CN108817393A - A kind of alkali resistance Al alloy composite and preparation method thereof - Google Patents

Abstract

The invention provides an alkali-resistant aluminum alloy composite material, the composite material is composed of a base material and a precursor, the base material is an aluminum alloy, and the mass fraction of each element in the aluminum alloy is Cu 3.8-4.9%, Cu 3.8-4.9%, 1.2-1.8% of Mg, 0.30-0.90% of Mn, and the rest is Al. The precursor is calcium carbonate CaCO ₃ particles coated with Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 metal glass alloy, the precursor accounts for 20-30% of the mass percentage of the substrate, and the particle diameter of the precursor is 50-100 μm. The preparation method comprises the following steps: preparing a precursor, preparing a base material, preparing a slab, extruding, solid solution, and aging treatment.

Description

Alkali-resistant aluminum alloy composite material and preparation method thereof

technical field

The invention belongs to the field of materials, and in particular relates to an alkali-resistant aluminum alloy composite material and a manufacturing method.

Background technique

Compared with steel drill pipes, aluminum alloy drill pipes have the advantages of light weight, fatigue resistance, high flexibility, corrosion resistance, cold resistance, and high critical speed. At present, more than 20 countries have started the development and application of aluminum alloy drilling pipes. my country is a country rich in offshore oil resources. In recent years, offshore oil drilling has developed rapidly. It is very promising to develop aluminum alloy drilling pipes in China. In particular, the oil and gas in the deep sea and continental shelf in the vast sea areas such as the East my country Sea, the Yellow Sea, and the South China Sea are very rich, so it is necessary to use aluminum alloy drilling pipes. However, in an alkaline environment, the oxide film on the surface of the aluminum alloy is continuously dissolved and accompanied by the hydrogen evolution process, resulting in "self-corrosion". The retardation effect causes the corrosion of the aluminum alloy material to intensify. Therefore, in order to solve the above problems, it is necessary to improve the alkali corrosion resistance of the aluminum alloy drill pipe material.

The anodized aluminum and aluminum alloy workpieces are sealed three times in sequence. The first sealing method is cold sealing, hot water sealing, organic acid sealing or rare earth metal salt sealing, and the second sealing is The method used for the hole is passivation or vitrification, and the method used for the third hole sealing is medium and high temperature heat sealing or boiling water sealing. The hole sealing method provided by the invention breaks through the existing single-step or two-step sealing.

At present, the main preparation method of aluminum-based composite materials known to be resistant to alkaline corrosion is to seal the porous oxide film on the surface of the aluminum alloy to improve its resistance to alkaline corrosion, and use cold sealing, hot water sealing, organic acid sealing or rare earth Methods such as metal salt sealing, passivation or vitrification. After searching the prior art documents, it is found that the Chinese patent announcement number is: CN106119924U, the announcement date is: 2016.06.21, and the title of the invention is: a seal that can improve the alkali resistance and corrosion resistance of aluminum and aluminum alloy anodic oxide films. The hole method is used to seal the aluminum and aluminum alloy workpieces after anodic oxidation treatment for three times in sequence. Using a multi-step process, the advantages of each step of hole sealing are fully utilized, and the passivation process is introduced as the middle hole sealing, which can significantly improve the durability. Corrosion, continuous acid and alkali performance, and has stronger alkali resistance. The disadvantage of this method is that the oxide film on the surface of the aluminum alloy is thin and easy to wear, and the new base material exposed after the wear has weakened alkali corrosion resistance. The Chinese patent announcement number is: CN 104233428A, the announcement date is 2014.09.26, and the title of the invention is: a method for improving the alkali resistance of anodized film on the surface of aluminum or aluminum alloy materials. The invention firstly grinds the aluminum or aluminum alloy materials, After polishing pretreatment, put it in an electrolyte solution containing organic acid, inorganic acid and soluble oxo acid salt for anodic oxidation treatment, seal the oxide film obtained from anodic oxidation treatment, and then seal the aluminum or aluminum alloy after sealing treatment A silane film layer is formed on the surface of the material to improve the alkali resistance of the anodized film on the surface of the aluminum or aluminum alloy material. The disadvantage is that the oxide film of the aluminum alloy material is sealed with a silane film layer, and the wear resistance of the polymer material is poor, and the alkali corrosion resistance layer is easily damaged under the action of friction.

Contents of the invention

In view of the above shortcomings, the present invention starts from improving the nature of aluminum alloy materials, uses aluminum alloy as the base material, adds calcium carbonate CaCO ₃ particles coated with Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 metallic glass alloy into the aluminum alloy, and uses spray deposition to add material Fabrication and Hot Extrusion Process for Alkaline Corrosion Resistant Aluminum Matrix Composites for Drill Pipe. The added Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 metallic glass alloy and calcium carbonate CaCO ₃ particles have ultrahigh corrosion resistance, and the corrosion rate is three orders of magnitude lower than that of ordinary Ni-based alloys. And it has good interfacial wettability and interfacial compatibility with the aluminum alloy matrix. Therefore, the aluminum-based composite material for drill pipes prepared by the present invention has good alkali corrosion resistance, and is of great significance for oil and gas exploitation in alkaline environments.

The technical problem to be solved by the invention is to overcome the defects of the prior art and improve the alkali corrosion resistance of the aluminum alloy material by changing the essence. The invention provides an aluminum-based composite material for an alkaline corrosion-resistant drill pipe and an additive manufacturing method.

The technical solution adopted to realize the technical problem of the present invention is as follows: firstly, the precursor Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 metallic glass alloy-coated calcium carbonate CaCO ₃ particles are prepared by spray deposition method. Secondly, aluminum alloy is used as the base material, and the base metal liquid and the precursor are simultaneously atomized and deposited on the base plate under the action of high-pressure argon gas to obtain an aluminum-based composite casting slab. Then the billet is hot-extruded and densified, and extruded into a pipe. Finally, the pipe is subjected to secondary solution aging heat treatment to obtain an aluminum-based composite material for drill pipes resistant to alkali corrosion.

The invention provides an alkali-resistant aluminum alloy composite material, which is characterized in that the composite material is composed of a base material and a precursor, the base material is an aluminum alloy, and the precursor is Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 metallic glass Alloy coated calcium carbonate CaCO ₃ particles.

Preferably, the precursor of the present invention accounts for 20-30% by weight of the substrate.

Preferably, the particle size of the precursor of the present invention is 50-100 μm.

Preferably, the mass fraction of each element in the aluminum alloy of the present invention is Cu 3.8-4.9%, Mg 1.2-1.8%, Mn 0.30-0.90%, and the rest is Al.

The invention provides a kind of preparation method of composite material, and this method comprises the following steps:

1) Preparation of precursor: Prepare Ni, Nb, Ti, and Hf metals according to the atomic ratio to configure the raw materials, place them in a crucible melting furnace and heat them to melt under the protection of argon, and then inject the melt into the molten metal in the spray deposition machine At the same time, CaCO ₃ with a particle size of 10 μm is injected into the solid fluidized conveyor; respectively, 2-3 MPa high-pressure helium gas is introduced into the metal liquid bag and the solid fluidized conveyor to make Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 Metal liquid and CaCO ₃ particles are atomized synchronously to form solid-liquid mixed droplets, which are rapidly solidified under the action of the cooler at the lower end of the atomization chamber, and deposited on the substrate to obtain precursor particles with a particle size of 50-100 μm and a deposition distance of 800 ~1000mm.

2) Prepare the base material: Al, Cu, Mn, Mg metal blocks are prepared according to the mass fraction to obtain the base material raw material, which is added to the crucible melting furnace for melting to obtain the aluminum alloy liquid;

3) Preparation of cast slab: The precursor particles obtained in step 1) are fully stirred and injected into the solid particle fluidized conveyor of the spray deposition equipment by ultrasonic vibration; the aluminum alloy liquid obtained in step 2) is injected into the molten metal ladle middle; argon gas with a pressure of 0.7-0.85Mpa is introduced into the conveyor and the molten metal bag at the same time to atomize the aluminum alloy liquid and the precursor at the same time, and deposit it on the substrate to obtain the cast slab;

4) Extrusion molding: put the cast slab obtained in step 3) into a hot extrusion machine to preheat to 450-500°C, keep it warm for 30 minutes, and then press the extrusion ratio to 3-5 at a temperature of 520°C. Hot extrusion molding under the condition of 1 ~ 3mm/s to obtain extruded pipes;

5) Solution and aging treatment: The extruded pipe obtained in step 4) is subjected to the first-stage solution treatment, the solution temperature is 470±5°C, and the holding time is 2 hours; then the second-stage solution treatment is performed, and the solution temperature is 490 ±5°C, holding time 1h, water cooling (room temperature), transfer time ≤12s; after the second stage of solution treatment, the pipe is subjected to artificial aging treatment, the aging temperature is 190±5°C, and holding time is 12h.

The invention also provides the application of the composite material in preparing drill pipes.

Beneficial effects of the present invention:

In the present invention, aluminum alloy is used as the base material, and calcium carbonate CaCO ₃ particles coated with Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 metallic glass alloy are added to the aluminum alloy, and the alkaline corrosion-resistant aluminum matrix composites for drill pipe. The added Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 metallic glass alloy and calcium carbonate CaCO ₃ particles have ultrahigh corrosion resistance, and the corrosion rate is three orders of magnitude lower than that of ordinary Ni-based alloys. And it has good interfacial wettability and interfacial compatibility with the aluminum alloy matrix. It overcomes the main shortcomings of the known patents, such as thin alkaline corrosion-resistant layer, short service life, and large waste liquid pollution, and provides an aluminum alloy for drill pipes with simple process, convenient operation, less material loss and large-scale production of alkaline corrosion resistance. The matrix composite material and its preparation method are of great significance for oil and gas exploitation in alkaline environment.

Description of drawings

Fig. 1: the flow chart of the preparation process of the aluminum-based composite material for the alkaline corrosion-resistant drill pipe of the present invention;

Figure 2: Schematic diagram of the working principle of the solid-liquid synchronous atomization device of the present invention; in the figure: 1-solid particles, 2-metal liquid, 3-solid particle fluidized conveyor, 4-metal liquid bag, 5-closing valve, 6 -Sealing plug, 7-Atomizer, 8-Cooler

Detailed ways

The present invention will be described in further detail below in conjunction with the examples, but the present invention is not limited to the following examples.

Embodiment 1: An aluminum-based composite material and additive manufacturing method for an alkaline corrosion-resistant drill pipe, the specific steps are as follows:

1) Preparation of precursor: Prepare Ni, Nb, Ti, and Hf metals according to the atomic ratio to configure the raw materials, place them in a crucible melting furnace and heat them to melt under the protection of argon, and then inject the melt into the molten metal in the spray deposition machine At the same time, CaCO ₃ with a particle size of 10 μm is injected into the solid fluidized conveyor; respectively, 3MPa high-pressure helium gas is introduced into the metal liquid bag and the solid fluidized conveyor to make Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 metal Liquid and CaCO ₃ particles are atomized synchronously to form solid-liquid mixed droplets, which are rapidly solidified under the action of the cooler at the lower end of the atomization chamber, and deposited on the substrate to obtain precursor particles with a particle size of 50-100 μm and a deposition distance of 800-1000 mm .

2) Prepare the base material: Al, Cu, Mn, Mg metal blocks are prepared according to the mass fraction of Cu 3.8%, Mg 1.4%, Mn 0.6%, and the rest is Al to prepare the base material raw material, which is added to the crucible melting furnace for melting to obtain aluminum alloy liquid;

3) Preparation of cast slab: The precursor particles obtained in step 1) are fully stirred by ultrasonic vibration and injected into the solid particle fluidized conveyor of the spray deposition equipment according to the mass percentage of the substrate at 20%; the aluminum obtained in step 2) is The alloy liquid is injected into the metal liquid bag; the pressure of 0.7-0.85Mpa argon gas is injected into the conveyor and the metal liquid bag at the same time to atomize the aluminum alloy liquid and the precursor at the same time, and deposit it on the substrate to obtain the cast slab;

4) Extrusion molding: put the cast slab obtained in step 3) into a hot extrusion machine to preheat to 500°C, keep it warm for 30 minutes, and then put it at a temperature of 520°C, an extrusion ratio of 5, and an extrusion speed of 3mm/s Under the conditions of hot extrusion, extruded pipes are obtained;

5) Solution and aging treatment: The extruded pipe obtained in step 4) is subjected to the first-stage solution treatment, the solution temperature is 470±5°C, and the holding time is 2 hours; then the second-stage solution treatment is performed, and the solution temperature is 490 ±5°C, holding time 1h, water cooling (room temperature), transfer time ≤12s; after the second stage of solution treatment, the pipe is subjected to artificial aging treatment, the aging temperature is 190±5°C, and holding time is 12h.

Embodiment 2: An aluminum-based composite material and additive manufacturing method for an alkaline corrosion-resistant drill pipe, the specific steps are as follows:

1) Preparation of precursor: Prepare Ni, Nb, Ti, and Hf metals according to the atomic ratio to configure the raw materials, place them in a crucible melting furnace and heat them to melt under the protection of argon, and then inject the melt into the molten metal in the spray deposition machine At the same time, CaCO ₃ with a particle size of 10 μm is injected into the solid fluidized conveyor; respectively, 3MPa high-pressure helium gas is introduced into the metal liquid bag and the solid fluidized conveyor to make Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 metal Liquid and CaCO ₃ particles are atomized synchronously to form solid-liquid mixed droplets, which are rapidly solidified under the action of the cooler at the lower end of the atomization chamber, and deposited on the substrate to obtain precursor particles with a particle size of 50-100 μm and a deposition distance of 800-1000 mm .

2) Prepare the base material: Al, Cu, Mn, Mg metal blocks are prepared according to the mass fraction of Cu 3.8%, Mg 1.4%, Mn 0.6%, and the rest is Al to prepare the base material raw material, which is added to the crucible melting furnace for melting to obtain aluminum alloy liquid;

3) Preparation of cast slab: The precursor particles obtained in step 1) are fully stirred by ultrasonic vibration and injected into the solid particle fluidized conveyor of the spray deposition equipment according to the mass percentage of the substrate at 25%; the aluminum obtained in step 2) is The alloy liquid is injected into the metal liquid bag; the pressure of 0.7-0.85Mpa argon gas is injected into the conveyor and the metal liquid bag at the same time to atomize the aluminum alloy liquid and the precursor at the same time, and deposit it on the substrate to obtain the cast slab;

4) Extrusion molding: put the cast slab obtained in step 3) into a hot extrusion machine to preheat to 500°C, keep it warm for 30 minutes, and then put it at a temperature of 520°C, an extrusion ratio of 5, and an extrusion speed of 3mm/s Under the conditions of hot extrusion, extruded pipes are obtained;

5) Solution and aging treatment: The extruded pipe obtained in step 4) is subjected to the first-stage solution treatment, the solution temperature is 470±5°C, and the holding time is 2 hours; then the second-stage solution treatment is performed, and the solution temperature is 490 ±5°C, holding time 1h, water cooling (room temperature), transfer time ≤12s; after the second stage of solution treatment, the pipe is subjected to artificial aging treatment, the aging temperature is 190±5°C, and holding time is 12h.

Embodiment 3: An aluminum-based composite material for an alkaline corrosion-resistant drill pipe and an additive manufacturing method, the specific steps are as follows:

1) Preparation of precursor: Prepare Ni, Nb, Ti, and Hf metals according to the atomic ratio to configure the raw materials, place them in a crucible melting furnace and heat them to melt under the protection of argon, and then inject the melt into the molten metal in the spray deposition machine At the same time, CaCO ₃ with a particle size of 10 μm is injected into the solid fluidized conveyor; respectively, 3MPa high-pressure helium gas is introduced into the metal liquid bag and the solid fluidized conveyor to make Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 metal Liquid and CaCO ₃ particles are atomized synchronously to form solid-liquid mixed droplets, which are rapidly solidified under the action of the cooler at the lower end of the atomization chamber, and deposited on the substrate to obtain precursor particles with a particle size of 50-100 μm and a deposition distance of 800-1000 mm .

2) Prepare the base material: Al, Cu, Mn, Mg metal blocks are prepared according to the mass fraction of Cu 3.8%, Mg 1.4%, Mn 0.6%, and the rest is Al to prepare the base material raw material, which is added to the crucible melting furnace for melting to obtain aluminum alloy liquid;

3) Preparation of cast slab: The precursor particles obtained in step 1) are fully stirred by ultrasonic vibration and injected into the solid particle fluidized conveyor of the spray deposition equipment according to the mass percentage of the substrate at 30%; the aluminum obtained in step 2) is The alloy liquid is injected into the metal liquid bag; the pressure of 0.7-0.85Mpa argon gas is injected into the conveyor and the metal liquid bag at the same time to atomize the aluminum alloy liquid and the precursor at the same time, and deposit it on the substrate to obtain the cast slab;

4) Extrusion molding: put the cast slab obtained in step 3) into a hot extrusion machine to preheat to 500°C, keep it warm for 30 minutes, and then put it at a temperature of 520°C, an extrusion ratio of 5, and an extrusion speed of 3mm/s Under the conditions of hot extrusion, extruded pipes are obtained;

5) Solution and aging treatment: The extruded pipe obtained in step 4) is subjected to the first-stage solution treatment, the solution temperature is 470±5°C, and the holding time is 2 hours; then the second-stage solution treatment is performed, and the solution temperature is 490 ±5°C, holding time 1h, water cooling (room temperature), transfer time ≤12s; after the second stage of solution treatment, the pipe is subjected to artificial aging treatment, the aging temperature is 190±5°C, and holding time is 12h.

The alkali resistance test results of the aluminum-based composite materials of the above-mentioned Examples 1-3 are shown in the table below.

Example PH13.5 Soaking time Example 1 no change 30min Example 2 no change 60min Example 3 no change 120min

Alkaline corrosion resistant drill pipe aluminum-based composite materials and additive manufacturing methods prepared by the above-mentioned three kinds of embodiment methods and multiple experiments, with aluminum alloy as the base material, Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 metallic glass alloy package The coated calcium carbonate CaCO ₃ particles were added to aluminum alloy, and the aluminum matrix composite material for drill pipe resistant to alkaline corrosion was prepared by spray deposition additive manufacturing and hot extrusion process. The added Ni ₆₀ Nb ₂₀ Ti _12.5 Hf _7.5 metallic glass alloy and calcium carbonate CaCO ₃ particles have ultrahigh corrosion resistance, and the corrosion rate is three orders of magnitude lower than that of common Ni-based alloys. And it has good interfacial wettability and interfacial compatibility with the aluminum alloy matrix. It overcomes the main shortcomings of the known patents, such as thin alkaline corrosion-resistant layer, short service life, and large waste liquid pollution, and provides an aluminum alloy for drill pipes with simple process, convenient operation, less material loss and large-scale production of alkaline corrosion resistance. The matrix composite material and its preparation method are of great significance for oil and gas exploitation in alkaline environment.

The specific embodiments described above have further described the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (6)

1. a kind of alkali resistance Al alloy composite, which is characterized in that the composite material is made of substrate and precursor, the base Material is aluminium alloy, and institute's presoma is Ni₆₀Nb₂₀Ti_12.5Hf_7.5The calcium carbonate granule of metallic glass alloys cladding.

2. composite material according to claim 1, which is characterized in that the precursor account for substrate mass percentage 20~ 30%.

3. composite material according to claim 1, which is characterized in that the partial size of the precursor is 50~100 μm.

4. composite material according to claim 1, which is characterized in that the mass fraction of each element is in the aluminium alloy Cu 3.8~4.9%, Mg 1.2~1.8%, Mn 0.30~0.90%, remaining is Al.

5. the preparation method of composite material according to claim 1-4, which is characterized in that this method includes following Step：

1) presoma is prepared：Ni, Nb, Ti, Hf metal are subjected to configuration raw material according to atomic ratio, are placed in crucible for smelting furnace in argon It is heated to melting under gas shielded, melt is then filled into the molten metal packet in jet deposition machine, while being 10 μm by partial size CaCO₃It is filled into solids fluidized conveyer；The high pressure of 2~3MPa is passed through into molten metal packet and solids fluidized conveyer respectively Helium is by Ni₆₀Nb₂₀Ti_12.5Hf_7.5Molten metal and CaCO₃The synchronous atomization of particle forms the drop of solid-liquid mixing, in spray chamber lower end Cooler acts on lower drop and quickly solidifies, and is deposited on substrate and obtains granular precursor, 50~100 μm of particle size, deposition away from From 800~1000mm.

2) substrate is prepared：Al, Cu, Mn, Mg metal block are carried out to be added to crucible for smelting with substrate material is made by mass fraction Furnace fusing, obtains aluminium alloy liquid；

3) slab is prepared：The granular precursor that will be obtained in step 1), ultrasonic vibration, which is sufficiently stirred, is filled into jet deposition equipment Solid particle fluidisation conveyer in；The aluminium alloy liquid that step 2) obtains is injected into molten metal packet；To conveyer and gold Belong to liquid packet while being passed through air pressure and be 0.7~0.85Mpa argon gas for aluminum alloy melt and presoma while being atomized, is deposited on substrate and obtains Obtain slab；

4) extrusion forming：The slab that step 3) obtains is put into heat extruder and is preheated to 450~500 DEG C, after keeping the temperature 30min, It is 520 DEG C in temperature, extrusion ratio is 3~5, and extrusion speed is hot extrusion molding under conditions of 1~3mm/s, obtains extruding tubing；

5) solid solution, ageing treatment：The extruding tubing that step 4) is obtained carries out first order solution treatment, solid solubility temperature 470 ± 5 DEG C, soaking time 2h；Second level solution treatment is carried out again, and 490 ± 5 DEG C of solid solubility temperature, soaking time 1h, water cooling (room temperature) turns Shift time≤12s；Tubing progress artificial aging processing after the solution treatment of the second level, 190 ± 5 DEG C of aging temp, soaking time 12h。

6. composite material according to claim 1-4 is preparing the application in drilling rod.