composite plate and a preparation method thereof, and belongs to the technical field of metal materials. The marine metal composite plate has a yield strength of 390-450 Mpa, a tensile strength of 490-560 Mpa, a shear strength of >200 Mpa, an interlayer bonding rate of 100%, a bonding layer thickness of 1.8-2.6 microns, a composite interface containing trace FeTi and Fe2Ti, no TiC brittle phase, no cracking in 180-degree inner bending and outer bending, and qualified corrosion performance. The metal composite plate prepared by the application has high interlayer bonding strength and high material yield rate, and has the advantages of corrosion resistance, light weight, high strength, high-temperature impact resistance and the like, and is suitable for ship manufacturing and other large-scale industrial manufacturing fields.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of metal materials, and relates to a marine metal composite plate and a preparation method thereof. BACKGROUND

[0002] At present, steel plates and some anticorrosive coatings are mainly used in domestic shipbuilding. Since the marine environment is very complex, the ship body and related parts are easily corroded, which greatly increases the maintenance cost of the ship and reduces the service life of the ship. Titanium metal and alloy have the advantages of corrosion resistance, lightweight, high strength, high temperature impact resistance and the like, and are called marine metals, and are suitable for marine engineering. However, the expensive cost limits its application, and the metal composite plate, as a substitute for a single rare metal, has the obvious advantages of saving the use amount of precious metal and reducing the manufacturing cost by 50-70%. The clad layer material of the metal composite plate can be titanium and its alloy, and the base layer can be ship steel.

[0003] Explosive cladding is a method of using explosive explosion to drive the inclined collision of the clad plate and the base plate to generate metal jet to remove the oxide film on the metal surface, and the atoms of the two metals are combined under the huge pressure. The method has the advantages of simple preparation process and low cost, and is used for preparing the composite plate with thick clad layer and base layer, and is an important method for producing medium-thick composite plates.

[0004] The explosive cladding method currently used to prepare the composite plate faces the following difficulties:

[0005] 1. The welding energy currently selected is mainly powdery explosive. In view of safety, the state civil explosive department requires that the production and use of powdery explosive be gradually cancelled, and the entire explosive cladding industry will face the difficulty of no available explosive.

[0006] 2. The current explosive cladding method mainly uses powdery explosive, and the uniformity of the powdery explosive is limited, and the stable detonation distance is also limited, thereby limiting the specification of the prepared metal composite plate.

[0007] 3. The current explosive cladding method uses the method of point-shaped gap support to keep the clad layer and the base layer at a certain distance, and then the inclined collision occurs. This method cannot guarantee the flatness of the large-area and ultra-thin metal clad layer, so that the jet cannot be smoothly discharged, which will cause the bonding quality of the composite plate to decrease, and even the clad layer metal is broken.

[0008] In summary, the manufacturing of large-area and ultra-thin metal composite plates has also become a problem that restricts the neck of the shipbuilding, military industry and high-end manufacturing industry in China. Therefore, it is urgent to research a new marine metal composite plate and a preparation method thereof. SUMMARY

[0009] In view of the above technical problems, the application provides a marine metal composite plate and a preparation method thereof.

[0010] The technical scheme adopted to solve the technical problems is as follows: the ship metal composite plate has a yield strength of 390-450 MPa, a tensile strength of 490-560 MPa, a shear strength of >200 MPa, an interlayer bonding rate of 100%, a bonding layer thickness of 1.8-2.6 μm, a composite interface containing trace FeTi and Fe2Ti, no TiC brittle phase, no cracking in 180-degree inner and outer bending, and qualified corrosion performance.

[0011] The preparation method of the above ship metal composite plate comprises the following steps:

[0012] a. performing surface rust removal and polishing treatment on the composite layer metal and the base layer metal, uniformly applying water-based glue on the bonding surfaces of the composite layer metal and the base layer metal, and firmly bonding them together;

[0013] b. bonding a sealing strip on the composite layer metal, pouring prepared liquid explosive, arranging a detonator, and initiating to obtain the metal composite plate;

[0014] c. preparing the metal composite plate into a plate or a coiled plate, and performing heat treatment to obtain the ship metal composite plate.

[0015] In the step a, the composite layer metal is a titanium plate and a titanium alloy plate selected from any one of TA1, TA2, TA8, TA9 and TA10, and the thickness of the titanium plate and the titanium alloy plate is ≥0.1 mm; and the base layer metal is a carbon steel plate.

[0016] In the step a, the water-based glue has a thickness of 1-2 mm; the glue content in the water-based glue is >25%, the pH is 7-7.5, the Na2O is <0.2%, the specific gravity is 1.165-1.175 g / cm3, and the viscosity is 1-5 mpa.s. 3

[0017] In the step b, the liquid explosive is composed of three components A, B and C, and the three components are prepared according to the following mass ratio:

[0018] A, 40 parts of magnesium nitrate, 35 parts of sodium nitrate, 3 parts of a surfactant, and 22 parts of water;

[0019] B, 40 parts of nitromethane, 40 parts of ethanol, 10 parts of ethylenediamine, and 10 parts of nitromethylammonium nitrate;

[0020] C, 26 parts of sodium chloride and 74 parts of water.

[0021] The preparation method of the above liquid explosive is as follows: the components A, B and C are prepared according to the ratio of A, B and C, and then mixed according to the ratio of A 45-60 parts, B 15-20 parts and C 20-40 parts to become the liquid explosive for explosive welding.

[0022] ​Further, the A component needs to satisfy the following conditions:

[0023] The purity of magnesium nitrate is > 99.5wt%, the bulk density is 0.8-0.9g / cm 3 , the average particle size is less than 200 mesh, and the water content is less than 0.05wt%;

[0024] The purity of sodium nitrate is > 99.5wt%, the bulk density is 2.2-2.3g / cm 3 , the average particle size is less than 200 mesh, and the water content is less than 0.05wt%;

[0025] The surfactant is tri-glycerol monostearate, and the water content is less than 0.3wt%.

[0026] Further, the B component needs to satisfy the following conditions:

[0027] The purity of nitromethane is > 98wt%, the density is 1.1-1.2g / cm 3 , the viscosity is less than 4mpa.S, and the water content is less than 0.3wt%;

[0028] The purity of ethanol is > 95wt%, the density is 0.79g / cm 3 , the viscosity is less than 1.1mpa.S, and the water content is less than 0.3wt%;

[0029] The purity of ethylenediamine is > 99.8wt%, the density is 0.89g / cm 3 , and the water content is less than 0.05wt%;

[0030] The purity of nitromethane is > 99.8wt%, the density is 1.2-1.3g / cm 3 , and the water content is less than 0.05wt%.

[0031] Further, the C component needs to satisfy the following conditions:

[0032] The purity of sodium chloride is > 95wt%, the bulk density is 2.1-2.3g / cm 3 , the average particle size is less than 100 mesh, and the water content is less than 0.5wt%.

[0033] In the above step c, the heat treatment step is: 400°C for 2h→540°C for 1.5h→630°C for 1h→cooling with the furnace.

[0034] The present application has the advantages that the yield strength of the marine metal composite plate can reach 390-450Mpa, the tensile strength can reach 490-560Mpa, the shear strength is far more than the national standard of 140MPa, can reach more than 200MPa, and the interlayer bonding rate is 100%. The inner bending and outer bending of 180 degrees do not crack, the corrosion performance is qualified, and the manufacturing and use of the ship can be met. The specification of the marine metal composite plate is not limited, the bonding rate and bonding strength are high, the bonding layer thickness is 1.8-2.6 microns, the thickness is uniform and moderate, there is only a small amount of FeTi and Fe2Ti, there is no TiC brittle phase, the bonding performance and corrosion resistance are ensured, and all detection indexes exceed the industry requirements.

[0035] The present application also provides a preparation method of the marine metal composite plate, and innovatively uses liquid explosives to replace traditional explosives, the advantages of the liquid explosives ensure that the indexes of the metal composite plate are greatly broken through; the water-based glue is used to replace the traditional point support, and the flatness of the large-area and ultra-thin metal can be ensured, the high temperature generated by explosion makes the water-based glue gasify instantly, and the gas can assist the jet to improve the welding quality.

[0036] The present application also provides a liquid explosive for explosion welding, which can replace the traditional powder explosives, solve the difficulty of no explosives available in the explosion composite industry, and has the following advantages: the explosive can be divided into three components ABC, the three components are not explosive when stored separately, become the special explosive for explosion welding after mixing, and can be used immediately, which is safe and convenient; the uniformity of the liquid explosive is far higher than that of the powder explosive, because the liquid diffusion uniformity is far higher than that of the physical mixing of solid particles, the liquid explosive can be infinitely stable detonation, and the specification of the metal composite plate is no longer limited; the work capacity of the liquid explosive is far higher than that of the powder explosive, and the bonding quality of the metal composite plate is greatly improved.

[0037] The metal composite plate prepared by the present application has high interlayer bonding strength and high material yield rate, has the advantages of corrosion resistance, lightweight, high strength, high temperature impact resistance and the like, and is suitable for ship manufacturing and other large-scale industrial manufacturing fields. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 It is an EDS line scanning diagram of the marine metal composite plate of the present application;

[0039] Figure 2 It is an XRD pattern of the marine metal composite plate of the present application;

[0040] Figure 3 It is a use state diagram before explosion compounding by the method of the present application;

[0041] Among them, 1 is a liquid explosive, 2 is a composite plate, 3 is a water-based glue, 4 is a base plate, and 5 is a detonator;

[0042] Figure 4 Figure for inner and outer bending 180-degree test of material for embodiment 1-3 and comparative example 1 of the present application;

[0043] Figure 5 Figure for macroscopic detection of comparative example 1 of the present application. DETAILED DESCRIPTION

[0044] The technical solution of the present application can be implemented in the following manner.

[0045] The ship metal composite plate has yield strength of 390-450Mpa, tensile strength of 490-560Mpa, shear strength of >200MPa, interlayer bonding rate of 100%, bonding layer thickness of 1.8-2.6μm, and composite interface containing trace FeTi and Fe2Ti without TiC brittle phase, and does not crack in inner and outer bending 180-degree.

[0046] The ship metal composite plate of the present application has bonding layer thickness of 1.8-2.6μm determined by EDS line scanning (as shown in Figure 1 The ship metal composite plate of the present application has only a small amount of FeTi and Fe2Ti without TiC brittle phase, and has good bonding performance and corrosion resistance, as analyzed by EDS point scanning and XRD spectrum (as shown in Figure 2 The ship metal composite plate of the present application has only a small amount of FeTi and Fe2Ti without TiC brittle phase, and has good bonding performance and corrosion resistance, as analyzed by EDS point scanning and XRD spectrum (as shown in

[0047] The preparation method of the above ship metal composite plate comprises the following steps:

[0048] a. The surface of the composite layer metal and the base layer metal is treated by rust removal and polishing, and water-based glue is uniformly applied on the bonding surface of the composite layer metal and the base layer metal, so that they are firmly bonded together;

[0049] b. The sealing strip is bonded on the composite layer metal, the prepared liquid explosive is poured, the detonator is arranged (as shown in Figure 3 ), and the metal composite plate is obtained by detonation;

[0050] c. The metal composite plate is prepared into a plate or a coiled material, and the ship metal composite plate is obtained after heat treatment, and the heat treatment process flow is: 400℃ for 2 hours, 540℃ for 1.5 hours, 630℃ for 1 hour, and cooling in the furnace.

[0051] In the step a, the multi-layer metal is titanium plate and titanium alloy plate, which is selected from any one of TA1, TA2, TA8, TA9 and TA10, and the thickness of the titanium plate and titanium alloy plate is greater than or equal to 0.1 mm; the base metal is carbon steel plate; the thickness of the water-based sol is 1-2 mm; the glue content in the water-based sol is greater than 25%, the pH is 7-7.5, the Na2O is less than 0.2%, and the specific gravity is 1.165-1.175 g / cm 3 , and the viscosity is 1-5 mpa.S.

[0052] In the step b, the liquid explosive is composed of three components A, B and C, which are prepared according to the following mass ratio:

[0053] A, 40 parts of magnesium nitrate, 35 parts of sodium nitrate, 3 parts of surfactant, and 22 parts of water;

[0054] B, 40 parts of nitromethane, 40 parts of ethanol, 10 parts of ethylenediamine, and 10 parts of nitromethylammonium;

[0055] C, 26 parts of sodium chloride and 74 parts of water.

[0056] The preparation method of the liquid explosive is as follows: according to the ratio of A, B and C, three components A, B and C are obtained, and then A 45-60 parts, B 15-20 parts and C 20-40 parts are mixed to obtain the liquid explosive for explosive welding.

[0057] Preferably, the purity of magnesium nitrate is greater than 99.5wt%, the bulk density is 0.8-0.9 g / cm 3 , the average particle size is less than 200 mesh, and the water content is less than 0.05wt%; the purity of sodium nitrate is greater than 99.5wt%, the bulk density is 2.2-2.3 g / cm 3 , the average particle size is less than 200 mesh, and the water content is less than 0.05wt%; the surfactant is triacylglycerol monostearate, and the water content is less than 0.3wt%; the purity of nitromethane is greater than 98wt%, the density is 1.1-1.2 g / cm 3 , the viscosity is less than 4 mpa.S, and the water content is less than 0.3wt%; the purity of ethanol is greater than 95wt%, the density is 0.79 g / cm 3 , the viscosity is less than 1.1 mpa.S, and the water content is less than 0.3wt%; the purity of ethylenediamine is greater than 99.8wt%, the density is 0.89 g / cm 3 , and the water content is less than 0.05wt%; the purity of nitromethylammonium is greater than 99.8wt%, the density is 1.2-1.3 g / cm 3 , and the water content is less than 0.05wt%; the purity of sodium chloride is greater than 95wt%, the bulk density is 2.1-2.3 g / cm 3The average particle size is less than 100 mesh, and the water content is less than 0.5 wt%.

[0058] The magnesium nitrate and sodium nitrate are oxidants and play an oxidizing role, the surfactant can prevent crystallization of the components, the nitromethane and ethanol are reducing agents and play a reducing role, the ethylenediamine and nitromethane are sensitizers and play a sensitizing role, and the sodium chloride is an inert additive and can effectively reduce the detonation velocity.

[0059] Table 1: Explosive components and performance tests

[0060]

[0061] The technical solutions and effects of the present application are further described below through actual examples.

[0062] Example

[0063] Example 1

[0064] The titanium-steel metal composite plate in this example is composed of the following materials: a titanium plate with a thickness of 0.5 mm, a length of 12000 mm, and a width of 2000 mm, and a steel plate with a thickness of 30 mm, a length of 12000 mm, and a width of 2000 mm, wherein the titanium plate serves as a cladding plate and the steel plate serves as a base plate.

[0065] The titanium-steel metal composite plate is prepared according to the preparation method of the ship metal composite plate, wherein the liquid explosive is the 1# explosive in Table 1.

[0066] The bonding state of the titanium-steel metal composite plate in the present application is detected by ultrasonic detection method according to the provisions of NB / T 47013.3, and the shear test, tensile test, and bending test of the titanium-steel metal composite plate are detected according to the provisions of GB / T 6396. The mechanical properties of the titanium-steel metal composite plate prepared in this example are shown in Table 2, and the interface is microscopically analyzed using SEM electron microscope, XRD diffraction pattern, EDS line scanning, and point scanning, and the results are shown in Table 2. The material is bent 180 degrees inside and outside, and neither cracks. Figure 4 as shown in 1#.

[0067] Example 2

[0068] The titanium-steel metal composite plate in this example is composed of the following materials: a titanium plate with a thickness of 1.5 mm, a length of 15000 mm, and a width of 2000 mm, and a steel plate with a thickness of 50 mm, a length of 15000 mm, and a width of 2000 mm, wherein the titanium plate serves as a cladding plate and the steel plate serves as a base plate.

[0069] The preparation method for marine metal composite plates was followed, wherein the liquid explosive used was explosive #2 from Table 1. Mechanical property testing and microscopic testing were performed as in Example 1, and the results are shown in Table 2. The material underwent 180-degree internal and external bending without cracking. Figure 4 As shown in Figure 2#.

[0070] Example 3

[0071] The titanium-steel metal composite plate in this embodiment is composed of the following materials: a titanium plate with a thickness of 2mm, a length of 17000mm, and a width of 2000mm; a steel plate with a thickness of 10mm, a length of 17000mm, and a width of 2000mm; the titanium plate serves as the composite plate, and the steel plate serves as the base plate.

[0072] The preparation method for marine metal composite plates was followed, wherein the liquid explosive used was explosive #3 from Table 1. Mechanical property testing and microscopic testing were performed as in Example 1, and the results are shown in Table 2. The material underwent 180-degree internal and external bending, and no cracks were observed. Figure 4 As shown in Figure 3#.

[0073] Comparative Example 1: Preparation of Marine Metal Composite Plates Produced by Conventional Explosive Welding Method

[0074] This comparative example titanium-steel metal composite plate is composed of the following materials: a titanium plate with a thickness of 0.5 mm, a length of 12000 mm, and a width of 2000 mm; a steel plate with a thickness of 30 mm, a length of 12000 mm, and a width of 2000 mm; the titanium plate serves as the composite plate, and the steel plate serves as the base plate; powdered explosives and point-like gap supports are used.

[0075] After lamination, macroscopic inspection revealed that the cladding metal was punctured in multiple places, with numerous cracks and wrinkles, such as... Figure 5 As shown in Table 2, the mechanical property testing and microscopic testing were the same as in Example 1; no cracks were observed when the material was bent 180 degrees internally and externally. Figure 4 As shown in Figure 4#.

[0076] Table 2 Mechanical properties and microscopic test results of the embodiments

[0077]

Claims

1. A method for the production of a marine metal composite panel, characterized in that It comprises the following steps: a. Surface rust removal and polishing treatment is performed on the clad metal and base metal, and water-based glue is evenly applied on the surface of the clad metal and base metal to be combined to firmly bond them together; The clad metal is titanium plate and titanium alloy plate, and is selected from any one of TA1, TA2, TA8, TA9 and TA10, with a thickness of ≥0.1 mm and a length of 15000-17000 mm; the base metal is carbon steel plate, with a length of 15000-17000 mm; The water sol is 1-2mm in thickness, >25% in glue content, 7-7.5 in pH, <0.2% in Na2O, 1.165-1.175g / cm in specific gravity and 1-5mpa.S in viscosity 3 ​ b. The sealing strip is bonded to the clad metal, liquid explosive prepared according to the method is poured into the clad metal, and a detonator is arranged to obtain a metal clad plate; The liquid explosive is composed of three components A, B and C, which are prepared according to the following mass ratio: A, magnesium nitrate 40 parts, sodium nitrate 35 parts, surfactant 3 parts, and water 22 parts; B, nitromethane 40 parts, ethanol 40 parts, ethylenediamine 10 parts, and nitromethylammonium 10 parts; C, sodium chloride 26 parts, and water 74 parts; The preparation method of the liquid explosive is as follows: components A, B and C are prepared according to the above ratio, and then mixed according to the ratio of A 45-60 parts, B 15-20 parts and C 20-40 parts to obtain the liquid explosive for explosive welding; c. The metal clad plate is prepared into a plate or a coiled plate, and then subjected to heat treatment of 400℃ for 2h→540℃ for 1.5h→630℃ for 1h→furnace cooling to obtain a marine metal clad plate.

2. The method of manufacturing a marine metal composite panel according to claim 1, characterized in that: In step b, component A needs to meet the following conditions: The purity of magnesium nitrate is >99.5 wt%, the bulk density is 0.8-0.9 g / cm 3 , the average particle size is less than 200 mesh, and the water content is less than 0.05 wt%; Sodium nitrate with purity > 99.5 wt%, bulk density 2.2-2.3 g / cm 3 , average particle size less than 200 mesh, moisture content less than 0.05 wt%; The surfactant is triacylglycerol monostearate, and the water content is less than 0.3wt%.

3. The method of manufacturing a marine metal composite panel according to claim 1, wherein: In step b, component B needs to meet the following conditions: Nitromethane purity > 98 wt%, density 1.1-1.2 g / cm 3 viscosity less than 4 mPa.s, water content less than 0.3 wt%; Ethanol purity > 95 wt%, density 0.79 g / cm 3 viscosity less than 1.1 mpa. S, water content less than 0.3 wt%; Ethylene diamine purity > 99.8 wt%, density 0.89 g / cm 3 moisture content less than 0.05 wt%; Nitromethylammonium purity > 99.8 wt%, density 1.2-1.3 g / cm 3 moisture content less than 0.05 wt%.

4. The method of manufacturing a marine metal composite panel according to claim 1, characterized in that: In step b, component C needs to meet the following conditions: Sodium chloride with purity > 95 wt%, bulk density 2.1-2.3 g / cm 3 , average particle size less than 100 mesh, moisture content less than 0.5 wt%.

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