CN115044959A - Corrosive agent for detecting diamond/aluminum-silicon composite material interface and using method thereof - Google Patents
Corrosive agent for detecting diamond/aluminum-silicon composite material interface and using method thereof Download PDFInfo
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Abstract
The invention discloses a corrosive agent for detecting a diamond/aluminum-silicon composite material interface, which comprises a corrosive solution I and a corrosive solution II, wherein the corrosive solution I comprises nitric acid, glycerol and water; the etching solution II comprises hydrofluoric acid, hypophosphorous acid, glycerol and water; the use method of the corrosive agent comprises the following steps: (1) processing the sample into a sheet sample, polishing, cleaning and drying; (2) electrolyzing and corroding the sample in a corrosive solution I; (3) electrolyzing and corroding the sample in the step (2) in a corrosive solution II; (4) observing diamond and aluminum matrix under scanning electron microscopeInterfaces and reaction products thereof; the corrosive agent can clearly and completely display Al at the diamond/aluminum-silicon composite material interface 4 C 3 The shapes of the phase and the silicon phase are high, the efficiency is high, the reproducibility is good, and the operation method is simple.
Description
Technical Field
The invention relates to a material interface corrosive, in particular to a corrosive for detecting a diamond/aluminum-silicon composite material interface and a using method thereof.
Background
The diamond/aluminum composite material has high thermal conductivity, low thermal expansion coefficient,The density is small, and the material is particularly suitable for high-performance electronic packaging heat dissipation materials used for chip semiconductors such as GaAs and GaN. The preparation method of the diamond/aluminum composite material mainly comprises two main types of powder metallurgy sintering method and melt pressure infiltration method, wherein the composite material prepared by the latter has higher heat conductivity coefficient (the volume fraction of diamond particles can reach 65 percent) and can form special-shaped parts, thereby having more development prospect. In the case of the melt pressure infiltration method, Al is generated by nucleation and growth due to interdiffusion of elements at the diamond/aluminum liquid contact site when the aluminum liquid is immersed into the diamond particle interstices 4 C 3 The interface product can increase the interface bonding force and effectively improve the thermal conductivity of the material, but on the other hand, the Al can be used for the 4 C 3 The phase has low thermal conductivity, hygroscopicity, and excessive Al 4 C 3 The phases not only reduce the thermal conductivity of the composite material, but also reduce its long-term service performance. The performance of the composite material depends on the interface structure, and for this reason, an effective Al display at the diamond/aluminum composite material interface must be found 4 C 3 The corrosive agent and the detection method thereof for the morphology and distribution of the phases realize the effective control of the organization and the performance of the corrosive agent by adjusting the preparation process.
There are several publications that disclose corrosive agents for detecting diamond/aluminum composite material interface and detection methods thereof: kleiner et Al prepared diamond/pure aluminum composites by gas pressure melt infiltration, fractured samples, electrochemically etched in aqueous nitric acid to remove aluminum matrix, and observed Al on the diamond surface under scanning electron microscope 4 C 3 Phase formation (S.Kleiner, Effect of diamond orientation on dispersion and carbide formation in contact with liquid aluminum, script Material 55(2006)291- "294"). However, this document does not describe the concentration of the nitric acid aqueous solution and electrochemical etching parameters (such as current density of the area to be etched, etching time, etc.), and the difficulty of control in actual operation is large. I.e. monje, etc. prepared diamond/pure aluminum composite material by using an air pressure melt infiltration method, and designed a special device for electrochemical corrosion of samples: inserting the rod-shaped sample (cathode)In a copper hollow cylinder (anode), O-shaped sealing rings are arranged at the upper end and the lower end of the inner side of the hollow cylinder, the radial distance between a sample and the hollow cylinder is fixed to be 3mm, then the device is placed in 10 percent (volume ratio) nitric acid aqueous solution, and the corrosion current density is controlled to be 2A/cm 2 It was found that Al formed on the surface of diamond could be better observed under a scanning electron microscope when the etching time was 2.5min 4 C 3 Morphology of the phases (I.E. Monje, Aluminum/diamond compositions: anisotropic method to morphology reactivity and selectivity at the interface, script Material 66(2012) 789-792). However, the electrochemical corrosion device provided by the document is complex, and particularly, the cylindrical diamond/aluminum composite material is extremely difficult to process, so that the practical application difficulty is great. In addition, the two examples adopt a single nitric acid aqueous solution as an etchant and an interface reactant Al 4 C 3 The phase will be partially dissolved in the etching solution along with the corrosion of the aluminum matrix, and the real appearance is difficult to display.
In recent years, diamond/aluminum-silicon composite materials have been widely studied because aluminum-silicon alloys have low melting points and good fluidity, so that the infiltration temperature is significantly lower than that of pure aluminum, the reaction degree of the diamond/aluminum matrix interface can be effectively controlled, and excessive Al is avoided 4 C 3 And (5) generating a phase. In addition, researches show that the silicon phase can be attached to partial surface of the diamond, so that Al can be reduced 4 C 3 The generation amount of the phase can further enhance the interface bonding force. Compared with pure aluminum matrix, Al at the interface of the diamond/aluminum-silicon composite material 4 C 3 The amount of phase formation is relatively small, and for this purpose a new corrosive and a method for testing the interface thereof must be found, first of all avoiding the need for Al 4 C 3 The corrosion damage of the phase is avoided, and the excessive corrosion of the silicon phase is avoided, so that the morphology of the two phases can be effectively displayed, and a basis is provided for controlling the structure and the performance of the composite material.
Disclosure of Invention
The invention aims to: the invention aims to provide a corrosive agent for detecting diamond/aluminum-silicon composite material interface, which can completely display Al 4 C 3 The morphology of the phase and the silicon phase is a composite materialControl of organization and performance provides basis; it is another object of the invention to provide a method of using the etchant.
The technical scheme is as follows: the invention discloses a corrosive agent for detecting a diamond/aluminum-silicon composite material interface, which comprises a corrosive solution I and a corrosive solution II, wherein the corrosive solution I comprises nitric acid, glycerol and water; the etching solution II comprises hydrofluoric acid, hypophosphorous acid, glycerol and water.
In the etching solution I, nitric acid can quickly remove a thicker aluminum covering layer to initially expose a diamond/aluminum matrix interface, and glycerol can inhibit pitting corrosion of the aluminum matrix to enable the corrosion removal process of the aluminum matrix to be more uniform.
In the etching solution II, Al is generated by hydrofluoric acid and hypophosphorous acid 4 C 3 The residual aluminum layer around the phase is further corroded and removed completely, and simultaneously, the corrosion removal process of the aluminum matrix can be more uniform by glycerol; furthermore, hypophosphorous acid prevents oxidation of silicon to SiO during electrolysis 2 The aluminum hypophosphite is dissolved by hydrofluoric acid, which is helpful for showing the real shape of the silicon phase, and the corrosion product aluminum hypophosphite is dissolved in water, which can ensure the continuous progress of the corrosion process.
Preferably, in the etching solution I, each 100mL of the etching solution I comprises 10-12 mL of nitric acid, 8-10 mL of glycerol and the balance of water; the mass fraction of the nitric acid is 65-70%.
Preparation of etching solution I: taking a small amount of water in a beaker, taking nitric acid, slowly adding the nitric acid into the beaker, stirring the nitric acid and the glass rod to uniformly mix the nitric acid and the glass rod, adding glycerol, stirring the mixture uniformly, finally adding water, mixing the glycerol and the water to a constant volume of 100 mL.
Preferably, in the etching solution II, every 100mL of the solution comprises 5-7 mL of hydrofluoric acid, 7-10 mL of hypophosphorous acid and the balance of water; 35-40% of hydrofluoric acid by mass; the hypophosphorous acid accounts for 85-85% by mass.
Preparation of etching solution II: taking a small amount of water in a beaker, respectively measuring hydrofluoric acid and hypophosphorous acid, slowly adding the hydrofluoric acid and the hypophosphorous acid into the beaker, stirring the hydrofluoric acid and the hypophosphorous acid by using a glass rod to uniformly mix the hydrofluoric acid and the hypophosphorous acid, adding glycerol into the beaker, uniformly stirring the mixture, finally adding water into the beaker, mixing the mixture and fixing the volume to 100 mL.
The use method of the corrosive agent comprises the following steps:
(1) processing a diamond/aluminum-silicon composite material sample into a sheet sample, polishing, cleaning and drying;
(2) connecting the corrosion sample with the positive electrode of a direct current power supply, connecting a platinum electrode with the negative electrode, then putting the positive electrode and the negative electrode into a corrosion solution I, turning on the direct current power supply to start electrolytic corrosion, then taking out the sample, cleaning and drying;
(3) connecting the sample in the step (2) with the positive electrode of a direct current power supply, connecting a platinum electrode with the negative electrode, then putting the positive electrode and the negative electrode into a corrosive solution II, turning on the direct current power supply to start electrolytic corrosion, then taking out the sample, cleaning the sample in alcohol and drying the sample;
(4) the interface of diamond and aluminum matrix and its reaction products were observed under a scanning electron microscope.
Preferably, in the diamond/aluminum-silicon composite material in the step (1), the weight percentage of silicon in the matrix is 5-9 wt%, and the balance is aluminum.
Preferably, the temperature of the etching solution I in the step (2) is 25 ℃, and the etching current density of electrolytic etching is 2A/cm 2 The electrolysis time is 10-14 s.
Wherein the corrosion current density is the current intensity of the direct current power supply divided by the area of the aluminum-silicon matrix part at the exposed part of the sample, and the area percentage of the aluminum-silicon matrix at the exposed part of the sample is equal to the volume percentage of the aluminum-silicon matrix in the diamond/aluminum-silicon composite material.
Preferably, the corrosion current density of electrolytic corrosion is 2A/cm under the condition that the temperature of the corrosion solution II in the step (3) is 25 DEG C 2 The electrolysis time is 16-20 s.
Preferably, in the step (1), a diamond/aluminum-silicon composite material sample is processed into a sheet sample by a laser cutting machine, a cutting surface is polished, and then the sheet sample is cleaned and dried; and then covering partial area of the sample by using insulating glue, and exposing the electrolytic corrosion surface to prepare a corrosion sample.
Preferably, the area of the corrosion sample immersed in the corrosion solution in the step (2) is 10mm × 3mm, and the other parts immersed in the corrosion solution are covered with the insulating paste.
The invention mechanism is as follows: compared with pure aluminum, the aluminum-silicon alloy has low melting point, good fluidity and lower infiltration temperature than pure aluminum, so the Al at the diamond/aluminum-silicon composite material interface 4 C 3 The amount of phase formation is small, and therefore, Al is avoided first 4 C 3 The corrosion damage of the phases is avoided, and the excessive corrosion of the silicon phase is avoided, so that the appearances of the two phases can be effectively displayed. The corrosive agent for testing the diamond-silicon-aluminum composite material comprises a corrosive solution I and a corrosive solution II. In the etching solution I, the nitric acid aqueous solution rapidly removes the thicker aluminum covering layer to initially expose the diamond/aluminum matrix interface, and the glycerol can inhibit the pitting corrosion of the aluminum matrix to make the corrosion removal process of the aluminum matrix more uniform, thereby preventing Al corrosion by controlling the electrolytic corrosion time 4 C 3 The phases cause corrosion damage. In the etching solution II, Al is generated by hydrofluoric acid and hypophosphorous acid 4 C 3 The residual aluminum layer around the aluminum alloy is further corroded and removed cleanly, and meanwhile, the corrosion removal process of the aluminum matrix is more uniform due to the glycerol; hydrofluoric acid and hypophosphorous acid are mainly used for etching aluminum matrix, while for Al 4 C 3 The corrosion of the phases is small; in addition, hypophosphorous acid has strong reducibility, and can prevent oxidation of silicon into SiO during electrolysis 2 The aluminum hypophosphite is dissolved by hydrofluoric acid, which is helpful for showing the real shape of the silicon phase, and the corrosion product aluminum hypophosphite is dissolved in water, which can ensure the continuous progress of the corrosion process.
Has the beneficial effects that: compared with the prior art, the invention has the following remarkable advantages: (1) the corrosive agent can clearly and completely display Al at the diamond/aluminum-silicon composite material interface 4 C 3 The shapes of the phase and the silicon phase are high, the efficiency is high, and the reproducibility is good; (2) the Al at the interface is ensured by adjusting the formula of the corrosive agents I and II and the two-step electrolysis process 4 C 3 Complete phase display, avoiding Al corrosion for a long time by using single nitric acid aqueous solution 4 C 3 Destruction of phase morphology; (3) the using method of the corrosive is simple to operate, high in efficiency and good in reproducibility.
Drawings
FIG. 1 is a photograph of the interface of the diamond/Al-Si composite material in example 1;
FIG. 2 is an EDS energy spectrum of Si particles at the diamond/Al-Si composite interface in example 1;
FIG. 3 is a photograph of the diamond/Al-Si composite interface in example 2;
FIG. 4 is a photograph of the diamond/Al-Si composite interface in example 3;
fig. 5 is a photograph of the diamond/aluminum silicon composite interface in comparative example 1.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
The invention discloses a corrosive agent for detecting a diamond/aluminum-silicon composite material interface, which comprises a corrosive solution I and a corrosive solution II, wherein the corrosive solution I comprises: 11mL of nitric acid with the mass fraction of 68%, 8mL of glycerol with the purity of 99%, and the balance of deionized water; the etching solution II comprises: 7mL of 35% hydrofluoric acid, 10mL of 80% hypophosphorous acid, 9mL of 99% glycerol and the balance of deionized water.
Preparing a corrosion solution I: taking a small amount of deionized water in a beaker, measuring 11mL of nitric acid, slowly adding the nitric acid into the beaker, stirring the nitric acid and the nitric acid by using a glass rod to uniformly mix the nitric acid and the nitric acid, adding 8mL of glycerol, uniformly stirring the nitric acid and the glycerol, finally adding deionized water, mixing the glycerol and fixing the volume to 100 mL.
Preparing a corrosion solution II: a small amount of deionized water is taken out of a beaker, 7mL of hydrofluoric acid and 10mL of hypophosphorous acid are respectively measured and slowly added into the beaker, a glass rod is used for stirring to enable the hydrofluoric acid and the hypophosphorous acid to be mixed uniformly, 9mL of glycerol is added to be stirred uniformly, and finally the deionized water is added to be mixed and the volume is 100 mL.
The use method of the corrosive agent for detecting the diamond/aluminum-silicon composite material interface comprises the following steps:
(1) preparing an electrolytic corrosion sample:
sample 1 is a diamond/aluminum silicon composite material (diamond volume fraction is 65 vol%, matrix is Al-9 wt% Si alloy), and is prepared by air pressure infiltration (infiltration temperature is 630 ℃, air pressure is 1.5MPa, and diamond/aluminum liquid contact time is 3 min). Cutting the composite material into sheets of 10mm multiplied by 2mm by a laser cutting machine, polishing cut surfaces, cleaning and drying; then, a part of the area of the test piece was covered with an insulating paste to expose an electrolytically etched surface of 10mm × 3mm (in which the area of the metal matrix occupied 35% of the area of the composite material), to obtain a etched test piece.
(2) Connecting a corrosion sample with the positive electrode of a direct current power supply, connecting a platinum electrode plate with the negative electrode, then putting the positive electrode and the negative electrode into a corrosion solution I at 25 ℃, ensuring that the electrolytic corrosion surface of the sample is completely immersed in the corrosion solution, turning on the direct current power supply, adjusting the voltage, and enabling the corrosion current density of a metal matrix at the exposed part of the corrosion sample to reach 2A/cm 2 Electrolyzing for 10s, taking out the sample, cleaning in alcohol and drying;
(3) connecting the sample corroded in the step (2) with the anode of a direct current power supply, connecting a platinum electrode with the cathode, then putting the anode and the cathode into a 25 ℃ corrosion solution II to ensure that the electrolytic corrosion surface of the sample is completely immersed in the corrosion solution, turning on the direct current power supply, adjusting the voltage to ensure that the corrosion current density of the metal matrix at the exposed part of the corrosion sample reaches 2A/cm 2 Electrolyzing for 18s, taking out the sample, washing in alcohol and drying;
(4) the interface between diamond and aluminum matrix was observed under a scanning electron microscope, and the result is shown in FIG. 1.
As can be seen from FIG. 1, Al 4 C 3 The phases are in fine particle shape and are sparsely attached to the surface of the diamond to grow, and are in selective non-uniform distribution on different surfaces. Related studies have shown that Al 4 C 3 Phases grow easily on the (111) plane of diamond, but grow harder on the (100) plane (I.E. Monje, Aluminum/diamond compositions: A precursor method to characteristics reactivity and selectivity at the interface, script Material 66(2012)789-792), consistent with the results of FIG. 1. In fig. 1, it can also be seen that coarse particles, which are characterized by EDS spectra (fig. 2), are attached to the diamond surface, which are silicon particles. Thus, the etchant of the present inventionThe method can conveniently and effectively test the interface structure of the diamond/aluminum-silicon composite material.
Example 2
The invention discloses a corrosive agent for detecting a diamond/aluminum-silicon composite material interface, which comprises a corrosive solution I and a corrosive solution II, wherein the corrosive solution I comprises: 10mL of nitric acid with the mass fraction of 70%, 9mL of glycerol with the purity of 99%, and the balance of deionized water; the etching solution II comprises: 6mL of hydrofluoric acid with the mass fraction of 38%, 9mL of hypophosphorous acid with the mass fraction of 83%, 10mL of glycerol with the purity of 99%, and the balance of deionized water.
Preparing a corrosion solution I: a small amount of deionized water is taken out of a beaker, 10mL of nitric acid is measured and slowly added into the beaker, a glass rod is used for stirring to enable the nitric acid and the nitric acid to be mixed uniformly, 9mL of glycerol is added to be stirred uniformly, and finally the deionized water is added to be mixed and the volume is adjusted to 100 mL.
Preparing a corrosion solution II: taking a small amount of deionized water into a beaker, respectively measuring 6mL of hydrofluoric acid and 9mL of hypophosphorous acid, slowly adding the deionized water into the beaker, stirring the mixture by using a glass rod to uniformly mix the hydrofluoric acid and the hypophosphorous acid, then adding 10mL of glycerol into the beaker, uniformly stirring the mixture, finally adding deionized water into the beaker, mixing the mixture and fixing the volume to 100 mL.
The use method of the corrosive agent for detecting the diamond/aluminum-silicon composite material interface comprises the following steps:
(1) preparing an electrolytic corrosion sample:
sample 2 is a diamond/aluminum silicon composite material (the volume fraction of diamond is 64 vol%, the matrix is Al-5 wt% Si alloy), and is prepared by air pressure infiltration (the infiltration temperature is 700 ℃, the air pressure is 1.5MPa, and the contact time of diamond/aluminum liquid is 3 min). Cutting the composite material into sheets of 10mm multiplied by 2mm by a laser cutting machine, polishing cut surfaces, cleaning and drying; then, a part of the area of the test piece was covered with an insulating paste to expose an electrolytically etched surface of 10mm × 3mm (in which the area of the metal matrix occupied 36% of the area of the composite material), to obtain a etched test piece.
(2) Connecting the corrosion sample with the positive electrode of a direct current power supply, connecting the platinum electrode plate with the negative electrode, and then putting the positive electrode and the negative electrode into a corrosion solution I at 25 ℃ to ensure the sampleThe electrolytic corrosion surface is completely immersed in the corrosion solution, a direct current power supply is switched on, the voltage is regulated, and the corrosion current density of the metal matrix at the exposed part of the corrosion sample reaches 2A/cm 2 Electrolyzing for 14s, taking out the sample, washing in alcohol and drying;
(3) connecting the sample corroded in the step (2) with the anode of a direct current power supply, connecting a platinum electrode with the cathode, then putting the anode and the cathode into a 25 ℃ corrosion solution II to ensure that the electrolytic corrosion surface of the sample is completely immersed in the corrosion solution, turning on the direct current power supply, adjusting the voltage to ensure that the corrosion current density of the metal matrix at the exposed part of the corrosion sample reaches 2A/cm 2 Electrolyzing for 20s, and then taking out the sample, cleaning the sample in alcohol and drying the sample;
(4) the interface between diamond and aluminum matrix was observed under a scanning electron microscope, and the result is shown in fig. 3.
As can be seen from FIG. 3, Al 4 C 3 Phase and silicon phase adhesion on diamond surface, wherein Al 4 C 3 The phases are selectively and non-uniformly distributed on different surfaces of the diamond. The infiltration temperature was higher (700 ℃ C.) and the silicon content was reduced (5 wt% Si) compared to example 1, thus Al 4 C 3 The phase size increases and the distribution density of the silicon phase decreases. Therefore, the corrosive agent and the inspection method thereof can conveniently and effectively inspect the interface structure of the diamond/aluminum-silicon composite material.
Example 3
The invention discloses a corrosive agent for detecting a diamond/aluminum-silicon composite material interface, which comprises a corrosive solution I and a corrosive solution II, wherein the corrosive solution I comprises: 12mL of 65% nitric acid, 10mL of 99% glycerol and the balance of deionized water; the etching solution II comprises: 5mL of hydrofluoric acid with the mass fraction of 40%, 7mL of hypophosphorous acid with the mass fraction of 85%, 8mL of glycerol with the purity of 99%, and the balance of deionized water.
Preparing a corrosion solution I: taking a small amount of deionized water into a beaker, measuring 12mL of nitric acid, slowly adding the nitric acid into the beaker, stirring the nitric acid and the beaker by using a glass rod to mix the nitric acid and the beaker uniformly, adding 10mL of glycerol, stirring the mixture uniformly, adding deionized water, mixing the mixture and fixing the volume to 100 mL.
Preparing a corrosion solution II: a small amount of deionized water is taken out of a beaker, 5mL of hydrofluoric acid and 7mL of hypophosphorous acid are respectively measured and slowly added into the beaker, a glass rod is used for stirring to enable the hydrofluoric acid and the hypophosphorous acid to be mixed uniformly, 8mL of glycerol is added to be stirred uniformly, and finally the deionized water is added to be mixed and the volume is 100 mL.
The use method of the corrosive agent for detecting the diamond/aluminum-silicon composite material interface comprises the following steps:
(1) preparation of electrolytic Corrosion samples
Sample 3 is a diamond/aluminum silicon composite material (diamond volume fraction is 63 vol%, matrix is Al-7 wt% Si alloy), and is prepared by air pressure infiltration (infiltration temperature is 750 ℃, air pressure is 1.5MPa, and diamond/aluminum liquid contact time is 3 min). Cutting the composite material into sheets of 10mm multiplied by 2mm by a laser cutting machine, polishing cut surfaces, cleaning and drying; then, a part of the area of the test piece was covered with an insulating paste to expose an electrolytically etched surface of 10mm × 3mm (in which the area of the metal matrix occupied 37% of the area of the composite material), to obtain a corroded test piece.
(2) Connecting a corrosion sample with the positive electrode of a direct current power supply, connecting a platinum electrode plate with the negative electrode, then putting the positive electrode and the negative electrode into a corrosion solution I at 25 ℃, ensuring that the electrolytic corrosion surface of the sample is completely immersed in the corrosion solution, turning on the direct current power supply, adjusting the voltage, and enabling the corrosion current density of a metal matrix at the exposed part of the corrosion sample to reach 2A/cm 2 Electrolyzing for 12s, taking out the sample, cleaning in alcohol and drying;
(3) connecting the sample corroded in the step (2) with the anode of a direct current power supply, connecting a platinum electrode with the cathode, then putting the anode and the cathode into a 25 ℃ corrosion solution II to ensure that the electrolytic corrosion surface of the sample is completely immersed in the corrosion solution, turning on the direct current power supply, adjusting the voltage to ensure that the corrosion current density of the metal matrix at the exposed part of the corrosion sample reaches 2A/cm 2 Electrolyzing for 16s, taking out the sample, cleaning in alcohol, and drying;
(4) the interface between diamond and aluminum matrix was observed under a scanning electron microscope, and the result is shown in FIG. 4.
As can be seen from FIG. 4, Al 4 C 3 Adhesion of phase and silicon phase to diamond surface, wherein Al 4 C 3 The phases are selectively and non-uniformly distributed on different surfaces of the diamond. Since the infiltration temperature of this example was high (750 ℃), Al 4 C 3 The phase size is obviously increased and is densely distributed on the surface of the diamond, and the distribution of the silicon phase is between the conditions of example 1 and example 2. Therefore, the corrosive agent and the inspection method thereof can conveniently and effectively inspect the interface structure of the diamond/aluminum-silicon composite material.
Comparative example 1
(1) Preparing an electrolytic corrosion sample:
exactly the same as in example 2.
(2) The preparation and corrosion method of the corrosive agent comprises the following steps:
refer to the article of I.E.Monje (I.E.Monje, Aluminum/diamond composites: A preliminary method to characteristics reactivity and selectivity at the interface, script materials 66(2012)789-792) for the display of diamond/pure Aluminum composite interface:
a. corrosive agent: taking a small amount of deionized water in a beaker, measuring 10mL of nitric acid with the mass percent of 68%, slowly adding the nitric acid into the beaker, stirring the nitric acid and the glass rod to uniformly mix the nitric acid and the glass rod, adding the deionized water into the beaker, mixing the nitric acid and the glass rod, and fixing the volume to 100 mL.
b. Electrochemical corrosion: connecting the corrosion sample with the positive electrode of a direct current power supply, connecting the platinum electrode plate with the negative electrode, then putting the positive electrode and the negative electrode into a corrosion solution at 25 ℃, ensuring that the electrolytic corrosion surface of the sample is completely immersed in the corrosion solution, turning on the direct current power supply, adjusting the voltage, and enabling the corrosion current density of the metal matrix at the exposed part of the corrosion sample to reach 2A/cm 2 Electrolyzing for 2.5min, taking out the sample, cleaning in alcohol, and drying;
c. the interface between diamond and aluminum matrix was observed under a scanning electron microscope, and the result is shown in fig. 5.
As can be seen from FIG. 5, Al is not seen on the diamond surface 4 C 3 The presence of the phase, only densely distributed corrosion pits are seen, which should be the interface reactant Al 4 C 3 The phase is removed by corrosion or the pit left after the phase is peeled off. The silicon phase particles were visible on the diamond surface, but were slightly smaller in size than in example 2, indicating that the silicon particles also suffered some erosion.
Through comparative analysis of electrolytic corrosion effect graphs of diamond/aluminum-silicon composite material interfaces of three examples, Al is shown as the impregnation temperature is increased 4 C 3 The particles are gradually coarsened, and the distribution on the interface is gradually changed from sparse to dense; along with the increase of the silicon content in the aluminum-silicon alloy, the quantity of the silicon phases on the surface of the diamond is increased gradually. The method can well detect the interface difference of the diamond/aluminum-silicon composite materials prepared at different infiltration temperatures and with different silicon contents, and provides an effective detection means for the research and production of the composite materials.
Claims (7)
1. The corrosive agent for detecting the diamond/aluminum-silicon composite material interface is characterized by comprising a corrosive solution I and a corrosive solution II, wherein the corrosive solution I comprises nitric acid, glycerol and water; the etching solution II comprises hydrofluoric acid, hypophosphorous acid, glycerol and water.
2. The etchant of claim 1, wherein each 100mL of the etching solution i comprises 10-12 mL of nitric acid, 8-10 mL of glycerol, and the balance of water; the mass fraction of the nitric acid is 65-70%.
3. The corrosive agent of claim 1, wherein each 100mL of the etching solution II comprises 5-7 mL of hydrofluoric acid, 7-10 mL of hypophosphorous acid, 8-10 mL of glycerol, and the balance of water; 35-40% of hydrofluoric acid by mass; the hypophosphorous acid accounts for 80-85% by mass.
4. A method of using the etchant of any of claims 1 to 3, comprising the steps of:
(1) processing a diamond/aluminum-silicon composite material sample into a sheet sample, polishing, cleaning and drying;
(2) connecting the corrosion sample with the positive electrode of a direct current power supply, connecting a platinum electrode with the negative electrode, then putting the positive electrode and the negative electrode into a corrosion solution I, turning on the direct current power supply to start electrolytic corrosion, then taking out the sample, cleaning and drying;
(3) connecting the sample in the step (2) with the positive electrode of a direct current power supply, connecting a platinum electrode with the negative electrode, then putting the positive electrode and the negative electrode into a corrosive solution II, turning on the direct current power supply to start electrolytic corrosion, then taking out the sample, cleaning the sample in alcohol and drying the sample;
(4) the interface of diamond and aluminum matrix and its reaction products were observed under a scanning electron microscope.
5. The use method of the corrosive agent according to claim 4, wherein the diamond/aluminum silicon composite material in the step (1) comprises 5-9 wt% of silicon and the balance of aluminum.
6. The method of claim 4, wherein the etching solution I in step (2) has an etching current density of 2A/cm at a temperature of 25 ℃ for electrolytic etching 2 The electrolysis time is 10-14 s.
7. The method of using the etchant according to claim 4, wherein the etching solution II in the step (3) has an etching current density of 2A/cm at a temperature of 25 ℃ for electrolytic etching 2 The electrolysis time is 16-20 s.
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| CN101935863A (en) * | 2009-06-30 | 2011-01-05 | 比亚迪股份有限公司 | Aluminum alloy electrolytic polishing solution, preparation method and aluminum alloy electrolytic polishing method |
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| CN114318341A (en) * | 2021-12-16 | 2022-04-12 | 东风汽车集团股份有限公司 | Aluminum alloy metallographic corrosion method and metallographic corrosion agent thereof |
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