CN113249730B - Titanium alloy wire copper modification method and application - Google Patents

Titanium alloy wire copper modification method and application Download PDF

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CN113249730B
CN113249730B CN202110434080.1A CN202110434080A CN113249730B CN 113249730 B CN113249730 B CN 113249730B CN 202110434080 A CN202110434080 A CN 202110434080A CN 113249730 B CN113249730 B CN 113249730B
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titanium alloy
alloy wire
copper
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CN113249730A (en
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姚正军
李祥硕
张莎莎
姚孟欣
彭道明
张冰怡
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Nanjing University of Aeronautics and Astronautics
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    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • C23C18/1694—Sequential heat treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Abstract

The invention provides a copper modification method for titanium alloy wires and application, belonging to the technical field of titanium alloy materials, and the specific method comprises the following steps: soaking the titanium alloy wire in alkaline solution, washing the titanium alloy wire subjected to alkaline washing with flowing water until the pH value of the surface is neutral, then placing the titanium alloy wire in activating solution for activating treatment, placing the activated titanium alloy wire in chemical copper plating solution for copper plating, and finally washing the titanium alloy wire with flowing water to obtain the titanium alloy wire containing a copper plating layer; and carrying out heat treatment on the titanium alloy wire containing the copper coating to obtain the copper modified titanium alloy wire. The invention provides a method for solving the problems of thick and large structures and obvious directionality of the titanium alloy manufactured by the additive, which can inhibit the directional growth of crystal grains, eliminate columnar crystals, eliminate anisotropy in mechanical property, improve the strength of a member, improve the elongation to a certain extent, obtain good comprehensive mechanical property and meet the requirement of quickly forming a large-scale bearing member by using an additive manufacturing technology.

Description

Titanium alloy wire copper modification method and application
The technical field is as follows:
the invention belongs to the technical field of titanium alloy materials, and particularly relates to a copper modification method for a titanium alloy wire and application thereof.
Background art:
the titanium alloy has the characteristics of high specific strength, high damage tolerance and the like, and is widely applied to large-scale bearing structures such as central wing boxes, wing stringers and the like. To meet the use requirements, such structures are usually manufactured by machining after forging, and a large amount of material is removed during machining, so that the material utilization rate of the manufacturing method is usually less than 20%, and the cost is high. The additive manufacturing technology (electric arc, electron beam, laser, etc.) using wire as raw material has the advantages of high deposition efficiency and near net shape, so that the additive manufacturing technology becomes an ideal solution for manufacturing large-scale complex load-bearing structures. However, due to the inherent characteristics of additive manufacturing techniques, the formed crystal grains are generally columnar crystals with a width greater than 300 μm, and the structure is coarse and has obvious directionality. Therefore, compared with the forged sample, the sample manufactured by the additive manufacturing method has a significant difference in mechanical properties such as tensile strength and has anisotropy.
Currently, methods for thinning and equiaxial manufacturing titanium alloy structures mostly focus on realization of additional physical fields in the additive manufacturing process, such as ultrasonic vibration (grant, patent No. CN201510967486.0), synchronous rolling (grant, patent No. cn201710009692.x), and the like. However, the methods need complicated additional equipment, have high requirements on the design of a control system and the feedback regulation capacity, and are not suitable for the rapid additive manufacturing of large bearing structures. Although equiaxial transformation of crystal grains can be realized by designing a heat treatment process (patent publication No. CN201911330681.7), the titanium alloy crystal grains are inevitably grown by keeping the temperature above the beta transition temperature for a long time, and the generation of anisotropy is reduced, but the mechanical properties are reduced. The refinement of the structure by adding alloy elements is a common regulation means, and is rarely used in the additive manufacturing technology taking wires as raw materials because: according to the traditional wire preparation method, a bar or a wire rod is subjected to drawing for multiple times to prepare wires, and due to the fact that brittle phases are generated due to the addition of high-content alloy elements, the wire is prone to defects such as uneven cross sections and even breakage and incapability of forming wires in the drawing process. Based on the method, the invention provides a copper modification method for the titanium alloy wire, and the copper modification method is applied to the field of additive manufacturing.
The invention content is as follows:
the invention aims to provide a copper modification method of a titanium alloy wire and an application thereof aiming at the defects of the prior art, wherein the mass fraction of copper element in the prepared copper modified titanium alloy wire is 2-8%. The Cu element has obvious component supercooling effect in titanium and titanium alloy, can obviously inhibit the directional growth of crystal grains, promotes the equiaxial of columnar crystals and eliminates the anisotropy in mechanical property. The equiaxial crystal grains have a certain improvement effect on the elongation rate while improving the strength of the member due to the reduction of the size of the crystal grains, and good comprehensive mechanical properties can be obtained.
The invention adopts the following technical scheme:
the invention provides a copper modification method for titanium alloy wires, which comprises the following steps:
s1, electroless copper plating treatment: soaking the titanium alloy wire in alkaline solution, washing the titanium alloy wire subjected to alkaline washing with flowing water until the pH value of the surface is neutral, then placing the titanium alloy wire in activating solution for activating treatment, placing the activated titanium alloy wire in chemical copper plating solution for copper plating, and finally washing the titanium alloy wire with flowing water to obtain the titanium alloy wire containing a copper plating layer;
s2, heat treatment: and (4) carrying out heat treatment on the titanium alloy wire containing the copper coating obtained in the step (S1) to obtain a copper-modified titanium alloy wire.
Further, the S1 specifically includes the following steps:
a. alkali washing: placing the titanium alloy wire in alkaline cleaning solution, and soaking for 5-10 minutes;
b. washing with water: washing the titanium alloy wire subjected to alkali washing by using flowing water until the pH value of the surface is neutral;
c. and (3) activation: placing the washed titanium alloy wire in an activation solution for activation for 2-4 minutes;
d. chemical plating: placing the activated titanium alloy wire in chemical copper plating solution, and chemically plating until the thickness of a copper layer meets the requirement, wherein the temperature is 20-60 ℃;
e. cleaning: and (3) cleaning the titanium alloy wire subjected to chemical plating by using flowing water to remove residual plating solution and attachments on the surface.
Further, in S1, the alkaline washing solution is NaOH or Na2CO3And a mixed solution of PEG-6000 and distilled water.
Further, the concentration of NaOH is 15-25 g/L, Na2CO3The concentration of the PEG-6000 is 10-15 g/L, and the concentration of the PEG-6000 is 0.1-1 g/L.
Further, in S1, the activator is NH3HF. HF solution, mixed solution of Sodium Dodecyl Sulfate (SDS) and distilled water.
Further, NH3The concentration of HF is 40-60 g/L, the concentration of HF solution is 20-45 mL/L (the volume of HF solution is 20-45 mL in every 1L of activator solution), and the concentration of sodium dodecyl sulfate is 0.05-0.1 g/L.
Further, NH3The concentration of HF is 45-60 g/L, the concentration of HF is 20-30 mL/L, and the concentration of sodium dodecyl sulfate is 0.05-0.1 g/L.
Further, in S1, the electroless copper plating solution includes five components, namely a main salt, a complexing agent, a reducing agent, a pH adjusting agent and an additive; wherein the main salt is CuSO4、CuCl2One or two of the components, the complexing agent is EDTA-2Na and potassium sodium tartrate, the reducing agent is 37% formaldehyde solution, the pH regulator is NaOH, and the additive is PEG-6000 and methanol.
Further, the main salt is CuSO4When the concentration is 9-20 g/L, the main salt is CuCl2When the concentration is 6-15 g/L; the concentration of the EDTA-2Na is 15-25 g/L, and the concentration of the potassium sodium tartrate is 10-17 g/L; the 37% formaldehyde solution is 8-15 mL/L (the volume of the 37% formaldehyde solution is 8-15 mL in every 1L of chemical copper plating solution); the concentration of NaOH is 7.5-14.5 g/L; the concentration of the PEG-6000 is 0.1-1 g/L, and the concentration of the methanol is 8-20 mL/L.
Further, the main salt is CuSO4When the concentration is 9-14.5 g/L, the main salt is CuCl2When the concentration is 6-12 g/L; the concentration of the EDTA-2Na is 15-20 g/L, and the concentration of the potassium sodium tartrate is 10-13.5 g/L; the 37% formaldehyde solution is 8-12 mL/L; the concentration of NaOH is 8-12.5 g/L; the concentration of the PEG-6000 is 0.1-0.5 g/L, and the concentration of the methanol is 10-12 mL/L.
Further, in S2, the heat treatment includes two processes of stabilizing treatment and diffusion heat treatment, wherein the stabilizing treatment temperature is 300-350 ℃, and the treatment time is 2-4 hours; the diffusion heat treatment temperature is 700-900 ℃, and the treatment time is 0.5-2 h.
Further, in the obtained copper modified titanium alloy wire, the mass fraction of copper element is 2-8%.
The invention also provides application of the copper modification method of the titanium alloy wire in the field of additive manufacturing.
The invention has the beneficial effects that:
(1) the invention provides a method for chemical plating modification of a titanium alloy wire surface, which can flexibly control the Cu content by controlling the thickness of a plating layer; the large-batch or small-batch modified wire materials are produced according to requirements without the traditional wire making process, so that the problems of incapability of drawing and wire making, low yield and the like caused by a large amount of brittle phases are avoided;
(2) the invention provides a method for solving the problems of thick and large structure and obvious directivity of the titanium alloy manufactured by the additive, and through the component supercooling effect of the Cu element, the directivity of grain growth is inhibited, columnar crystals are eliminated, and the anisotropy in mechanical property is eliminated; the equiaxial crystal grains can improve the strength of the member due to the reduction of the size of the crystal grains, and simultaneously has certain improvement effect on the elongation, so that good comprehensive mechanical property can be obtained, and the requirement of rapidly forming a large-scale bearing member by using an additive manufacturing technology is met.
Description of the drawings:
FIG. 1 is a photograph of a macroscopic metallographic structure of a Ti-6Al-4V alloy member made by electron beam fuse additive manufacturing, showing a columnar beta-grain morphology with a width greater than 0.5mm and a length much greater than 5 mm;
FIG. 2 is a photograph of a metallographic structure of a copper-modified Ti-6Al-4V alloy member manufactured by electron beam fuse additive manufacturing according to example 2 of the present invention, in which crystal grains are equiaxed grains and have a width of about 100 μm;
FIG. 3 is a photomicrograph of a cross-section of a wire modified by the process of example 2 of the present invention, in which the outer circle is a circular ring-shaped copper modified layer with a width of about 30 μm.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
This example carried out surface copper modification of 1mm diameter TC4 titanium wire
(1) Solution preparation:
alkali wash: NaOH 15g/L, Na2CO3 15g/L、PEG-6000 1g/L；
Activating agent: NH (NH)360g/L of HF, 20mL/L of 40% HF and 0.06g/L of Sodium Dodecyl Sulfate (SDS);
chemical copper plating solution: CuSO49g/L, EDTA2Na 15g/L, 17g/L potassium sodium tartrate, 8 mL/L37% formaldehyde solution, 7.5g/L NaOH, PEG-60000.1 g/L and 10mL/L methanol.
(2) Modification of TC4 titanium wire copper:
s1, electroless copper plating treatment: placing a TC4 titanium wire in an alkaline solution for soaking for 10 minutes, washing the TC4 titanium wire subjected to alkaline washing by flowing water until the pH value of the surface is neutral, placing the TC4 titanium wire subjected to water washing in an activating solution for activating for 4 minutes, then placing the activated TC4 titanium wire in a chemical copper plating solution, chemically plating until the thickness of a copper layer meets the requirement, and finally cleaning by flowing water to remove residual plating solution and attachments on the surface so as to obtain the TC4 titanium wire containing a copper plating layer, wherein the temperature of the activating solution is 55 ℃;
s2, heat treatment: and (3) carrying out heat treatment on the TC4 titanium wire containing the copper coating obtained in the S1, wherein the heat treatment specifically comprises the following steps: the copper modified TC4 titanium wire is obtained by stabilizing treatment for 2.5h at 300 ℃ and then diffusion heat treatment for 2h at 700 ℃.
The implementation effect is as follows: the copper-modified TC4 titanium wire obtained in the embodiment has the advantages that the crystal grains of the copper-plated layer deposited on the surface are compact, the combination with the matrix is good, and the copper content of the wire is 2.1% by mass. The sample part structure obtained by electron beam fuse material increase manufacturing is isometric crystal, the tensile strength is 901MPa, and the elongation is 15%.
Example 2
This example carried out surface copper modification of 1mm diameter TC4 titanium wire
(1) Solution preparation:
alkali wash: NaOH 20g/L, Na2CO3 12g/L、PEG-6000 0.8g/L；
Activating agent: NH3HF 55g/L, 40% HF 45mL/L and Sodium Dodecyl Sulfate (SDS)0.05 g/L;
chemical copper plating solution: CuCl212g/L, EDTA2, 2Na 20g/L, 10g/L of potassium sodium tartrate, 10mL/L of 37% formaldehyde solution, 12g/L of NaOH, 01 g/L of PEG-60001 and 8mL/L of methanol.
(2) TC4 titanium wire copper modification:
s1, electroless copper plating treatment: soaking a TC4 titanium wire in an alkaline solution for 8 minutes, washing the TC4 titanium wire subjected to alkaline washing with flowing water until the pH value of the surface is neutral, putting the TC4 titanium wire subjected to water washing in an activating solution for activating for 2.5 minutes, then putting the TC4 titanium wire subjected to activation in a chemical copper plating solution, chemically plating until the thickness of a copper layer meets the requirement, and controlling the temperature to be 30 ℃, and finally washing with flowing water to remove residual plating solution and attachments on the surface to obtain the TC4 titanium wire containing a copper plating layer;
s2, heat treatment: and (3) carrying out heat treatment on the TC4 titanium wire containing the copper coating obtained in the S1, wherein the heat treatment specifically comprises the following steps: the stabilizing treatment is carried out for 2.5h at 350 ℃, and then the diffusion heat treatment is carried out for 1h at 840 ℃ to obtain the copper modified TC4 titanium wire.
The implementation effect is as follows: the copper-modified TC4 titanium wire obtained in the embodiment has the advantages that the crystal grains of the copper-plated layer deposited on the surface are compact, the combination with the matrix is good, and the copper content of the wire is 4.2% by mass. The sample piece structure obtained through electron beam fuse material increase manufacturing is isometric crystal, the tensile strength is 921MPa, and the elongation is 11%.
Example 3
This example surface copper-modified TC4 titanium wire with a diameter of 1.2mm
(1) Solution preparation:
alkali wash: NaOH 25g/L, Na2CO3 17g/L、PEG-6000 0.1g/L；
Activating agent: NH3HF 40g/L, 40% HF 30mL/L and Sodium Dodecyl Sulfate (SDS)0.1 g/L;
chemical copper plating solution: CuSO414.5g/L, EDTA 2g/L of 2Na 25g/L, 13.5g/L of sodium potassium tartrate, 15mL/L of 37% formaldehyde solution, 14.5g/L of NaOH, PEG-60000.5 g/L and 20mL/L of methanol.
(2) Modification of TC4 titanium wire copper:
s1, electroless copper plating treatment: placing a TC4 titanium wire in an alkaline solution for soaking for 10 minutes, washing the TC4 titanium wire subjected to alkaline washing by flowing water until the pH value of the surface is neutral, placing the TC4 titanium wire subjected to water washing in an activating solution for activating for 4 minutes, then placing the activated TC4 titanium wire in a chemical copper plating solution, chemically plating until the thickness of a copper layer meets the requirement, and at the temperature of 25 ℃, finally cleaning by flowing water to remove residual plating solution and attachments on the surface to obtain the TC4 titanium wire containing a copper plating layer;
s2, heat treatment: and (3) carrying out heat treatment on the TC4 titanium wire containing the copper plating layer obtained in the step S1, wherein the heat treatment specifically comprises the following steps: firstly, stabilizing at 350 ℃ for 2h, and then, carrying out diffusion heat treatment at 700 ℃ for 2h to obtain the copper modified TC4 titanium wire.
The implementation effect is as follows: the copper-modified TC4 titanium wire obtained in the embodiment has the advantages that the crystal grains of the copper-plated layer deposited on the surface are compact, the combination with the matrix is good, and the copper content in the wire is 7.9% by mass. The sample piece structure obtained by electron beam fuse material additive manufacturing is isometric crystal, the tensile strength is 941MPa, and the elongation is 5%.
Referring to fig. 1 to 3, wherein fig. 1 is a microstructure photograph of a Ti-6Al-4V alloy component manufactured by electron beam fuse additive manufacturing, it can be seen that fig. 1 shows a columnar β -grain morphology, a width of which is greater than 0.5mm, and a length of which is much greater than 5 mm. FIG. 2 is a photograph of metallographic structure of a copper modified Ti-6Al-4V alloy member manufactured by electron beam fuse additive manufacturing in example 2 of the present invention, and it can be seen that the crystal grains shown in FIG. 2 are equiaxed grains having a width of about 100 μm, which is much smaller than the width shown in FIG. 1; FIG. 3 is a photomicrograph of a cross-section of the wire produced in example 2 of the present invention, in which the outer circle is circular, i.e., the copper modified layer, and the width thereof is about 30 μm. Therefore, the copper modified titanium alloy wire prepared by the process can obviously inhibit the directional growth of crystal grains, promote the equiaxial of columnar crystals and reduce the size of the crystal grains.
TABLE 1 comparison of mechanical Properties of titanium alloys deposited by electron beam fuse
Figure RE-GDA0003161749520000061
Referring to table 1, table 1 shows the comparison of the mechanical properties of the copper-modified titanium alloy wire prepared in embodiments 1 to 3 of the present invention and a Ti6Al4V sample, and it can be seen from table 1 that the tensile strength of the copper-modified titanium alloy wire prepared by the process of the present invention is generally higher than 900MPa, and within a certain range, the copper-modified titanium alloy wire can improve the elongation and has a certain improvement effect on the elongation. In addition, the copper-plated layer deposited on the surface of the copper-modified TC4 titanium wire in the embodiment 1-3 is compact in crystal grain, good in combination with a substrate, and remarkably superior to that of a Ti-6Al-4V alloy component manufactured by electron beam fuse additive manufacturing in mechanical property, and can meet the requirement of rapidly forming a large-scale bearing component by using an additive manufacturing technology.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention, it should be noted that, for those skilled in the art, several modifications and decorations without departing from the principle of the present invention should be regarded as the protection scope of the present invention.

Claims (5)

1. A copper modification method for titanium alloy wires is characterized by comprising the following steps:
s1, electroless copper plating treatment:
soaking the titanium alloy wire in alkaline solution, washing the titanium alloy wire subjected to alkaline washing with flowing water until the pH value of the surface is neutral, then placing the titanium alloy wire in activating solution for activating treatment, placing the activated titanium alloy wire in chemical copper plating solution for copper plating, and finally washing the titanium alloy wire with flowing water to obtain the titanium alloy wire containing a copper plating layer; the activating solution is NH3HF. HF, sodium dodecyl sulfate and steamA mixed solution of distilled water; the chemical copper plating solution comprises five components of main salt, a complexing agent, a reducing agent, a pH regulator and an additive; wherein the main salt is CuSO4、CuCl2One or two of the components are EDTA-2Na and potassium sodium tartrate, the reducing agent is formaldehyde solution with the mass fraction of 37%, the pH regulator is NaOH, and the additives are PEG-6000 and methanol;
s2, heat treatment:
carrying out heat treatment on the titanium alloy wire containing the copper coating obtained in the S1 to obtain a copper modified titanium alloy wire; the heat treatment comprises two processes of stabilizing treatment and diffusion heat treatment, wherein the stabilizing treatment temperature is 300-350 ℃, and the treatment time is 2-4 h; the temperature of the diffusion heat treatment is 700-900 ℃, and the treatment time is 0.5-2 h;
in activating solution, NH3The concentration of HF is 40-60 g/L, the concentration of HF is 20-45 mL/L, and the concentration of sodium dodecyl sulfate is 0.05-0.1 g/L;
in the chemical copper plating solution, the main salt is CuSO4When the concentration is 9-20 g/L, the main salt is CuCl2When the concentration is 6-15 g/L; the concentration of the EDTA-2Na is 15-25 g/L, and the concentration of the potassium sodium tartrate is 10-17 g/L; the formaldehyde solution with the mass fraction of 37% is 8-15 mL/L; the concentration of NaOH is 7.5-14.5 g/L; the concentration of the PEG-6000 is 0.1-1 g/L, and the concentration of the methanol is 8-20 mL/L.
2. The method for modifying copper in titanium alloy wire according to claim 1, wherein in S1, the alkaline solution is NaOH or Na2CO3And a mixed solution of PEG-6000 and distilled water.
3. The method for modifying copper in titanium alloy wire according to claim 2, wherein the concentration of NaOH in the alkaline solution is 15-25 g/L, Na is added2CO3The concentration of (A) is 10-15 g/L, and the concentration of PEG-6000 is 0.1-1 g/L.
4. The copper modification method for titanium alloy wires according to claim 1, wherein the mass fraction of copper element in the obtained copper-modified titanium alloy wires is 2-8%.
5. The application of the copper modification method for the titanium alloy wire of claims 1 to 4 in the field of additive manufacturing.
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