High-quality copper-nickel composite interface cone and preparation method thereof

Abstract

The application relates to the technical field of inductively coupled plasma mass spectrometry (ICP-MS), and particularly relates to a high-quality copper-nickel composite interface cone and a preparation method thereof. The interface cone high-thermal-conductivity base body and the metal nickel layer are deposited on a seed plate by adopting an electrodeposition technology, a high-thickness high-temperature-resistant corrosion-resistant coating material is further electrodeposited at the cone opening of the cone opening tip, and the copper-nickel composite interface cone is prepared. The method adjusts the electrodeposition process parameters in the electrodeposition mode, prepares a complex multi-material composite structure, has the advantages of high bonding strength, stable process, simple operation, uniform crystal grains, low porosity and the like, and can realize full-circle deposition coating, and meets the working of the interface cone part under severe high-temperature corrosion conditions.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of inductively coupled plasma mass spectrometry (ICP-MS), and particularly relates to a high-quality copper-nickel composite interface cone and a preparation method thereof. BACKGROUND

[0002] The interface cone is a key component of the plasma mass spectrometer, which is divided into a sampling cone and a skimmer cone, and plays an important role in high-temperature plasma extraction, ion transmission and focusing, and vacuum differential. The characteristics of the interface cone directly affect the sensitivity, noise, service life, and acid and alkali resistance of the instrument. The working environment of the interface cone component is harsh, which is in a high-temperature (about 6000K) and strong acid and alkali environment, so the interface cone component is required to have high-temperature resistance, corrosion resistance, and good heat conduction performance.

[0003] In the prior art, Chinese patent CN201549467U discloses a glow discharge ion source mass spectrometry interface device, the interface cone and the skimmer cone are made of pure nickel material or stainless steel material, which is easy to install, durable, and has good use effect, but does not mention the high-temperature resistance and corrosion resistance of the interface cone component; Chinese patent CN212461599U discloses a new inductively coupled plasma mass spectrometer sampling cone, a heat dissipation and heat resistance effect is achieved by installing a protection heat dissipation device on the cone body, and heat dissipation fins are arranged on the side surface of the heat dissipation column, and the materials are all copper, but the structure design of the sampling cone is relatively complex, and the cost is high; Chinese patent CN117758330A discloses a corrosion prevention treatment method for an ICP-MS interface nickel cone, a hard chromium layer and a titanium alloy layer are plated on the surface of the nickel cone in sequence, but the above-mentioned technology still has a certain degree of corrosion in actual application.

[0004] In summary, in the prior art, the interface cone device still has a certain degree of corrosion in acidic and alkaline media, and the above-mentioned corrosion will be aggravated in a high-temperature and oxygen-containing environment; in addition, for heat resistance, a heat dissipation device is installed on the cone body, which has a complex structure, and a heat dissipation material is prepared by using a traditional high-temperature smelting method and a mechanical alloying method, for example, Chinese patent CN111128929A uses a traditional calendering forming process and a mechanical processing process to prepare a heat dissipation material, the material has poor bonding force, is difficult to use for a long time in a high-temperature and corrosive working environment, and the heterogeneous material composite forming process is complex and has high production cost. SUMMARY

[0005] In order to solve the problems of poor bonding force of heterogeneous materials and short service life of the interface cone, the present application provides a high-quality copper-nickel composite interface cone and a preparation method thereof, a copper or copper alloy substrate is prepared by direct electrodeposition on a conical structure plate, nickel is directly electrodeposited on the substrate, and a nickel or platinum coating layer is secondarily electrodeposited on the cone mouth and is subjected to shot peening strengthening, so that a uniform and dense high-quality copper-nickel interface cone for ICP-MS is prepared, and the specific preparation method is as follows:

[0006] A preparation method of a high-quality copper-nickel composite interface cone comprises the following steps:

[0007] Step 1: process a titanium material or a stainless steel material into an electrodeposition seed plate, the seed plate structure comprising a circular ring base and a conical structure on the base, the bottom surface of the conical structure being connected with the inner circle of the circular ring base, and a conical opening being formed at the end of the conical structure;

[0008] Step 2: perform insulation treatment on the inner side surface of the seed plate, and then place the seed plate in a copper-containing solution with a copper content of 80-150 g / L to perform single-sided electrodeposition on the outer side surface, the electrodeposition thickness being 1-3 mm, and a copper or copper alloy base being obtained by stripping, and the copper or copper alloy base being machined to have a thickness of 0.1-0.3 mm at the conical opening of the conical structure;

[0009] Step 3: place the copper or copper alloy base in a nickel-containing solution with a nickel content of 80-100 g / L to perform pulse electrodeposition, the electrodeposition thickness being 0.3-0.5 mm, and a copper-nickel composite interface cone being prepared;

[0010] Step 4: place the end of the conical structure of the copper-nickel composite interface cone in a nickel-containing or platinum-containing solution to perform electrodeposition, the electrodeposition thickness being 0.5-0.8 mm, and then perform strengthening treatment on the end of the conical structure to obtain a high-quality copper-nickel composite interface cone.

[0011] Further, the copper-containing solution in step 2 is one or more of a copper sulfate solution, a copper chloride solution, a beryllium-nickel-copper solution, and a tungsten-copper solution.

[0012] Further, the process parameters of the electrodeposition process in step 2 are as follows: temperature 30-50℃, current density 100-200 A / m 2 , pH value 1-3, and electrodeposition time 24-48 h.

[0013] Further, the nickel-containing solution in step 3 is one or more of a nickel chloride or a nickel sulfate. Further, the process parameters of the pulse electrodeposition process in step 3 are as follows: pulse duty ratio (1:3)-(4:1), electrodeposition temperature 20-30℃, current density 30-40 A / m 2 , pH value 3.5-5.5, and electrodeposition time 16-24 h.

[0014] Further, in step 4, the part from the conical opening to 1 / 3-1 / 2 of the conical structure below the conical opening of the copper-nickel composite interface cone is placed in a nickel-containing or platinum-containing solution.

[0015] Further, the concentration of nickel or platinum in the solution containing nickel or platinum in step 4 is 120-150 g / L, and the parameters of the electrodeposition process are: temperature 30-50℃, current density 40-100 A / m 2 , pH value 1-3, and electrodeposition time 20-30 h.

[0016] Further, shot peening treatment is performed in step 4, and the shot peening strength is 0.5-1.0 MPa, and the coverage is 100-200%.

[0017] The high-quality copper-nickel composite interface cone prepared according to the above method comprises a circular ring base and a conical structure on the base, the bottom surface of the conical structure is connected with the inner circle of the circular ring base, the copper-nickel composite interface cone comprises, from inside to outside, a copper or copper alloy base, a nickel layer, and a nickel or nickel alloy or platinum alloy coating layer outside the nickel layer at the end of the conical structure; the thickness of the copper or copper alloy base is 1-3 mm, and the density is 99.80-99.98%; the purity of the nickel layer is ≥99.99%, the density is 99.90-99.98%, the thickness is 0.3-0.5 mm, the porosity is ≤1%, the grain size is ≤1 μm, the roughness is ≤1 μm, and the defect rate is ≤0.5%; the thickness of the nickel or nickel alloy or platinum alloy coating layer is 0.5-0.8 mm, and the hardness is ≥120 HV.

[0018] Further, the outer diameter of the circular ring base is 50-80 mm, the taper of the conical structure is 100-150%, and the opening diameter of the conical structure is 0.7-1.2 mm.

[0019] The interface cone prepared by the method has the following advantages: the thickness and density of the deposited layer can be controlled by adjusting the parameters such as the electrodeposition current, voltage, temperature, current density and acidity, and uniform deposition can be achieved without using dispersants; under the process conditions of the method, the density of the copper substrate can reach 99.80-99.98%, and the problems of difficulty in controlling the composition and thickness of the copper or copper alloy prepared by smelting, easy introduction of impurities, high energy consumption and high cost can be completely avoided; meanwhile, the purity of the electrodeposited nickel layer prepared is greater than or equal to 99.99%, the density is 99.90-99.98%, the thickness is 0.3-0.5 mm, the porosity is less than or equal to 1%, the grain size is less than or equal to 1 μm, the roughness is less than or equal to 1 μm, and the defect rate is less than or equal to 0.5%, so that the heterogeneous metal bonding force is high and the uniformity is high; meanwhile, the taper mouth is subjected to large thickness treatment (i.e., secondary electrodeposition of a nickel coating or a platinum coating) and shot peening strengthening, so that the corrosion problem of the existing interface cone in an acidic or alkaline medium in actual detection can be solved. The method for preparing the interface cone solves the problem of great difficulty in traditional welding process of heterogeneous materials, and the process is simple, and the interface cone prepared can withstand a water-cooled working environment of 4000-6000 K for a continuous working time of greater than or equal to 1000 h, and has a service life of greater than or equal to 24 months, and can withstand strong acid and alkali environment corrosion of pH = 1-3 and pH = 8-9. BRIEF DESCRIPTION OF DRAWINGS

[0020] The embodiments of the present application are further described below with reference to the accompanying drawings, in which:

[0021] Figure 1 A process flow chart of the method for preparing the high-quality copper-nickel composite interface cone is shown;

[0022] Figure 2 A structure cross-sectional view of the copper-nickel composite interface cone prepared by the method is shown;

[0023] Figure 3 A structure schematic view of the copper-nickel composite interface cone prepared by the method is shown.

[0024] In the drawings, 1 is an electrodeposited copper or copper alloy substrate, 2 is an electrodeposited nickel layer, and 3 is a nickel or nickel alloy or platinum alloy coating. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application is further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0026] The method for preparing the high-quality copper-nickel composite interface cone specifically comprises the following steps:

[0027] Step 1: process titanium or stainless steel into an electrodeposition seed plate, the seed plate structure comprises a circular ring base and a conical structure on the base, the bottom surface of the conical structure is connected with the inner circle of the circular ring base, and a tapered opening is formed at the end of the conical structure;

[0028] Step 2: insulate the inner side of the seed plate, and then perform single-sided electrodeposition on the outer side of the seed plate in a copper-containing solution with a copper content of 80-150 g / L, the electrodeposition thickness is 1-3 mm, the copper or copper alloy substrate is obtained by stripping, and the copper or copper alloy substrate is machined to a thickness of 0.1-0.3 mm at the tapered opening of the conical structure; the copper-containing solution is one or more of copper sulfate solution, copper chloride solution, beryllium nickel copper solution, and tungsten copper solution, and the process parameters of the electrodeposition process are: temperature 30-50℃, current density 100-200A / m 2 , pH value 1-3, and electrodeposition time 24-48h.

[0029] Step 3: place the copper or copper alloy substrate in a nickel-containing solution with a nickel content of 80-100 g / L for pulse electrodeposition, the electrodeposition thickness is 0.3-0.5 mm, and a copper-nickel composite interface cone is prepared; the nickel-containing solution is one or more of nickel chloride or nickel sulfate, and the process parameters of the pulse electrodeposition process are: pulse duty cycle (1:3)-(4:1), electrodeposition temperature 20-30℃, current density 30-40A / m 2 , pH value 3.5-5.5, and electrodeposition time 16-24h.

[0030] Step 4: place the end of the copper-nickel composite interface cone in a nickel-containing or platinum-containing solution for electrodeposition thickening treatment, the electrodeposition thickness is 0.5-0.8 mm, and then perform strengthening treatment on the end of the conical structure to obtain a high-quality copper-nickel composite interface cone. The thickening treatment part specifically refers to the part from the tapered opening to 1 / 3-1 / 2 of the conical structure below the tapered opening, which is a nickel or nickel alloy or platinum alloy coating; the concentration of nickel or platinum in the nickel-containing or platinum-containing solution is 120-150 g / L, the temperature is 30-50℃, the current density is 40-100A / m 2 , the pH value is 1-3, the electrodeposition time is 20-30h, the strengthening treatment is shot peening strengthening treatment, the shot peening intensity is 0.5-1.0MPa, and the coverage is 100-200%.

[0031] Example 1

[0032] A method for preparing a high-quality copper-nickel composite interface cone, comprising the following steps:

[0033] (1) A titanium plate is processed into a circular ring-shaped base and a conical structure on the base. The outer diameter of the circular ring-shaped base of the seed plate is 50 mm, the taper of the conical structure is 100%, the opening diameter of the conical structure is 0.7 mm, and the thickness is 1 mm. A titanium seed plate for electrodeposition is prepared.

[0034] (2) After the inner side of the titanium seed plate is insulated, it is placed in a copper sulfate solution containing 80 g / L of copper, the power is turned on, the temperature is controlled at 30°C, the current density is 100 A / m 2 , the pH value is 1, the thickness of the copper matrix after electrodeposition is 1 mm, and the electrodeposition time is 24 h. The copper matrix is peeled off, and the matrix is machined. The thickness of the copper or copper alloy matrix at the conical opening of the conical structure is 0.1 mm.

[0035] (3) The copper matrix is placed in a nickel chloride solution with a nickel content of 90 g / L for pulse electrodeposition. The pulse duty cycle is 1:3, the electrodeposition temperature is 20°C, the current density is 30 A / m 2 , the pH value is 3.5, and the electrodeposition time is 20 h. A copper-nickel composite interface cone is prepared.

[0036] (4) The conical opening of the copper-nickel composite interface cone is placed in a nickel-containing solution to a depth of 1 / 2 of the conical structure below the conical opening for secondary electrodeposition. The nickel content is 120 g / L, the electrodeposition temperature is 30°C, the current density is 40 A / m 2 , the pH value is 1, the electrodeposition time is 20 h, a large thickness nickel coating is formed near the conical opening, the conical coating thickness is 0.5 mm, the conical coating is shot peened with a shot peening intensity of 0.5 MPa and a coverage of 100%, and after surface treatment, the high-quality copper-nickel composite interface cone is obtained.

[0037] The purity of the electrodeposited nickel layer is 99.992%, the density is 99.95%, the thickness is 0.3 mm, the porosity of the electrodeposited layer is 0.8%, the grain size is 1 μm, the roughness is 1 μm, and the defect rate is 0.5%; the thickness of the conical opening is 0.9 mm, and the hardness is 120 HV. The copper-nickel composite interface cone can work continuously for 1200 h in a 4000K water-cooled working environment, the interface cone has a service life of 24 months, and can withstand strong acid and alkali environment corrosion at pH = 1 and pH = 8.

[0038] Example 2

[0039] A method for preparing a high-quality copper-nickel composite interface cone, comprising the following steps:

[0040] (1) A stainless steel plate is processed into a circular ring-shaped base and a conical structure on the base. The outer diameter of the circular ring-shaped base of the seed plate is 80 mm, the taper of the conical structure is 120%, the opening diameter of the conical structure is 1.0 mm, and the thickness is 2 mm. A stainless steel seed plate for electrodeposition is prepared.

[0041] (2) The inner side of the stainless steel seed plate is coated with insulating material to make a cathode, which is placed in a copper chloride solution containing 150 g / L of copper, connected to a pulse power supply, and controlled at a temperature of 50°C and a current density of 200 A / m 2 , a pH value of 3, and an electrodeposition time of 48 h. The copper substrate has a thickness of 2 mm after electrodeposition. The copper substrate is stripped and machined, and the copper or copper alloy substrate at the tip of the conical structure has a thickness of 0.2 mm.

[0042] (3) The copper substrate is placed in a nickel sulfate solution containing 80 g / L of nickel, and pulse electrodeposition is performed at a pulse duty cycle of 4:1, an electrodeposition temperature of 30°C, and a current density of 40 A / m 2 , a pH value of 5, and an electrodeposition time of 24 h to prepare a copper-nickel composite interface cone.

[0043] (4) The tip of the copper-nickel composite interface cone is placed in a platinum-containing solution for secondary electrodeposition at a platinum content of 150 g / L, an electrodeposition temperature of 50°C, and a current density of 100 A / m 2 , a pH value of 3, to form a platinum coating around the tip. The electrodeposition time is 30 h, and the coating thickness at the tip is 0.5 mm. The tip coating is subjected to shot peening with a shot peening intensity of 0.7 MPa and a coverage of 120%. After surface treatment, the high-quality copper-nickel composite interface cone is obtained.

[0044] The purity of the electrodeposited nickel layer is 99.992%, the density is 99.95%, the electrodeposited nickel thickness is 0.5 mm, the electrodeposited layer porosity is 0.6%, the grain size is 0.7 μm, the roughness is 0.8 μm, and the defect rate is 0.4%. The tip thickness is 1.2 mm, and the hardness is 130 HV. The copper-nickel composite interface cone can work continuously for 1000 h in a 6000K water-cooled working environment, has a service life of 30 months, and can withstand strong acid and alkali environment corrosion at pH = 3 and pH = 9.

[0045] Example 3

[0046] A method for preparing a high-quality copper-nickel composite interface cone, comprising the following steps:

[0047] (1) A titanium plate is processed into a conical structure including a circular ring base and a conical structure on the base. The outer diameter of the circular ring base of the seed plate is 70 mm, the taper of the conical structure is 130%, the opening diameter of the tip is 1.2 mm, and the thickness is 1.2 mm. A titanium seed plate for electrodeposition is prepared.

[0048] (2) After the inner side of the titanium seed plate is insulated, it is placed in a beryllium nickel copper solution containing 100 g / L of copper, connected to a power supply, controlled at a temperature of 40°C, and a current density of 150 A / m 2The copper base has a thickness of 1.5 mm after the electrodeposition, and the electrodeposition time is 36 h. The copper base is stripped and machined, and the thickness of the copper or copper alloy base at the taper opening of the tapered structure is 0.3 mm.

[0049] (3) The copper base is placed in a nickel sulfate solution with a nickel content of 80 g / L, and pulse electrodeposition is performed at a pulse duty cycle of 2:1, an electrodeposition temperature of 25°C, and a current density of 30 A / m 2 The copper-nickel composite interface taper is prepared by electrodeposition for 18 h at a pH value of 4.

[0050] (4) The copper-nickel composite interface taper is placed in a platinum-containing solution for secondary electrodeposition at a platinum content of 120 g / L, an electrodeposition temperature of 40°C, and a current density of 80 A / m 2 The platinum coating is formed near the taper opening at a pH value of 2, and the electrodeposition time is 20 h. The thickness of the coating on the taper opening is 0.8 mm. The coating on the taper opening is subjected to shot peening at a shot peening intensity of 0.8 MPa and a coverage of 150%. After surface treatment, the high-quality copper-nickel composite interface taper is obtained.

[0051] The purity of the electrodeposited nickel layer is 99.991%, the density is 99.98%, the thickness of the electrodeposited nickel is 0.4 mm, the porosity of the electrodeposited layer is 0.9%, the grain size is 0.6 μm, the roughness is 0.8 μm, and the defect rate is 0.5%. The thickness of the taper opening is 1.5 mm, and the hardness is 130 HV. The interface nickel taper can continuously work for 1000 h in a 5000K water-cooled working environment, the service life of the interface taper is 30 months, and the interface taper can withstand strong acid and alkali environment corrosion at pH=2 and pH=8.

[0052] The above describes some exemplary embodiments of the present application. It can be understood that the above-described embodiments are only used to explain the present application and do not constitute a limitation on the protection scope of the present application. The features in these embodiments can be recombined in a suitable manner, and the schemes obtained thereby are still within the protection scope required by the present application. Based on the above-described embodiments, all other embodiments obtained by those skilled in the art without making creative efforts, i.e., all modifications, equivalent replacements, and improvements, etc. made within the spirit and principles of the present application, are also within the protection scope required by the present application.

Claims

1. A method for manufacturing a high-quality copper-nickel composite interface cone, characterized in that The method comprises the following steps: Step 1: titanium or stainless steel is processed into an electrodeposition seed plate, the structure of the seed plate comprises a circular ring base and a conical structure on the base, the bottom surface of the conical structure is connected with the inner circle of the circular ring base, and a tapered opening is formed at the end of the conical structure; Step 2: the inner side of the seed plate is subjected to insulation treatment, and then the seed plate is placed in a copper-containing solution with a copper content of 80-150 g / L for single-sided electrodeposition on the outer side, the electrodeposition thickness is 1-3 mm, the copper or copper alloy substrate is obtained by stripping, and the copper or copper alloy substrate is machined to have a thickness of 0.1-0.3 mm at the tapered opening of the conical structure; Step 3: the copper or copper alloy substrate is placed in a nickel-containing solution with a nickel content of 80-100 g / L for pulse electrodeposition, the electrodeposition thickness is 0.3-0.5 mm, and a copper-nickel composite interface cone is prepared; Step 4: the end of the conical structure of the copper-nickel composite interface cone is placed in a nickel-containing or platinum-containing solution for electrodeposition, the electrodeposition thickness is 0.5-0.8 mm, and then the end of the conical structure is subjected to strengthening treatment to obtain a high-quality copper-nickel composite interface cone.

2. The method for preparing a high-quality copper-nickel composite interface tap according to claim 1, characterized in that, The copper-containing solution in step 2 is one or more of a copper sulfate solution, a copper chloride solution, a beryllium-nickel-copper solution, and a tungsten-copper solution.

3. The method for preparing a high-quality copper-nickel composite interface tap according to claim 1, characterized in that, The process parameters of the step 2 electrodeposition process are: temperature 30-50℃, current density 100-200 A / m 2 , pH value 1-3, electrodeposition time 24-48 h.

4. The method for preparing a high-quality copper-nickel composite interface tap according to claim 1, characterized in that, The nickel-containing solution in step 3 is one or more of nickel chloride or nickel sulfate.

5. The method for preparing a high-quality copper-nickel composite interface tap according to claim 1, characterized in that, The process parameters of the pulse electrodeposition process described in step 3 are: pulse duty ratio 1:3-4:1, electrodeposition temperature 20-30℃, current density 30-40 A / m 2 , pH value 3.5-5.5, electrodeposition time 16-24 h.

6. The method for preparing a high-quality copper-nickel composite interface tap according to claim 1, characterized in that, In step 4, the part of the conical structure from the tapered opening to 1 / 3-1 / 2 of the conical structure below the tapered opening is placed in the nickel-containing or platinum-containing solution.

7. The method for preparing a high-quality copper-nickel composite interface tap according to claim 1, characterized in that, The concentration of nickel or platinum in the nickel or platinum containing solution in step 4 is 120-150 g / L, and the electro-deposition process parameters are: temperature 30-50℃, current density 40-100 A / m 2 , pH value 1-3, and electro-deposition time 20-30 h.

8. The method for preparing a high-quality copper-nickel composite interface tap according to claim 1, characterized in that, In step 4, shot peening strengthening treatment is performed, the shot peening strength is 0.5-1.0 MPa, and the coverage is 100-200%.

9. The high quality copper-nickel composite interface cone prepared according to the method of any one of claims 1-8, characterized in that, The copper-nickel composite interface cone comprises a circular ring base and a conical structure on the base, the bottom surface of the conical structure is connected with the inner circle of the circular ring base, the copper-nickel composite interface cone sequentially comprises a copper or copper alloy substrate and a nickel layer from inside to outside, and the nickel layer outside the end of the conical structure is a nickel or nickel alloy or platinum alloy coating layer; the thickness of the copper or copper alloy substrate is 1-3 mm, and the density is 99.80-99.98%; the purity of the nickel layer is ≥99.99%, the density is 99.90-99.98%, the thickness is 0.3-0.5 mm, the porosity is ≤1%, the grain size is ≤1 μm, the roughness is ≤1 μm, and the defect rate is ≤0.5%; the thickness of the nickel or nickel alloy or platinum alloy coating layer is 0.5-0.8 mm, and the hardness is ≥120 HV.

10. The high quality copper-nickel composite interface cone of claim 9, wherein, The outer diameter of the circular ring base is 50-80 mm, the taper of the conical structure is 100-150%, and the opening diameter of the tapered opening of the conical structure is 0.7-1.2 mm.

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